Pathways of anaerobic organic matter decomposition in tundra soils from Barrow, Alaska

DOE PAGES

Herndon, Elizabeth M.; Mann, Benjamin F.; Chowdhury, Taniya Roy; ...

2015-11-23

Arctic tundra soils store a large quantity of organic carbon that is susceptible to decomposition and release to the atmosphere as methane (CH 4) and carbon dioxide (CO 2) under a warming climate. Anaerobic processes that generate CH 4 and CO 2 remain unclear because previous studies have focused on aerobic decomposition pathways. To predict releases of CO 2 and CH 4 from tundra soils, it is necessary to identify pathways of soil organic matter decomposition under the anoxic conditions that are prevalent in Arctic ecosystems. Here molecular and spectroscopic techniques were used to monitor biological degradation of water-extractable organicmore » carbon (WEOC) during anoxic incubation of tundra soils from a region of continuous permafrost in northern Alaska. Organic and mineral soils from the tundra active layer were incubated at –2, +4, or +8°C for up to 60 days to mimic the short-term thaw season. Results suggest that, under anoxic conditions, fermentation converted complex organic molecules into simple organic acids that were used in concomitant Fe-reduction and acetoclastic methanogenesis reactions. Nonaromatic compounds increased over time as WEOC increased. Organic acid metabolites initially accumulated in soils but were mostly depleted by day 60 because organic acids were consumed to produce Fe(II), CO 2, and CH 4. We conclude that fermentation of nonprotected organic matter facilitates methanogenesis and Fe reduction reactions, and that the proportion of organic acids consumed by methanogenesis increases relative to Fe reduction with increasing temperature. As a result, the decomposition pathways observed in this study are important to consider in numerical modeling of greenhouse gas production in the Arctic.« less

Litter decomposition over broad spatial and long time scales investigated by advanced solid-state NMR: insight into effects of climate, litter quality, and time

NASA Astrophysics Data System (ADS)

Mao, J.; Chen, N.; Harmon, M. E.; Li, Y.; Cao, X.; Chappell, M.

2012-12-01

Advanced 13C solid-state NMR techniques were employed to study the chemical structural changes of litter decomposition across broad spatial and long time scales. The fresh and decomposed litter samples of four species (Acer saccharum (ACSA), Drypetes glauca (DRGL), Pinus resinosa (PIRE), and Thuja plicata (THPL)) incubated for up to 10 years at four sites under different climatic conditions (from Arctic to tropical forest) were examined. Decomposition generally led to an enrichment of cutin and surface wax materials, and a depletion of carbohydrates causing overall composition to become more similar compared with original litters. However, the changes of main constituents in the four litters were inconsistent with the four litters following different pathways of decomposition at the same site. As decomposition proceeded, waxy materials decreased at the early stage and then gradually increased in PIRE; DRGL showed a significant depletion of lignin and tannin while the changes of lignin and tannin were relative small and inconsistent for ACSA and THPL. In addition, the NCH groups, which could be associated with either fungal cell wall chitin or bacterial wall petidoglycan, were enriched in all litters except THPL. Contrary to the classic lignin-enrichment hypothesis, DRGL with low-quality C substrate had the highest degree of composition changes. Furthermore, some samples had more "advanced" compositional changes in the intermediate stage of decomposition than in the highly-decomposed stage. This pattern might be attributed to the formation of new cross-linking structures, that rendered substrates more complex and difficult for enzymes to attack. Finally, litter quality overrode climate and time factors as a control of long-term changes of chemical composition.

N2-fixing red alder indirectly accelerates ecosystem nitrogen cycling

USGS Publications Warehouse

Perakis, Steven S.; Matkins, Joselin J.; Hibbs, David E.

2012-01-01

Symbiotic N2-fixing tree species can accelerate ecosystem N dynamics through decomposition via direct pathways by producing readily decomposed leaf litter and increasing N supply to decomposers, as well as via indirect pathways by increasing tissue and detrital N in non-fixing vegetation. To evaluate the relative importance of these pathways, we compared three-year decomposition and N dynamics of N2-fixing red alder leaf litter (2.34 %N) to both low-N (0.68 %N) and high-N (1.21 %N) litter of non-fixing Douglas-fir, and decomposed each litter source in four forests dominated by either red alder or Douglas-fir. We also used experimental N fertilization of decomposition plots to assess elevated N availability as a potential mechanism of N2-fixer effects on litter mass loss and N dynamics. Direct effects of N2-fixing red alder on decomposition occurred primarily as faster N release from red alder than Douglas-fir litter, but direct increases in N supply to decomposers via fertilization did not stimulate decomposition of any litter. Fixed N indirectly influenced detrital dynamics by increasing Douglas-fir tissue and litter N concentrations, which accelerated litter N release without accelerating mass loss. By increasing soil N, tissue N, and the rate of N release from litter of non-fixers, we conclude that N2-fixing vegetation can indirectly foster plant-soil feedbacks that contribute to the persistence of elevated N availability in terrestrial ecosystems.

Combustion modeling and kinetic rate calculations for a stoichiometric cyclohexane flame. 1. Major reaction pathways.

PubMed

Zhang, Hongzhi R; Huynh, Lam K; Kungwan, Nawee; Yang, Zhiwei; Zhang, Shaowen

2007-05-17

The Utah Surrogate Mechanism was extended in order to model a stoichiometric premixed cyclohexane flame (P = 30 Torr). Generic rates were assigned to reaction classes of hydrogen abstraction, beta scission, and isomerization, and the resulting mechanism was found to be adequate in describing the combustion chemistry of cyclohexane. Satisfactory results were obtained in comparison with the experimental data of oxygen, major products and important intermediates, which include major soot precursors of C2-C5 unsaturated species. Measured concentrations of immediate products of fuel decomposition were also successfully reproduced. For example, the maximum concentrations of benzene and 1,3-butadiene, two major fuel decomposition products via competing pathways, were predicted within 10% of the measured values. Ring-opening reactions compete with those of cascading dehydrogenation for the decomposition of the conjugate cyclohexyl radical. The major ring-opening pathways produce 1-buten-4-yl radical, molecular ethylene, and 1,3-butadiene. The butadiene species is formed via beta scission after a 1-4 internal hydrogen migration of 1-hexen-6-yl radical. Cascading dehydrogenation also makes an important contribution to the fuel decomposition and provides the exclusive formation pathway of benzene. Benzene formation routes via combination of C2-C4 hydrocarbon fragments were found to be insignificant under current flame conditions, inferred by the later concentration peak of fulvene, in comparison with benzene, because the analogous species series for benzene formation via dehydrogenation was found to be precursors with regard to parent species of fulvene.

Methylamine adsorption and decomposition on B12N12 nanocage: A density functional theory study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-08-01

Density functional theory calculations are performed to investigate the adsorption and decomposition of methylamine (CH3NH2) on the surface of a B12N12 fullerene-like nanocage. Two adsorption types and two reaction channels are identified. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3NH2. The pathways of CH3NH2 decomposition via bond scission of the Csbnd N and Nsbnd H bonds are examined. The results indicate that Nsbnd H bond scission is the most favorable pathway on the B12N12 surface. The side reaction that generates CH3 and NH2 fragments is endothermic by 15.6 kcal/mol with an energy-barrier height of 81.5 kcal/mol. For the CH3NH2 decomposition on the B12N12 surface, the rate-determining step appears to be as the following reaction: CH3NH → CH3N + H.

Hydrogen scrambling in ethane induced by intense laser fields: statistical analysis of coincidence events.

PubMed

Kanya, Reika; Kudou, Tatsuya; Schirmel, Nora; Miura, Shun; Weitzel, Karl-Michael; Hoshina, Kennosuke; Yamanouchi, Kaoru

2012-05-28

Two-body Coulomb explosion processes of ethane (CH(3)CH(3)) and its isotopomers (CD(3)CD(3) and CH(3)CD(3)) induced by an intense laser field (800 nm, 1.0 × 10(14) W/cm(2)) with three different pulse durations (40 fs, 80 fs, and 120 fs) are investigated by a coincidence momentum imaging method. On the basis of statistical treatment of the coincidence data, the contributions from false coincidence events are estimated and the relative yields of the decomposition pathways are determined with sufficiently small uncertainties. The branching ratios of the two body decomposition pathways of CH(3)CD(3) from which triatomic hydrogen molecular ions (H(3)(+), H(2)D(+), HD(2)(+), D(3)(+)) are ejected show that protons and deuterons within CH(3)CD(3) are scrambled almost statistically prior to the ejection of a triatomic hydrogen molecular ion. The branching ratios were estimated by statistical Rice-Ramsperger-Kassel-Marcus calculations by assuming a transition state with a hindered-rotation of a diatomic hydrogen moiety. The hydrogen scrambling dynamics followed by the two body decomposition processes are discussed also by using the anisotropies in the ejection directions of the fragment ions and the kinetic energy distribution of the two body decomposition pathways.

Synthesizing the Use of Carbon Isotope (14C and 13C) Approaches to Understand Rates and Pathways for Permafrost C Mobilization and Mineralization

NASA Astrophysics Data System (ADS)

Estop-Aragones, C.; Olefeldt, D.; Schuur, E.

2015-12-01

To better understand the permafrost carbon (C) feedback it is important to synthesize our current knowledge, and knowledge gaps, of how permafrost thaw can cause in situ mineralization or downstream mobilization of aged soil organic carbon (SOC) and the rate of this release. This potential loss of old SOC may occur via gaseous flux of CO2 and CH4 exchanged between soil and the atmosphere and via waterborne flux as DOC, POC (and their subsequent decomposition and release to the atmosphere). Carbon isotope (14C and 13C) approaches have been used to estimate both rates and pathways for permafrost C mobilization and mineralization. Radiocarbon (14C) has been used to estimate the contribution of aged C to overall respiration or waterborne C export. We aim to contrast results from radiocarbon studies, in order to assess differences between ecosystems (contrasting wet and dry ecosystems), thaw histories (active layer deepening or thermokarst landforms), greenhouse gas considered (CO2 and CH4) and seasons. We propose to also contrast methodologies used for assessing the contribution of aged C to overall C balance, and include studies using 13C data. Biological fractionation of 13C during both uptake and decomposition has been taken advantage of both in order to aid the interpretation of 14C data and on its own to assess sources and mineralization pathways. For example, 13C data has been used to differentiate between CH4 production pathways, and the relative contribution of anaerobic CO2 production to overall respiration. Overall, carbon isotope research is proving highly valuable for our understanding of permafrost C dynamics following thaw, and there is a current need to synthesize the available literature.

Designing Stability into Thermally Reactive Plumbylenes.

PubMed

Bačić, Goran; Zanders, David; Mallick, Bert; Devi, Anjana; Barry, Seán T

2018-06-26

Lead analogues of N-heterocyclic carbenes (NHPbs) are the least understood members of this increasingly important class of compounds. Here we report the design, preparation, isolation, structure, volatility, and decomposition pathways of a novel aliphatic NHPb: rac- N  2 , N  3 -di- tert-butylbutane-2,3-diamido lead(II) (1Pb). The large steric bulk of the tert-butylamido moieties and rac-butane backbone successfully hinder redox decomposition pathways observed for diamidoethylene and -ethane backbone analogues, pushing the onset of thermal decomposition from below 0 °C to above 150 °C. With an exceptionally high vapor pressure of 1 Torr at 94 ± 2 °C and excellent thermal stability among Pb(II) complexes, 1Pb is a promising precursor for the chemical vapor deposition (CVD) and atomic layer deposition (ALD) of functional lead-containing materials.

Efficient dehydrogenation of formic acid using Al12N12 nanocage: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-11-01

We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al12N12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al12N12, i.e. molecular and dissociative monodentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al12N12 nanocage. Our results reveal that for the decomposition of HCOOH into CO2 and H2, the most favorable pathway should be the Csbnd H bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the Csbnd H bond breaking.

The Irreversible Loss of a Decomposition Pathway Marks the Single Origin of an Ectomycorrhizal Symbiosis

PubMed Central

Wolfe, Benjamin E.; Tulloss, Rodham E.; Pringle, Anne

2012-01-01

Microbial symbioses have evolved repeatedly across the tree of life, but the genetic changes underlying transitions to symbiosis are largely unknown, especially for eukaryotic microbial symbionts. We used the genus Amanita, an iconic group of mushroom-forming fungi engaged in ectomycorrhizal symbioses with plants, to identify both the origins and potential genetic changes maintaining the stability of this mutualism. A multi-gene phylogeny reveals one origin of the symbiosis within Amanita, with a single transition from saprotrophic decomposition of dead organic matter to biotrophic dependence on host plants for carbon. Associated with this transition are the losses of two cellulase genes, each of which plays a critical role in extracellular decomposition of organic matter. However a third gene, which acts at later stages in cellulose decomposition, is retained by many, but not all, ectomycorrhizal species. Experiments confirm that symbiotic Amanita species have lost the ability to grow on complex organic matter and have therefore lost the capacity to live in forest soils without carbon supplied by a host plant. Irreversible losses of decomposition pathways are likely to play key roles in the evolutionary stability of these ubiquitous mutualisms. PMID:22815710

Thermal Decomposition of Energetic Materials. 2. Deuterium Isotope Effects and Isotopic Scrambling in Condensed-Phase Decomposition of Octahydro-1, 3,5,7-Tetranitro-1,3,5,7-Tetrazocine

DTIC Science & Technology

1993-02-01

HMX , 1) and hexahydro- 1,3,5-trinitro-s-triazine decomposition of H MX show that the identity and rates of release ( RDX , 11) are energetic ingredients...quadruple scission pathway Reviews$ of the literature on RDX and HMX have discussed HMX -- 4H2C=N-NO2 (R2) the roles of unimolecular decomposition and...N-NO2 -- CH 2O + NO (R3) lavior otCyclotrimethylene-trinitraminr ( RDX ) and Cycloteiramethylene- tctranitramine ( HMX ). In Fundamentals of Solid

Mycorrhizal associations of trees have different indirect effects on organic matter decomposition

Treesearch

Melanie K. Taylor; Richard A. Lankau; Nina Wurzburger; Franciska de Vries

2016-01-01

1. Organic matter decomposition is the main process by which carbon (C) is lost from terrestrialecosystems, and mycorrhizal associations of plants (i.e. arbuscular mycorrhizas (AM) and ectomycorrhizas(ECM)) may have different indirect effects on this loss pathway. AM and ECM plants differin the soil...

Cerebrospinal fluid PCR analysis and biochemistry in bodies with severe decomposition.

PubMed

Palmiere, Cristian; Vanhaebost, Jessica; Ventura, Francesco; Bonsignore, Alessandro; Bonetti, Luca Reggiani

2015-02-01

The aim of this study was to assess whether Neisseria meningitidis, Listeria monocytogenes, Streptococcus pneumoniae and Haemophilus influenzae can be identified using the polymerase chain reaction technique in the cerebrospinal fluid of severely decomposed bodies with known, noninfectious causes of death or whether postmortem changes can lead to false positive results and thus erroneous diagnostic information. Biochemical investigations, postmortem bacteriology and real-time polymerase chain reaction analysis in cerebrospinal fluid were performed in a series of medico-legal autopsies that included noninfectious causes of death with decomposition, bacterial meningitis without decomposition, bacterial meningitis with decomposition, low respiratory tract infections with decomposition and abdominal infections with decomposition. In noninfectious causes of death with decomposition, postmortem investigations failed to reveal results consistent with generalized inflammation or bacterial infections at the time of death. Real-time polymerase chain reaction analysis in cerebrospinal fluid did not identify the studied bacteria in any of these cases. The results of this study highlight the usefulness of molecular approaches in bacteriology as well as the use of alternative biological samples in postmortem biochemistry in order to obtain suitable information even in corpses with severe decompositional changes. Copyright © 2014 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

Theoretical studies of the decomposition mechanisms of 1,2,4-butanetriol trinitrate.

PubMed

Pei, Liguan; Dong, Kehai; Tang, Yanhui; Zhang, Bo; Yu, Chang; Li, Wenzuo

2017-12-06

Density functional theory (DFT) and canonical variational transition-state theory combined with a small-curvature tunneling correction (CVT/SCT) were used to explore the decomposition mechanisms of 1,2,4-butanetriol trinitrate (BTTN) in detail. The results showed that the γ-H abstraction reaction is the initial pathway for autocatalytic BTTN decomposition. The three possible hydrogen atom abstraction reactions are all exothermic. The rate constants for autocatalytic BTTN decomposition are 3 to 10 40 times greater than the rate constants for the two unimolecular decomposition reactions (O-NO 2 cleavage and HONO elimination). The process of BTTN decomposition can be divided into two stages according to whether the NO 2 concentration is above a threshold value. HONO elimination is the main reaction channel during the first stage because autocatalytic decomposition requires NO 2 and the concentration of NO 2 is initially low. As the reaction proceeds, the concentration of NO 2 gradually increases; when it exceeds the threshold value, the second stage begins, with autocatalytic decomposition becoming the main reaction channel.

Thermal decomposition pathways of ethane

NASA Astrophysics Data System (ADS)

Gordon, Mark S.; Truong, Thanh N.; Pople, John A.

1986-10-01

The alternate thermal decomposition pathways for ethane in its ground state have been investigated, using ab initio electronic structure calculations. Single-point energies were obtained at the full MP4/6-311 G ∗∗ level, using 6-31 G ∗ geometries for reactant, products, and transition states. The thermodynamically favored products are ethylene and molecular hydrogen, but a very large barrier (130 kcal/mol) is found for the direct 1,2-elimination of hydrogen. When calculated barriers are taken into account, the lowest-energy process is the homolytic cleavage of the C-C bond to form two methyl radicals.

Development of rate expressions for the thermal decomposition of RDX

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

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215{degrees}C, and one that controls solid-phase decomposition at temperatures below 200{degrees}C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450{degrees}C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

Development of rate expressions for the thermal decomposition of RDX

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

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215[degrees]C, and one that controls solid-phase decomposition at temperatures below 200[degrees]C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450[degrees]C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode?

PubMed

Chen, Y-X; Heinen, M; Jusys, Z; Behm, R J

2006-12-05

We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate.

Photodegradation Pathways in Arid Ecosystems

NASA Astrophysics Data System (ADS)

King, J. Y.; Lin, Y.; Adair, E. C.; Brandt, L.; Carbone, M. S.

2013-12-01

Recent interest in improving our understanding of decomposition patterns in arid and semi-arid ecosystems and under potentially drier future conditions has led to a flurry of research related to abiotic degradation processes. Oxidation of organic matter by solar radiation (photodegradation) is one abiotic degradation process that contributes significantly to litter decomposition rates. Our meta-analysis results show that increasing solar radiation exposure corresponds to an average increase of 23% in litter mass loss rate with large variation among studies associated primarily with environmental and litter chemistry characteristics. Laboratory studies demonstrate that photodegradation results in CO2 emissions. Indirect estimates suggest that photodegradation could account for as much as 60% of ecosystem CO2 emissions from dry ecosystems, but these CO2 fluxes have not been measured in intact ecosystems. The current data suggest that photodegradation is important, not only for understanding decomposition patterns, but also for modeling organic matter turnover and ecosystem C cycling. However, the mechanisms by which photodegradation operates, along with their environmental and litter chemistry controls, are still poorly understood. Photodegradation can directly influence decomposition rates and ecosystem CO2 flux via photochemical mineralization. It can also indirectly influence biotic decomposition rates by facilitating microbial degradation through breakdown of more recalcitrant compounds into simpler substrates or by suppressing microbial activity directly. All of these pathways influence the decomposition process, but the relative importance of each is uncertain. Furthermore, a specific suite of controls regulates each of these pathways (e.g., environmental conditions such as temperature and relative humidity; physical environment such as canopy architecture and contact with soil; and litter chemistry characteristics such as lignin and cellulose content), and these controls have not yet been identified or quantified. To advance our understanding of photodegradation and its role in decomposition and in ecosystem C cycling, we must characterize its mechanisms and their associated controls and incorporate this understanding into biogeochemical models. Our objective is to summarize the current state of understanding of photodegradation and discuss some paths forward to address remaining critical gaps in knowledge about its mechanisms and influence on ecosystem C balance.

Time-resolved spectroscopic measurements of shock-wave induced decomposition in cyclotrimethylene trinitramine (RDX) crystals: anisotropic response.

PubMed

Dang, Nhan C; Dreger, Zbigniew A; Gupta, Yogendra M; Hooks, Daniel E

2010-11-04

Plate impact experiments on the (210), (100), and (111) planes were performed to examine the role of crystalline anisotropy on the shock-induced decomposition of cyclotrimethylenetrinitramine (RDX) crystals. Time-resolved emission spectroscopy was used to probe the decomposition of single crystals shocked to peak stresses ranging between 7 and 20 GPa. Emission produced by decomposition intermediates was analyzed in terms of induction time to emission, emission intensity, and the emission spectra shapes as a function of stress and time. Utilizing these features, we found that the shock-induced decomposition of RDX crystals exhibits considerable anisotropy. Crystals shocked on the (210) and (100) planes were more sensitive to decomposition than crystals shocked on the (111) plane. The possible sources of the observed anisotropy are discussed with regard to the inelastic deformation mechanisms of shocked RDX. Our results suggest that, despite the anisotropy observed for shock initiation, decomposition pathways for all three orientations are similar.

Ab initio investigation of the thermal decomposition of n-butylcyclohexane.

PubMed

Ali, Mohamad Akbar; Dillstrom, V Tyler; Lai, Jason Y W; Violi, Angela

2014-02-13

Environmental and energy security concerns have motivated an increased focus on developing clean, efficient combustors, which increasingly relies on insight into the combustion chemistry of fuels. In particular, naphthenes (cycloalkanes and alkylcycloalkanes) are important chemical components of distillate fuels, such as diesel and jet fuels. As such, there is a growing interest in describing napthene reactivity with kinetic mechanisms. Use of these mechanisms in predictive combustion models aids in the development of combustors. This study focuses on the pyrolysis of n-butylcyclohexane (n-BCH), an important representative of naphthenes in jet fuels. Seven different unimolecular decomposition pathways of C-C bond fission were explored utilizing ab initio/DFT methods. Accurate reaction energies were computed using the high-level quantum composite G3B3 method. Variational transition state theory, Rice-Ramsperger-Kassel-Marcus/master equation simulations provided temperature- and pressure-dependent rate constants. Implementation of these pathways into an existing chemical kinetic mechanism improved the prediction of experimental OH radical and H2O speciation in shock tube oxidation. Simulations of this combustion showed a change in the expected decomposition chemistry of n-BCH, predicting increased production of cyclic alkyl radicals instead of straight-chain alkenes. The most prominent reaction pathway for the decomposition of n-BCH is n-BCH = C3H7 + C7H13. The results of this study provide insight into the combustion of n-BCH and will aid in the future development of naphthene kinetic mechanisms.

A Subspace Approach to the Structural Decomposition and Identification of Ankle Joint Dynamic Stiffness.

PubMed

Jalaleddini, Kian; Tehrani, Ehsan Sobhani; Kearney, Robert E

2017-06-01

The purpose of this paper is to present a structural decomposition subspace (SDSS) method for decomposition of the joint torque to intrinsic, reflexive, and voluntary torques and identification of joint dynamic stiffness. First, it formulates a novel state-space representation for the joint dynamic stiffness modeled by a parallel-cascade structure with a concise parameter set that provides a direct link between the state-space representation matrices and the parallel-cascade parameters. Second, it presents a subspace method for the identification of the new state-space model that involves two steps: 1) the decomposition of the intrinsic and reflex pathways and 2) the identification of an impulse response model of the intrinsic pathway and a Hammerstein model of the reflex pathway. Extensive simulation studies demonstrate that SDSS has significant performance advantages over some other methods. Thus, SDSS was more robust under high noise conditions, converging where others failed; it was more accurate, giving estimates with lower bias and random errors. The method also worked well in practice and yielded high-quality estimates of intrinsic and reflex stiffnesses when applied to experimental data at three muscle activation levels. The simulation and experimental results demonstrate that SDSS accurately decomposes the intrinsic and reflex torques and provides accurate estimates of physiologically meaningful parameters. SDSS will be a valuable tool for studying joint stiffness under functionally important conditions. It has important clinical implications for the diagnosis, assessment, objective quantification, and monitoring of neuromuscular diseases that change the muscle tone.

COMPADRE: an R and web resource for pathway activity analysis by component decompositions.

PubMed

Ramos-Rodriguez, Roberto-Rafael; Cuevas-Diaz-Duran, Raquel; Falciani, Francesco; Tamez-Peña, Jose-Gerardo; Trevino, Victor

2012-10-15

The analysis of biological networks has become essential to study functional genomic data. Compadre is a tool to estimate pathway/gene sets activity indexes using sub-matrix decompositions for biological networks analyses. The Compadre pipeline also includes one of the direct uses of activity indexes to detect altered gene sets. For this, the gene expression sub-matrix of a gene set is decomposed into components, which are used to test differences between groups of samples. This procedure is performed with and without differentially expressed genes to decrease false calls. During this process, Compadre also performs an over-representation test. Compadre already implements four decomposition methods [principal component analysis (PCA), Isomaps, independent component analysis (ICA) and non-negative matrix factorization (NMF)], six statistical tests (t- and f-test, SAM, Kruskal-Wallis, Welch and Brown-Forsythe), several gene sets (KEGG, BioCarta, Reactome, GO and MsigDB) and can be easily expanded. Our simulation results shown in Supplementary Information suggest that Compadre detects more pathways than over-representation tools like David, Babelomics and Webgestalt and less false positives than PLAGE. The output is composed of results from decomposition and over-representation analyses providing a more complete biological picture. Examples provided in Supplementary Information show the utility, versatility and simplicity of Compadre for analyses of biological networks. Compadre is freely available at http://bioinformatica.mty.itesm.mx:8080/compadre. The R package is also available at https://sourceforge.net/p/compadre.

The Algicidal Fungus Trametes versicolor F21a Eliminating Blue Algae via Genes Encoding Degradation Enzymes and Metabolic Pathways Revealed by Transcriptomic Analysis.

PubMed

Dai, Wei; Chen, Xiaolin; Wang, Xuewen; Xu, Zimu; Gao, Xueyan; Jiang, Chaosheng; Deng, Ruining; Han, Guomin

2018-01-01

The molecular mechanism underlying the elimination of algal cells by fungal mycelia has not been fully understood. Here, we applied transcriptomic analysis to investigate the gene expression and regulation at time courses of Trametes versicolor F21a during the algicidal process. The obtained results showed that a total of 193, 332, 545, and 742 differentially expressed genes were identified at 0, 6, 12, and 30 h during the algicidal process, respectively. The gene ontology terms were enriched into glucan 1,4-α-glucosidase activity, hydrolase activity, lipase activity, and endopeptidase activity. The KEGG pathways were enriched in degradation and metabolism pathways including Glycolysis/Gluconeogenesis, Pyruvate metabolism, the Biosynthesis of amino acids, etc. The total expression levels of all Carbohydrate-Active enZYmes (CAZyme) genes for the saccharide metabolism were increased by two folds relative to the control. AA5, GH18, GH5, GH79, GH128, and PL8 were the top six significantly up-regulated modules among 43 detected CAZyme modules. Four available homologous decomposition enzymes of other species could partially inhibit the growth of algal cells. The facts suggest that the algicidal mode of T. versicolor F21a might be associated with decomposition enzymes and several metabolic pathways. The obtained results provide a new candidate way to control algal bloom by application of decomposition enzymes in the future.

Photodissociation dynamics of nitromethane and methyl nitrite by infrared multiphoton dissociation imaging with quasiclassical trajectory calculations: signatures of the roaming pathway.

PubMed

Dey, Arghya; Fernando, Ravin; Abeysekera, Chamara; Homayoon, Zahra; Bowman, Joel M; Suits, Arthur G

2014-02-07

We combine the techniques of infrared multiphoton dissociation (IRMPD) with state selective ion imaging to probe roaming dynamics in the unimolecular dissociation of nitromethane and methyl nitrite. Recent theoretical calculations suggest a "roaming-mediated isomerization" pathway of nitromethane to methyl nitrite prior to decomposition. State-resolved imaging of the NO product coupled with infrared multiphoton dissociation was carried out to examine this unimolecular decomposition near threshold. The IRMPD images for the NO product from nitromethane are consistent with the earlier IRMPD studies that first suggested the importance of an isomerization pathway. A significant Λ-doublet propensity is seen in nitromethane IRMPD but not methyl nitrite. The experimental observations are augmented by quasiclassical trajectory calculations for nitromethane and methyl nitrite near threshold for each dissociation pathway. The observation of distinct methoxy vibrational excitation for trajectories from nitromethane and methyl nitrite dissociation at the same total energy show that the nitromethane dissociation bears a nonstatistical signature of the roaming isomerization pathway, and this is possibly responsible for the nitromethane Λ-doublet propensity as well.

Thermal Decomposition of Nitromethane and Reaction between CH3 and NO2.

PubMed

Matsugi, Akira; Shiina, Hiroumi

2017-06-08

The thermal decomposition of gaseous nitromethane and the subsequent bimolecular reaction between CH 3 and NO 2 have been experimentally studied using time-resolved cavity-enhanced absorption spectroscopy behind reflected shock waves in the temperature range 1336-1827 K and at a pressure of 100 kPa. Temporal evolution of NO 2 was observed following the pyrolysis of nitromethane (diluted to 80-140 ppm in argon) by monitoring the absorption around 400 nm. The primary objectives of the current work were to evaluate the rate constant for the CH 3 + NO 2 reaction (k 2 ) and to examine the contribution of the roaming isomerization pathway in nitromethane decomposition. The resultant rate constant can be expressed as k 2 = (9.3 ± 1.8) × 10 -10 (T/K) -0.5 cm 3 molecule -1 s -1 , which is in reasonable agreement with available literature data. The decomposition of nitromethane was found to predominantly proceed with the C-N bond fission process with the branching fraction of 0.97 ± 0.06. Therefore, the upper limit of the branching fraction for the roaming pathway was evaluated to be 0.09.

Decomposition of hydroxy amino acids in foraminiferal tests; kinetics, mechanism and geochronological implications

USGS Publications Warehouse

Bada, J.L.; Shou, M.-Y.; Man, E.H.; Schroeder, R.A.

1978-01-01

The diagenesis of the hydroxy amino acids serine and threonine in foraminiferal tests has been investigated. The decomposition pathways of these amino acids are complex; the principal reactions appear to be dehydration, aldol cleavage and decarboxylation. Stereochemical studies indicate that the ??-amino-n-butyric acid (ABA) detected in foraminiferal tests is the end product of threonine dehydration pathway. Decomposition of serine and threonine in foraminiferal tests from two well-dated Caribbean deep-sea cores, P6304-8 and -9, has been found to follow irreversible first-order kinetics. Three empirical equations were derived for the disappearance of serine and threonine and the appearance of ABA. These equations can be used as a new geochronological method for dating foraminiferal tests from other deep-sea sediments. Preliminary results suggest that ages deduced from the ABA kinetics equation are most reliable because "species effect" and contamination problems are not important for this nonbiological amino acid. Because of the variable serine and threonine contents of modern foraminiferal species, it is likely that the accurate age estimates can be obtained from the serine and threonine decomposition equations only if a homogeneous species assemblage or single species sample isolated from mixed natural assemblages is used. ?? 1978.

Distinct Cortical Pathways for Music and Speech Revealed by Hypothesis-Free Voxel Decomposition

PubMed Central

Norman-Haignere, Sam

2015-01-01

SUMMARY The organization of human auditory cortex remains unresolved, due in part to the small stimulus sets common to fMRI studies and the overlap of neural populations within voxels. To address these challenges, we measured fMRI responses to 165 natural sounds and inferred canonical response profiles (“components”) whose weighted combinations explained voxel responses throughout auditory cortex. This analysis revealed six components, each with interpretable response characteristics despite being unconstrained by prior functional hypotheses. Four components embodied selectivity for particular acoustic features (frequency, spectrotemporal modulation, pitch). Two others exhibited pronounced selectivity for music and speech, respectively, and were not explainable by standard acoustic features. Anatomically, music and speech selectivity concentrated in distinct regions of non-primary auditory cortex. However, music selectivity was weak in raw voxel responses, and its detection required a decomposition method. Voxel decomposition identifies primary dimensions of response variation across natural sounds, revealing distinct cortical pathways for music and speech. PMID:26687225

Distinct Cortical Pathways for Music and Speech Revealed by Hypothesis-Free Voxel Decomposition.

PubMed

Norman-Haignere, Sam; Kanwisher, Nancy G; McDermott, Josh H

2015-12-16

The organization of human auditory cortex remains unresolved, due in part to the small stimulus sets common to fMRI studies and the overlap of neural populations within voxels. To address these challenges, we measured fMRI responses to 165 natural sounds and inferred canonical response profiles ("components") whose weighted combinations explained voxel responses throughout auditory cortex. This analysis revealed six components, each with interpretable response characteristics despite being unconstrained by prior functional hypotheses. Four components embodied selectivity for particular acoustic features (frequency, spectrotemporal modulation, pitch). Two others exhibited pronounced selectivity for music and speech, respectively, and were not explainable by standard acoustic features. Anatomically, music and speech selectivity concentrated in distinct regions of non-primary auditory cortex. However, music selectivity was weak in raw voxel responses, and its detection required a decomposition method. Voxel decomposition identifies primary dimensions of response variation across natural sounds, revealing distinct cortical pathways for music and speech. Copyright © 2015 Elsevier Inc. All rights reserved.

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

Computer modeling of adsorption and decomposition pathways of boundary-layer lubricants on clean aluminum(111) surface, and adhesive metal transfer at the aluminum/steel interface: The ab-initio study

NASA Astrophysics Data System (ADS)

Zhong, Jun

Density functional theory (DFT) is employed to study lubricant adsorption and decomposition pathways, and adhesive metal transfer on clean aluminum surfaces. In this dissertation, density functional theory (DFT-GGA) is used to investigate the optimal adsorption geometries and binding energies of vinyl-phosphonic and ethanoic acids on an A1(111) surface. Tri-bridged, bi-bridged and uni-dentate coordinations for adsorbates are examined to determine the optimal binding sites on the surface. An analysis of the charge density of states (DOS) of oxygen involved in reacting with aluminum ions reveals changes in the atomic bonding configuration. For these acid molecules, the favorable decomposition pathways lead to fragments of vinyl- and alkylchains bonding to the Al(111) surface with phosphorous and carbon ions. Final optimal decomposition geometries and binding energies for various decomposition stages are also discussed. In addition, ab-initio molecular dynamics (AIMD) is carried out to explore collisions of aliphatic lubricants like butanol-alcohol and butanoic-acid with the Al(111) surface. Simulation results indicate that functional oxygen groups on these molecules could react with the "islands of nascent aluminum" and oxidize the surface. Favorable decomposition pieces on the surface, which were corroborated with experiment and DFT calculations, are found to contribute to the effectiveness of a particular molecule for boundary thinfilm lubrication to reduce the wear of aluminum. Finally, ab-initio molecular dynamics is also applied to investigations of the interaction between aluminum and hematite surfaces with and without a vinyl-phosphonic acid (VPA) lubricant. Without the lubricant, hematite is found to react with Al strongly (thermit reaction). This removes relatively large fragments from the surface of the aluminum substrate when this substrate is rubbed with a harder steel-roller under an external shock contact-load exceeding the ability of the substrate to support the aluminum-oxide film. Adhesive wear is found to significantly raise the temperature of system. Addition of VPA lubricant is found to retard the reaction of hematite with aluminum by forming an effective barrier between the two surfaces.

Better Decomposition Heuristics for the Maximum-Weight Connected Graph Problem Using Betweenness Centrality

NASA Astrophysics Data System (ADS)

Yamamoto, Takanori; Bannai, Hideo; Nagasaki, Masao; Miyano, Satoru

We present new decomposition heuristics for finding the optimal solution for the maximum-weight connected graph problem, which is known to be NP-hard. Previous optimal algorithms for solving the problem decompose the input graph into subgraphs using heuristics based on node degree. We propose new heuristics based on betweenness centrality measures, and show through computational experiments that our new heuristics tend to reduce the number of subgraphs in the decomposition, and therefore could lead to the reduction in computational time for finding the optimal solution. The method is further applied to analysis of biological pathway data.

The Algicidal Fungus Trametes versicolor F21a Eliminating Blue Algae via Genes Encoding Degradation Enzymes and Metabolic Pathways Revealed by Transcriptomic Analysis

PubMed Central

Dai, Wei; Chen, Xiaolin; Wang, Xuewen; Xu, Zimu; Gao, Xueyan; Jiang, Chaosheng; Deng, Ruining; Han, Guomin

2018-01-01

The molecular mechanism underlying the elimination of algal cells by fungal mycelia has not been fully understood. Here, we applied transcriptomic analysis to investigate the gene expression and regulation at time courses of Trametes versicolor F21a during the algicidal process. The obtained results showed that a total of 193, 332, 545, and 742 differentially expressed genes were identified at 0, 6, 12, and 30 h during the algicidal process, respectively. The gene ontology terms were enriched into glucan 1,4-α-glucosidase activity, hydrolase activity, lipase activity, and endopeptidase activity. The KEGG pathways were enriched in degradation and metabolism pathways including Glycolysis/Gluconeogenesis, Pyruvate metabolism, the Biosynthesis of amino acids, etc. The total expression levels of all Carbohydrate-Active enZYmes (CAZyme) genes for the saccharide metabolism were increased by two folds relative to the control. AA5, GH18, GH5, GH79, GH128, and PL8 were the top six significantly up-regulated modules among 43 detected CAZyme modules. Four available homologous decomposition enzymes of other species could partially inhibit the growth of algal cells. The facts suggest that the algicidal mode of T. versicolor F21a might be associated with decomposition enzymes and several metabolic pathways. The obtained results provide a new candidate way to control algal bloom by application of decomposition enzymes in the future. PMID:29755442

Gas evolution from cathode materials: A pathway to solvent decomposition concomitant to SEI formation.

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

Browning, Katie L; Baggetto, Loic; Unocic, Raymond R

This work reports a method to explore the catalytic reactivity of electrode surfaces towards the decomposition of carbonate solvents [ethylene carbonate (EC), dimethyl carbonate (DMC), and EC/DMC]. We show that the decomposition of a 1:1 wt% EC/DMC mixture is accelerated over certain commercially available LiCoO2 materials resulting in the formation of CO2 while over pure EC or DMC the reaction is much slower or negligible. The solubility of the produced CO2 in carbonate solvents is high (0.025 grams/mL) which masks the effect of electrolyte decomposition during storage or use. The origin of this decomposition is not clear but it ismore » expected to be present on other cathode materials and may affect the analysis of SEI products as well as the safety of Li-ion batteries.« less

pH controls over methanogenesis and iron reduction along soil depth profile in Arctic tundra

NASA Astrophysics Data System (ADS)

Zheng, J.; Gu, B.; Wullschleger, S. D.; Graham, D. E.

2017-12-01

Increasing soil temperature in the Arctic is expected to accelerate rates of soil organic matter decomposition. However, the magnitude of this impact is uncertain due to the many physical, chemical, and biological processes that control the decomposition pathways. Varying soil redox conditions present a key control over pathways of organic matter decomposition by diverting the flow of reductants among different electron accepting processes and further driving acid-base reactions that alter soil pH. In this study we investigated the pH controls over anaerobic carbon mineralization, methanogenesis, Fe(III) reduction and the interplay between these processes across a range of pH and redox conditions. pH manipulation experiments were conducted by incubating soils representing organic, mineral, cryoturbated transitional layers and permafrost. In the experiments we sought to understand (1) if methanogenesis or Fe(III) reduction had similar pH optima; (2) if this pH response also occurs at `upstream' fermentation process; and (3) if pH alters organo-mineral association or organic matter sorption and desorption and its availability for microbial degradation. Our preliminary results suggest that the common bell-shaped pH response curve provides a good fit for both Fe(III) reduction and methanogenesis, with optimum pH at 6.0-7.0. Exceptions to this were found in transitional layer where methanogenesis rates positively correlated with increasing pH, with maximum rates measured at pH 8.5. It is likely that the transitional layer harbors distinct groups of methanogens that prefer a high pH. Variations in the optimum pH of Fe(III) reduction and methanogenesis may play a significant role in regulating organic matter decomposition pathways and thus greenhouse gas production in thawing soils. These results support biogeochemical modeling efforts to accurately simulate organic matter decomposition under changing redox and pH conditions.

More of the same? In situ leaf and root decomposition rates do not vary between 80 native and nonnative deciduous forest species.

PubMed

Jo, Insu; Fridley, Jason D; Frank, Douglas A

2016-01-01

Invaders often have greater rates of production and produce more labile litter than natives. The increased litter quantity and quality of invaders should increase nutrient cycling through faster litter decomposition. However, the limited number of invasive species that have been included in decomposition studies has hindered the ability to generalize their impacts on decomposition rates. Further, previous decomposition studies have neglected roots. We measured litter traits and decomposition rates of leaves for 42 native and 36 nonnative woody species, and those of fine roots for 23 native and 25 nonnative species that occur in temperate deciduous forests throughout the Eastern USA. Among the leaf and root traits that differed between native and invasive species, only leaf nitrogen was significantly associated with decomposition rate. However, native and nonnative species did not differ systematically in leaf and root decomposition rates. We found that among the parameters measured, litter decomposer activity was driven by litter chemical quality rather than tissue density and structure. Our results indicate that litter decomposition rate per se is not a pathway by which forest woody invasive species affect North American temperate forest soil carbon and nutrient processes. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Preparation, characterization and thermolysis of phenylenediammonium dinitrate salts.

PubMed

Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip

2008-02-11

Four phenylenediammonium dinitrate salts were prepared and characterized by elemental, Infrared spectroscopy (IR), Ultraviolet spectroscopy (UV) and gravimetric methods. These dinitrates find application in propellant, explosives and pyrotechnics. Their thermal decomposition has been studied using thermogravimetry (TG) and simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC). Kinetics parameters were evaluated by model fitting and isoconversional methods. Their thermolytic pathways have also been suggested, which involves decomposition followed by ignition.

Are litter decomposition and fire linked through plant species traits?

PubMed

Cornelissen, Johannes H C; Grootemaat, Saskia; Verheijen, Lieneke M; Cornwell, William K; van Bodegom, Peter M; van der Wal, René; Aerts, Rien

2017-11-01

Contents 653 I. 654 II. 657 III. 659 IV. 661 V. 662 VI. 663 VII. 665 665 References 665 SUMMARY: Biological decomposition and wildfire are connected carbon release pathways for dead plant material: slower litter decomposition leads to fuel accumulation. Are decomposition and surface fires also connected through plant community composition, via the species' traits? Our central concept involves two axes of trait variation related to decomposition and fire. The 'plant economics spectrum' (PES) links biochemistry traits to the litter decomposability of different fine organs. The 'size and shape spectrum' (SSS) includes litter particle size and shape and their consequent effect on fuel bed structure, ventilation and flammability. Our literature synthesis revealed that PES-driven decomposability is largely decoupled from predominantly SSS-driven surface litter flammability across species; this finding needs empirical testing in various environmental settings. Under certain conditions, carbon release will be dominated by decomposition, while under other conditions litter fuel will accumulate and fire may dominate carbon release. Ecosystem-level feedbacks between decomposition and fire, for example via litter amounts, litter decomposition stage, community-level biotic interactions and altered environment, will influence the trait-driven effects on decomposition and fire. Yet, our conceptual framework, explicitly comparing the effects of two plant trait spectra on litter decomposition vs fire, provides a promising new research direction for better understanding and predicting Earth surface carbon dynamics. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

Plant Identity Influences Decomposition through More Than One Mechanism

PubMed Central

McLaren, Jennie R.; Turkington, Roy

2011-01-01

Plant litter decomposition is a critical ecosystem process representing a major pathway for carbon flux, but little is known about how it is affected by changes in plant composition and diversity. Single plant functional groups (graminoids, legumes, non-leguminous forbs) were removed from a grassland in northern Canada to examine the impacts of functional group identity on decomposition. Removals were conducted within two different environmental contexts (fertilization and fungicide application) to examine the context-dependency of these identity effects. We examined two different mechanisms by which the loss of plant functional groups may impact decomposition: effects of the living plant community on the decomposition microenvironment, and changes in the species composition of the decomposing litter, as well as the interaction between these mechanisms. We show that the identity of the plant functional group removed affects decomposition through both mechanisms. Removal of both graminoids and forbs slowed decomposition through changes in the decomposition microenvironment. We found non-additive effects of litter mixing, with both the direction and identity of the functional group responsible depending on year; in 2004 graminoids positively influenced decomposition whereas in 2006 forbs negatively influenced decomposition rate. Although these two mechanisms act independently, their effects may be additive if both mechanisms are considered simultaneously. It is essential to understand the variety of mechanisms through which even a single ecosystem property is affected if we are to predict the future consequences of biodiversity loss. PMID:21858210

Exploring Patterns of Soil Organic Matter Decomposition with Students through the Global Decomposition Project (GDP) and the Interactive Model of Leaf Decomposition (IMOLD)

NASA Astrophysics Data System (ADS)

Steiner, S. M.; Wood, J. H.

2015-12-01

As decomposition rates are affected by climate change, understanding crucial soil interactions that affect plant growth and decomposition becomes a vital part of contributing to the students' knowledge base. The Global Decomposition Project (GDP) is designed to introduce and educate students about soil organic matter and decomposition through a standardized protocol for collecting, reporting, and sharing data. The Interactive Model of Leaf Decomposition (IMOLD) utilizes animations and modeling to learn about the carbon cycle, leaf anatomy, and the role of microbes in decomposition. Paired together, IMOLD teaches the background information and allows simulation of numerous scenarios, and the GDP is a data collection protocol that allows students to gather usable measurements of decomposition in the field. Our presentation will detail how the GDP protocol works, how to obtain or make the materials needed, and how results will be shared. We will also highlight learning objectives from the three animations of IMOLD, and demonstrate how students can experiment with different climates and litter types using the interactive model to explore a variety of decomposition scenarios. The GDP demonstrates how scientific methods can be extended to educate broader audiences, and data collected by students can provide new insight into global patterns of soil decomposition. Using IMOLD, students will gain a better understanding of carbon cycling in the context of litter decomposition, as well as learn to pose questions they can answer with an authentic computer model. Using the GDP protocols and IMOLD provide a pathway for scientists and educators to interact and reach meaningful education and research goals.

Method of manufacturing aerogel composites

DOEpatents

Cao, W.; Hunt, A.J.

1999-03-09

Disclosed herewith is a process of forming an aerogel composite which comprises introducing a gaseous material into a formed aerogel monolith or powder, and causing decomposition of said gaseous material in said aerogel in amounts sufficient to cause deposition of the decomposition products of the gas on the surfaces of the pores of the said aerogel.

Method of manufacturing aerogel composites

DOEpatents

Cao, Wanqing; Hunt, Arlon Jason

1999-01-01

Disclosed herewith is a process of forming an aerogel composite which comprises introducing a gaseous material into a formed aerogel monolith or powder, and causing decomposition of said gaseous material in said aerogel in amounts sufficient to cause deposition of the decomposition products of the gas on the surfaces of the pores of the said aerogel.

Litter chemistry, community shift, and non-additive effects drive litter decomposition changes following invasion by a generalist pathogen

Treesearch

Richard C. Cobb; David M. Rizzo

2016-01-01

Forest pathogens have strong potential to shape ecosystem function by altering litterfall, microclimate, and changing community structure. We quantified changes in litter decomposition from a set of distinct diseases caused by Phytophthora ramorum, an exotic generalist pathogen. Phytophthora ramorum causes leaf blight and...

Abiotic mechanism for the formation of atmospheric nitrous oxide from ammonium nitrate.

PubMed

Rubasinghege, Gayan; Spak, Scott N; Stanier, Charles O; Carmichael, Gregory R; Grassian, Vicki H

2011-04-01

Nitrous oxide (N2O) is an important greenhouse gas and a primary cause of stratospheric ozone destruction. Despite its importance, there remain missing sources in the N2O budget. Here we report the formation of atmospheric nitrous oxide from the decomposition of ammonium nitrate via an abiotic mechanism that is favorable in the presence of light, relative humidity and a surface. This source of N2O is not currently accounted for in the global N2O budget. Annual production of N2O from atmospheric aerosols and surface fertilizer application over the continental United States from this abiotic pathway is estimated from results of an annual chemical transport simulation with the Community Multiscale Air Quality model (CMAQ). This pathway is projected to produce 9.3(+0.7/-5.3) Gg N2O annually over North America. N2O production by this mechanism is expected globally from both megacities and agricultural areas and may become more important under future projected changes in anthropogenic emissions.

Novel fragmentation pathways of anionic adducts of steroids formed by electrospray anion attachment involving regioselective attachment, regiospecific decompositions, charge-induced pathways, and ion-dipole complex intermediates.

PubMed

Rannulu, Nalaka S; Cole, Richard B

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion](-) adducts of these steroids revealed that fluoride adduct [M + F](-) precursors first lose HF to produce [M - H](-) and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d(4)-pregnenolone, are also discussed.

Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

NASA Astrophysics Data System (ADS)

Rannulu, Nalaka S.; Cole, Richard B.

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study

NASA Astrophysics Data System (ADS)

Jiang, Zhao; Qin, Pei; Fang, Tao

2017-02-01

The study of formic acid decomposition on transition metal surfaces is important to obtain useful information for vapor phase catalysis involving HCOOH and for the development of direct formic acid fuel cells. In this study, periodic density functional theory calculations have been employed to investigate the dissociation pathways of HCOOH on Cu (111) surface. About adsorption, it is found that the adsorption of HCOO, COOH, HCO, CO, OH and H on Cu (111) are considered chemisorption, whereas HCOOH, CO2, H2O and H2 have the weak interaction with Cu (111) surface. Furthermore, the minimum energy pathways are analyzed for the decomposition of HCOOH to CO2 and CO through the scission of Hsbnd O, Csbnd H and Csbnd O bonds. It is found that HCOOH, HCOO and COOH prefer to dissociate in the related reactions rather than desorb. For the decomposition, it is indicated that HCO and COOH are the main dissociated intermediates of trans-HCOOH, CO2 is the main dissociated intermediates of bidentate-HCOO, and CO is the main dissociated product of cis-COOH. The co-adsorbed H atom is beneficial for the formation of CO2 from cis-COOH. Besides, it is found that the most favorable path for HCOOH decomposition on Cu (111) surface is HCOOH-HCO-CO (Path 5), where the step of CO formation from HCO dehydrogenation is considered to be the rate-determining step. The results also show that CO is preferentially formed as the dominant product of HCOOH on Cu (111) surface.

First-principles calculated decomposition pathways for LiBH4 nanoclusters

PubMed Central

Huang, Zhi-Quan; Chen, Wei-Chih; Chuang, Feng-Chuan; Majzoub, Eric H.; Ozoliņš, Vidvuds

2016-01-01

We analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found that the bulk material decomposes into LiH and B, with Li2B12H12 as a kinetically inhibited intermediate phase, (LiBH4)n nanoclusters with n ≤ 12 are predicted to decompose into mixed LinBn clusters via a series of intermediate clusters of LinBnHm (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products. PMID:27189731

[Contribution of soil fauna to litter decomposition of Abies faxoniana and Rhododendron lapponicum across an alpine timberline ecotone in Western Sichuan, China.

PubMed

Wang, Li Feng; He, Run Lian; Yang, Lin; Chen, Ya Mei; Liu, Yang; Zhang, Jian

2016-11-18

Soil fauna is an important biological factor in regulation litter decomposition. In order to quantify the contributions of soil fauna to the mass losses of litter of two dominant species fir (Abies faxoniana) and rhododendron (Rhododendron lapponicum) in the alpine timberline ecotone (coniferous forest-timberline-alpine meadow) of western Sichuan, China, a field litterbag experiment was conducted from May 2013 to November 2014. Samples of air-dried leaf litter were placed in nylon litterbags of two different mesh sizes, i.e. 3.00 mm (with the soil animals) and 0.04 mm (excluded the soil animals). The results showed that the decomposition rate of A. faxoniana (k: 0.209-0.243) was higher than that of R. lapponicum (k: 0.173-0.189) across the timberline ecotone. Soil fauna had significant contributions to litter decomposition of two species, the contributions of soil fauna to mass loss showed a decreasing trend with increasing altitude. From the coniferous forest to the alpine meadow, the mass losses caused by soil fauna for the fir litter accounted for 15.2%, 13.2% and 9.8%, respectively and that for the rhododendron litter accounted for 20.1%, 17.5% and 12.4%, respectively. Meanwhile, the daily average contributions caused by soil fauna for the fir and rhododendron litter decomposition accounted for 0.17%, 0.13%, 0.12% and 0.26%, 0.25%, 0.23%, respectively. Relatively, soil fauna had more influence on alpine rhododendron decomposition. Two-way ANOVA showed that species, altitude and their interaction had significant impact on the litter mass loss and decomposition rate caused by soil fauna. The daily average contribution caused by soil fauna for the fir and rhododendron litter decomposition accounted for 0.25% and 0.44% in the first growing season, then 0.10% and 0.19% in the second growing season, both were higher than that of snow-covered season (0.07% and 0.12%). Regression analysis showed that the environmental factors (daily average temperature, freezing and thawing cycles and snow thickness) explained 42.7% and 50.9% in the mass loss as well as 43.2% and 55.6% in the contribution rate of fir and rhododendron litter decomposition. These results suggest that soil fauna contributes strongly to litter decomposition in the alpine ecosystem, and it is of great significance to thorough understanding and recognizing material cycle through the role of soil fauna in the litter decomposition.

Excited electronic state decomposition mechanisms and dynamics of nitramine energetic materials and model systems

NASA Astrophysics Data System (ADS)

Greenfield, Margo

Energetic materials play an important role in aeronautics, the weapon industry, and the propellant industry due to their broad applications as explosives and fuels. RDX (1,3,5-trinitrohexahydro-s-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) are compounds which contain high energy density. Although RDX and HMX have been studied extensively over the past several decades a complete understanding of their decomposition mechanisms and dynamics is unknown. Time of flight mass spectroscopy (TOFMS) UV photodissociation (ns) experiments of gas phase RDX, HMX, and CL-20 generate the NO molecule as the initial decomposition product. Four different vibronic transitions of the initial decomposition product, the NO molecule, are observed: A2Sigma(upsilon'=0)←X 2pi(upsilon"=0,1,2,3). Simulations of the rovibronic intensities for the A←X transitions demonstrate that NO dissociated from RDX, HMX, and CL-20 is rotationally cold (˜20 K) and vibrationally hot (˜1800 K). Conversely, experiments on the five model systems (nitromethane, dimethylnitramine (DMNA), nitropyrrolidine, nitropiperidine and dinitropiperazine) produce rotationally hot and vibrationally cold spectra. Laser induced fluorescence (LIF) experiments are performed to rule out the possible decomposition product OH, generated along with NO, perhaps from the suggested HONO elimination mechanism. The OH radical is not observed in the fluorescence experiments, indicating the HONO decomposition intermediate is not an important pathway for the excited electronic state decomposition of cyclic nitramines. The NO molecule is also employed to measure the dynamics of the excited state decomposition. A 226 nm, 180 fs light pulse is utilized to photodissociate the gas phase systems. Stable ion states of DMNA and nitropyrrolidine are observed while the energetic materials and remaining model systems present the NO molecule as the only observed product. Pump-probe transients of the resonant A←X (0-0) transition of the NO molecule show a constant signal indicating these materials decompose faster than the time duration of the 226 nm laser light. Calculational results together with the experimental results indicate the energetic materials decompose through an internal conversion to very highly excited (˜5 eV of vibrational energy) vibrational states of their ground electronic state, while the model systems follow an excited electronic state decomposition pathway.

Moisture controls decomposition rate in thawing tundra

Treesearch

C.E. Hicks-Pries; E.A.G. Schuur; S.M. Natali; J.G. Vogel

2013-01-01

Permafrost thaw can affect decomposition rates by changing environmental conditions and litter quality. As permafrost thaws, soils warm and thermokarst (ground subsidence) features form, causing some areas to become wetter while other areas become drier. We used a common substrate to measure how permafrost thaw affects decomposition rates in the surface soil in a...

Spider foraging strategy affects trophic cascades under natural and drought conditions.

PubMed

Liu, Shengjie; Chen, Jin; Gan, Wenjin; Schaefer, Douglas; Gan, Jianmin; Yang, Xiaodong

2015-07-23

Spiders can cause trophic cascades affecting litter decomposition rates. However, it remains unclear how spiders with different foraging strategies influence faunal communities, or present cascading effects on decomposition. Furthermore, increased dry periods predicted in future climates will likely have important consequences for trophic interactions in detritus-based food webs. We investigated independent and interactive effects of spider predation and drought on litter decomposition in a tropical forest floor. We manipulated densities of dominant spiders with actively hunting or sit-and-wait foraging strategies in microcosms which mimicked the tropical-forest floor. We found a positive trophic cascade on litter decomposition was triggered by actively hunting spiders under ambient rainfall, but sit-and-wait spiders did not cause this. The drought treatment reversed the effect of actively hunting spiders on litter decomposition. Under drought conditions, we observed negative trophic cascade effects on litter decomposition in all three spider treatments. Thus, reduced rainfall can alter predator-induced indirect effects on lower trophic levels and ecosystem processes, and is an example of how such changes may alter trophic cascades in detritus-based webs of tropical forests.

Spider foraging strategy affects trophic cascades under natural and drought conditions

PubMed Central

Liu, Shengjie; Chen, Jin; Gan, Wenjin; Schaefer, Douglas; Gan, Jianmin; Yang, Xiaodong

2015-01-01

Spiders can cause trophic cascades affecting litter decomposition rates. However, it remains unclear how spiders with different foraging strategies influence faunal communities, or present cascading effects on decomposition. Furthermore, increased dry periods predicted in future climates will likely have important consequences for trophic interactions in detritus-based food webs. We investigated independent and interactive effects of spider predation and drought on litter decomposition in a tropical forest floor. We manipulated densities of dominant spiders with actively hunting or sit-and-wait foraging strategies in microcosms which mimicked the tropical-forest floor. We found a positive trophic cascade on litter decomposition was triggered by actively hunting spiders under ambient rainfall, but sit-and-wait spiders did not cause this. The drought treatment reversed the effect of actively hunting spiders on litter decomposition. Under drought conditions, we observed negative trophic cascade effects on litter decomposition in all three spider treatments. Thus, reduced rainfall can alter predator-induced indirect effects on lower trophic levels and ecosystem processes, and is an example of how such changes may alter trophic cascades in detritus-based webs of tropical forests. PMID:26202370

Molecular Mechanisms in the shock induced decomposition of FOX-7

NASA Astrophysics Data System (ADS)

Mishra, Ankit; Tiwari, Subodh C.; Nakano, Aiichiro; Vashishta, Priya; Kalia, Rajiv; CACS Team

Experimental and first principle computational studies on FOX 7 have either involved a very small system consisting of a few atoms or they did not take into account the decomposition mechanisms under extreme conditions of temperature and pressure. We have performed a large-scale reactive MD simulation using ReaxFF-lg force field to study the shock decomposition of FOX 7. The chemical composition of the principal decomposition products correlates well with experimental observations. Furthermore, we observed that the production of N2 and H2O was inter molecular in nature and was through different chemical pathways. Moreover, the production of CO and CO2 was delayed due to production of large stable C,O atoms cluster. These critical insights into the initial processes involved in the shock induced decomposition of FOX-7 will greatly help in understanding the factors playing an important role in the insensitiveness of this high energy material. This research is supported by AFOSR Award No. FA9550-16-1-0042.

Use of Direct Dynamics Simulations to Determine Unimolecular Reaction Paths and Arrhenius Parameters for Large Molecules.

PubMed

Yang, Li; Sun, Rui; Hase, William L

2011-11-08

In a previous study (J. Chem. Phys.2008, 129, 094701) it was shown that for a large molecule, with a total energy much greater than its barrier for decomposition and whose vibrational modes are harmonic oscillators, the expressions for the classical Rice-Ramsperger-Kassel-Marcus (RRKM) (i.e., RRK) and classical transition-state theory (TST) rate constants become equivalent. Using this relationship, a molecule's unimolecular rate constants versus temperature may be determined from chemical dynamics simulations of microcanonical ensembles for the molecule at different total energies. The simulation identifies the molecule's unimolecular pathways and their Arrhenius parameters. In the work presented here, this approach is used to study the thermal decomposition of CH3-NH-CH═CH-CH3, an important constituent in the polymer of cross-linked epoxy resins. Direct dynamics simulations, at the MP2/6-31+G* level of theory, were used to investigate the decomposition of microcanonical ensembles for this molecule. The Arrhenius A and Ea parameters determined from the direct dynamics simulation are in very good agreement with the TST Arrhenius parameters for the MP2/6-31+G* potential energy surface. The simulation method applied here may be particularly useful for large molecules with a multitude of decomposition pathways and whose transition states may be difficult to determine and have structures that are not readily obvious.

Density functional study of the decomposition pathways of SiH₃ and GeH₃ at the Si(100) and Ge(100) surfaces.

PubMed

Ceriotti, M; Montalenti, F; Bernasconi, M

2012-03-14

By means of first-principles calculations we studied the decomposition pathways of SiH₃ on Ge(100) and of GeH₃ on Si(100), of interest for the growth of crystalline SiGe alloys and Si/Ge heterostructures by plasma-enhanced chemical vapor deposition. We also investigated H desorption via reaction of two adsorbed SiH₂/GeH₂ species (β₂ reaction) or via Eley-Rideal abstraction of surface H atoms from the impinging SiH₃ and GeH₃ species. The calculated activation energies for the different processes suggest that the rate-limiting step for the growth of Si/Ge systems is still the β₂ reaction of two SiH₂ as in the growth of crystalline Si.

Thermal Decomposition Mechanism of Butyraldehyde

NASA Astrophysics Data System (ADS)

Hatten, Courtney D.; Warner, Brian; Wright, Emily; Kaskey, Kevin; McCunn, Laura R.

2013-06-01

The thermal decomposition of butyraldehyde, CH_3CH_2CH_2C(O)H, has been studied in a resistively heated SiC tubular reactor. Products of pyrolysis were identified via matrix-isolation FTIR spectroscopy and photoionization mass spectrometry in separate experiments. Carbon monoxide, ethene, acetylene, water and ethylketene were among the products detected. To unravel the mechanism of decomposition, pyrolysis of a partially deuterated sample of butyraldehyde was studied. Also, the concentration of butyraldehyde in the carrier gas was varied in experiments to determine the presence of bimolecular reactions. The results of these experiments can be compared to the dissociation pathways observed in similar aldehydes and are relevant to the processing of biomass, foods, and tobacco.

Aerogel composites and method of manufacture

DOEpatents

Cao, Wanqing; Hunt, Arlon Jason

1999-01-01

Disclosed herewith is a process of forming an aerogel composite which comprises introducing a gaseous material into a formed aerogel monolith or powder, and causing decomposition of said gaseous material in said aerogel in amounts sufficient to cause deposition of the decomposition products of the gas on the surfaces of the pores of the said aerogel. Also disclosed are the composites made by the process.

Permafrost Thaw, Soil Moisture and Plant Community Change Alter Organic Matter Decomposition in Alaskan Tundra

NASA Astrophysics Data System (ADS)

Natali, S.; Mauritz, M.; Pegoraro, E.; Schuur, E.

2015-12-01

Climate warming in arctic tundra has been associated with increased plant productivity and a shift in plant community composition, specifically an increase in shrub cover, which can impact soil organic matter through changes in the size and composition of the leaf litter pool. Shifts in litter quantity and quality will in turn interact with changes in the soil environment as the climate continues to warm. We examined the effects of permafrost thaw, soil moisture changes, and plant community composition on leaf litter decomposition in an upland tundra ecosystem in Interior Alaska. We present warming and drying effects on decomposition rates of graminoid-dominated and shrub-dominated leaf litter mixtures over three years (2 cm depth), and annual decomposition of a common cellulose substrate (0-10 cm and 10-20 cm) over five years at a permafrost thaw and soil drying experiment. We expected that warming and drying would increase decomposition, and that decomposition would be greater in the shrub litter than in the graminoid litter mix. Decomposition of Betula nana, the dominant shrub, was 50% greater in the shrub-dominated litter mix compared to the graminoid-dominated litter. Surprisingly, there was no significant difference in total litter mass loss between graminoid and shrub litter mixtures, despite significant differences in decomposition rates of the dominant plant species when decomposed alone and in community mixtures. Drying decreased decomposition of B. nana and of the shrub community litter overall, but after two years there was no detected warming effect on shrub-community decomposition. In contrast to leaf litter decomposition, both warming and drying increased decomposition of the common substrate. Warming caused an almost twofold increase in cellulose decomposition in surface soil (0-10cm), and drying caused a twofold increase in cellulose decomposition from deeper organic layer soils (10-20cm). These results demonstrate the importance of interactions among temperature, moisture and vegetation changes on organic matter decomposition, and the potential for increased plant productivity and vegetation changes to alter the size and composition of the soil organic matter pool.

Modeling the Metabolism of Arabidopsis thaliana: Application of Network Decomposition and Network Reduction in the Context of Petri Nets.

PubMed

Koch, Ina; Nöthen, Joachim; Schleiff, Enrico

2017-01-01

Motivation: Arabidopsis thaliana is a well-established model system for the analysis of the basic physiological and metabolic pathways of plants. Nevertheless, the system is not yet fully understood, although many mechanisms are described, and information for many processes exists. However, the combination and interpretation of the large amount of biological data remain a big challenge, not only because data sets for metabolic paths are still incomplete. Moreover, they are often inconsistent, because they are coming from different experiments of various scales, regarding, for example, accuracy and/or significance. Here, theoretical modeling is powerful to formulate hypotheses for pathways and the dynamics of the metabolism, even if the biological data are incomplete. To develop reliable mathematical models they have to be proven for consistency. This is still a challenging task because many verification techniques fail already for middle-sized models. Consequently, new methods, like decomposition methods or reduction approaches, are developed to circumvent this problem. Methods: We present a new semi-quantitative mathematical model of the metabolism of Arabidopsis thaliana . We used the Petri net formalism to express the complex reaction system in a mathematically unique manner. To verify the model for correctness and consistency we applied concepts of network decomposition and network reduction such as transition invariants, common transition pairs, and invariant transition pairs. Results: We formulated the core metabolism of Arabidopsis thaliana based on recent knowledge from literature, including the Calvin cycle, glycolysis and citric acid cycle, glyoxylate cycle, urea cycle, sucrose synthesis, and the starch metabolism. By applying network decomposition and reduction techniques at steady-state conditions, we suggest a straightforward mathematical modeling process. We demonstrate that potential steady-state pathways exist, which provide the fixed carbon to nearly all parts of the network, especially to the citric acid cycle. There is a close cooperation of important metabolic pathways, e.g., the de novo synthesis of uridine-5-monophosphate, the γ-aminobutyric acid shunt, and the urea cycle. The presented approach extends the established methods for a feasible interpretation of biological network models, in particular of large and complex models.

Modeling the Metabolism of Arabidopsis thaliana: Application of Network Decomposition and Network Reduction in the Context of Petri Nets

PubMed Central

Koch, Ina; Nöthen, Joachim; Schleiff, Enrico

2017-01-01

Motivation: Arabidopsis thaliana is a well-established model system for the analysis of the basic physiological and metabolic pathways of plants. Nevertheless, the system is not yet fully understood, although many mechanisms are described, and information for many processes exists. However, the combination and interpretation of the large amount of biological data remain a big challenge, not only because data sets for metabolic paths are still incomplete. Moreover, they are often inconsistent, because they are coming from different experiments of various scales, regarding, for example, accuracy and/or significance. Here, theoretical modeling is powerful to formulate hypotheses for pathways and the dynamics of the metabolism, even if the biological data are incomplete. To develop reliable mathematical models they have to be proven for consistency. This is still a challenging task because many verification techniques fail already for middle-sized models. Consequently, new methods, like decomposition methods or reduction approaches, are developed to circumvent this problem. Methods: We present a new semi-quantitative mathematical model of the metabolism of Arabidopsis thaliana. We used the Petri net formalism to express the complex reaction system in a mathematically unique manner. To verify the model for correctness and consistency we applied concepts of network decomposition and network reduction such as transition invariants, common transition pairs, and invariant transition pairs. Results: We formulated the core metabolism of Arabidopsis thaliana based on recent knowledge from literature, including the Calvin cycle, glycolysis and citric acid cycle, glyoxylate cycle, urea cycle, sucrose synthesis, and the starch metabolism. By applying network decomposition and reduction techniques at steady-state conditions, we suggest a straightforward mathematical modeling process. We demonstrate that potential steady-state pathways exist, which provide the fixed carbon to nearly all parts of the network, especially to the citric acid cycle. There is a close cooperation of important metabolic pathways, e.g., the de novo synthesis of uridine-5-monophosphate, the γ-aminobutyric acid shunt, and the urea cycle. The presented approach extends the established methods for a feasible interpretation of biological network models, in particular of large and complex models. PMID:28713420

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

PubMed

Chambreau, Steven D; Popolan-Vaida, Denisia M; Vaghjiani, Ghanshyam L; Leone, Stephen R

2017-05-18

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies. Products include NH 3 , H 2 O, NO, hydroxylamine (HA), HNO 3 , and a small amount of NO 2 at high temperature. No N 2 O was detected under these experimental conditions, despite the fact that N 2 O is one of the expected products according to the generally accepted thermal decomposition mechanism of HAN. Upon introduction of iridium catalyst, a significant enhancement of the NO/HA ratio was observed. This observation indicates that the formation of NO via decomposition of HA is an important pathway in the catalytic decomposition of HAN.

Beneficial reuse and sustainability: the fate of organic compounds in land-applied waste.

PubMed

Overcash, Michael; Sims, Ronald C; Sims, Judith L; Nieman, J Karl C

2005-01-01

Land application systems, also referred to as beneficial reuse systems, are engineered systems that have defined and permitted application areas based on site and waste characteristics to determine the land area size requirement. These terrestrial systems have orders of magnitude greater microbial capability and residence time to achieve decomposition and assimilation compared with aquatic systems. In this paper we focus on current information and information needs related to terrestrial fate pathways in land treatment systems. Attention is given to conventional organic chemicals as well as new estrogenic and pharmaceutical chemicals of commerce. Specific terrestrial fate pathways addressed include: decomposition, bound residue formation, leaching, runoff, and crop uptake. Molecular decomposition and formation of bound residues provide the basis for the design and regulation of land treatment systems. These mechanisms allow for assimilation of wastes and nondegradation of the environment and accomplish the goal of sustainable land use. Bound residues that are biologically produced are relatively immobile, degrade at rates similar to natural soil materials, and should present a significantly reduced risk to the environment as opposed to parent contaminants. With regard to leaching and runoff pathways, no comprehensive summary or mathematical model of organic chemical migration from land treatment systems has been developed. For the crop uptake pathway, a critical need exists to develop information for nonagricultural chemicals and to address full-scale performance and monitoring at more land application sites. The limited technology choices for treatment of biosolids, liquids, and other wastes implies that acceptance of some risks and occurrence of some benefits will continue to characterize land application practices that contribute directly to the goal of beneficial reuse and sustainability.

Heats of Formation for Cyclic C4Fn, n=4-8, and their Cations

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Ricca, Alessandra; Arnold, James (Technical Monitor)

2000-01-01

Heats of formation for cyclic C4F8 and C4F8+ are determined at the G3MP2 level. The several decomposition pathways are investigated. The calculations confirm that C4F8+ rearranges and its decomposition is responsible for both the C2F4+ and C3F5+ species observed in experiment. The heats of formation are presented for C4Fn and C4Fn+, n = 4-8.

Effect of pressure on rate of burning /decomposition with flame/ of liquid hydrazine.

NASA Technical Reports Server (NTRS)

Antoine, A. C.

1966-01-01

Liquid hydrazine decomposition process to determine what chemical or physical changes may be occurring that cause breaks in burning rate/ pressure curves, measuring flame temperature and light emission

Demonstration of the Catalytic Decomposition of Hydrogen Peroxide

NASA Astrophysics Data System (ADS)

Conklin, Alfred R., Jr.; Kessinger, Angela

1996-09-01

Catalytic decomposition is demonstrated by placing hydrogen peroxide solutions in a one liter graduated cylinder and adding soap, food coloring, and potassium iodide. Released oxygen is trapped by the soap producing bubbles. The volume of bubbles is proportional to the concentration of hydrogen peroxide. Chloride and bromide do not cause decomposition. Increased reactant temperature increases the volume of bubbles formed.

Response of an Alpine Tundra in the Southern Rocky Mountains to Climate Change by 2100: Projections of Water, Carbon, and Nitrogen Cycling under RCP 4.5 and RCP 8.5 Scenarios

NASA Astrophysics Data System (ADS)

Dong, Z.; Driscoll, C. T.; Hayhoe, K.; Pourmokhtarian, A.; Stoner, A. M. K.

2016-12-01

Biogeochemical cycling of water, carbon, and nitrogen in alpine tundra ecosystems are closely related to the water and nutrient supply and ecosystem function of watersheds. While studies on the response of alpine tundra to climate change have largely focused on ecosystem structure, research on response of ecosystem function and element cycling are less well established. Using downscaled future climate scenarios under Representative Concentration Pathways (RCP) and revised algorithm of the ecosystem model, PnET-BGC, we investigated water, carbon, and nitrogen cycling of an alpine tundra ecosystem under different projections of future climate change at Saddle site of Niwot Ridge, Colorado. Simulations from this study suggest that future water supply from the alpine tundra was well predicted by the Budyko curve, which contrasts with findings from several previous studies. Although foliar display is projected to decrease due to summer water stress, an extend growing season and increasing atmospheric CO2 concentrations reverse its effects on carbon fixation by allowing longer period of photosynthesis and greater photosynthetic rate per leaf area. As a result of the increasing carbon sequestration, large increases in carbon storage are projected in living and dead biomass. Decomposition of soil organic carbon and mineralization of soil organic nitrogen increase with temperature and soil moisture, but also related to the period of snow cover which likely enhances microbial activity and associated soil decomposition and N immobilization. Future increase in winter precipitation leads to increasing snow water content which increases spring soil moisture and decomposition. Shorter future snow cover period and decreased summer soil moisture caused lower decomposition in both seasons, therefore negligible long-term pattern is projected. Future net N mineralization generally followed the pattern of organic carbon decomposition, but slightly increased because of decreasing winter immobilization due to projected shorter snow cover period. Nitrogen uptake is projected to be higher under radiative forcing scenarios of higher primary production and greater net N mineralization.

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

PubMed Central

Tian, Zhenyu; Pitz, William J.; Fournet, René; Glaude, Pierre-Alexander; Battin-Leclerc, Frédérique

2013-01-01

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics. PMID:23762016

Decomposition pathways in age hardening of Ti-Al-N films

NASA Astrophysics Data System (ADS)

Rachbauer, R.; Massl, S.; Stergar, E.; Holec, D.; Kiener, D.; Keckes, J.; Patscheider, J.; Stiefel, M.; Leitner, H.; Mayrhofer, P. H.

2011-07-01

The ability to increase the thermal stability of protective coatings under work load gives rise to scientific and industrial interest in age hardening of complex nitride coating systems such as ceramic-like Ti1-xAlxN. However, the decomposition pathway of these systems from single-phase cubic to the thermodynamically stable binary nitrides (cubic TiN and wurtzite AlN), which are essential for age hardening, are not yet fully understood. In particular, the role of decomposition kinetics still requires more detailed investigation. In the present work, the combined effect of annealing time and temperature upon the nano-structural development of Ti0.46Al0.54N thin films is studied, with a thermal exposure of either 1 min or 120 min in 100 °C steps from 500 °C to 1400 °C. The impact of chemical changes at the atomic scale on the development of micro-strain and mechanical properties is studied by post-annealing investigations using X-ray diffraction, nanoindentation, 3D-atom probe tomography and high-resolution transmission electron microscopy. The results clearly demonstrate that the spinodal decomposition process, triggering the increase of micro-strain and hardness, although taking place throughout the entire volume, is enhanced at high diffusivity paths such as grain or column boundaries and followed within the grains. Ab initio calculations further show that the early stages of wurtzite AlN precipitation are connected with increased strain formation, which is in excellent agreement with experimental observations.

Can thinning slash cause a nitrogen deficiency in pumice soils of central Oregon?

Treesearch

P.H. Cochran

1968-01-01

Decomposition of thinning slash deposited on the soil surface should have no direct adverse effect on the soil nitrogen available to higher plants in the pumice soil region. Decomposition of roots of cut trees would immobilize nitrogen in the soil immediately adjacent to the root during the decomposition period, which appears to be short for the smaller roots. However...

Pressure-dependent competition among reaction pathways from first- and second-O 2 additions in the low-temperature oxidation of tetrahydrofuran

DOE PAGES

Antonov, Ivan O.; Zador, Judit; Rotavera, Brandon; ...

2016-07-21

Here, we report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10–2000 Torr and T = 400–700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O 2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO 2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely ofmore » central importance in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O 2 and QOOH + O 2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH.« less

Pathways of economic inequalities in maternal and child health in urban India: a decomposition analysis.

PubMed

Goli, Srinivas; Doshi, Riddhi; Perianayagam, Arokiasamy

2013-01-01

Children and women comprise vulnerable populations in terms of health and are gravely affected by the impact of economic inequalities through multi-dimensional channels. Urban areas are believed to have better socioeconomic and maternal and child health indicators than rural areas. This perception leads to the implementation of health policies ignorant of intra-urban health inequalities. Therefore, the objective of this study is to explain the pathways of economic inequalities in maternal and child health indicators among the urban population of India. Using data from the third wave of the National Family Health Survey (NFHS, 2005-06), this study calculated relative contribution of socioeconomic factors to inequalities in key maternal and child health indicators such as antenatal check-ups (ANCs), institutional deliveries, proportion of children with complete immunization, proportion of underweight children, and Infant Mortality Rate (IMR). Along with regular CI estimates, this study applied widely used regression-based Inequality Decomposition model proposed by Wagstaff and colleagues. The CI estimates show considerable economic inequalities in women with less than 3 ANCs (CI = -0.3501), institutional delivery (CI = -0.3214), children without fully immunization (CI = -0.18340), underweight children (CI = -0.19420), and infant deaths (CI = -0.15596). Results of the decomposition model reveal that illiteracy among women and her partner, poor economic status, and mass media exposure are the critical factors contributing to economic inequalities in maternal and child health indicators. The residuals in all the decomposition models are very less; this implies that the above mentioned factors explained maximum inequalities in maternal and child health of urban population in India. Findings suggest that illiteracy among women and her partner, poor economic status, and mass media exposure are the critical pathways through which economic factors operate on inequalities in maternal and child health outcomes in urban India.

Pathways of Economic Inequalities in Maternal and Child Health in Urban India: A Decomposition Analysis

PubMed Central

Goli, Srinivas; Doshi, Riddhi; Perianayagam, Arokiasamy

2013-01-01

Background/Objective Children and women comprise vulnerable populations in terms of health and are gravely affected by the impact of economic inequalities through multi-dimensional channels. Urban areas are believed to have better socioeconomic and maternal and child health indicators than rural areas. This perception leads to the implementation of health policies ignorant of intra-urban health inequalities. Therefore, the objective of this study is to explain the pathways of economic inequalities in maternal and child health indicators among the urban population of India. Methods Using data from the third wave of the National Family Health Survey (NFHS, 2005–06), this study calculated relative contribution of socioeconomic factors to inequalities in key maternal and child health indicators such as antenatal check-ups (ANCs), institutional deliveries, proportion of children with complete immunization, proportion of underweight children, and Infant Mortality Rate (IMR). Along with regular CI estimates, this study applied widely used regression-based Inequality Decomposition model proposed by Wagstaff and colleagues. Results The CI estimates show considerable economic inequalities in women with less than 3 ANCs (CI  = −0.3501), institutional delivery (CI  = −0.3214), children without fully immunization (CI  = −0.18340), underweight children (CI  = −0.19420), and infant deaths (CI  = −0.15596). Results of the decomposition model reveal that illiteracy among women and her partner, poor economic status, and mass media exposure are the critical factors contributing to economic inequalities in maternal and child health indicators. The residuals in all the decomposition models are very less; this implies that the above mentioned factors explained maximum inequalities in maternal and child health of urban population in India. Conclusion Findings suggest that illiteracy among women and her partner, poor economic status, and mass media exposure are the critical pathways through which economic factors operate on inequalities in maternal and child health outcomes in urban India. PMID:23555587

Theoretical study of the decomposition mechanism of environmentally friendly insulating medium C3F7CN in the presence of H2O in a discharge

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tian, Shuangshuang; Deng, Zaitao; Tang, Ju

2017-08-01

C3F7CN has been the focus of the alternative gas research field over the past two years because of its excellent insulation properties and environmental characteristics. Experimental studies on its insulation performance have made many achievements. However, few studies on the formation mechanism of the decomposition components exist. A discussion of the decomposition characteristics of insulating media will provide guidance for scientific experimental research and the work that must be completed before further engineering application. In this study, the decomposition mechanism of C3F7CN in the presence of trace H2O under discharge was calculated based on the density functional theory and transition state theory. The reaction heat, Gibbs free energy, and activation energy of different decomposition pathways were investigated. The ionization parameters and toxicity of C3F7CN and various decomposition products were analyzed from the molecular structure perspective. The formation mechanism of the C3F7CN discharge decomposition components and the influence of trace water were evaluated. This paper confirms that C3F7CN has excellent decomposition characteristics, which provide theoretical support for later experiments and related engineering applications. However, the existence of trace water has a negative impact on C3F7CN’s insulation performance. Thus, strict trace water content standards should be developed to ensure dielectric insulation and the safety of maintenance personnel.

Effects of defects on thermal decomposition of HMX via ReaxFF molecular dynamics simulations.

PubMed

Zhou, Ting-Ting; Huang, Feng-Lei

2011-01-20

Effects of molecular vacancies on the decomposition mechanisms and reaction dynamics of condensed-phase β-HMX at various temperatures were studied using ReaxFF molecular dynamics simulations. Results show that three primary initial decomposition mechanisms, namely, N-NO(2) bond dissociation, HONO elimination, and concerted ring fission, exist at both high and lower temperatures. The contribution of the three mechanisms to the initial decomposition of HMX is influenced by molecular vacancies, and the effects vary with temperature. At high temperature (2500 K), molecular vacancies remarkably promote N-N bond cleavage and concerted ring breaking but hinder HONO formation. N-N bond dissociation and HONO elimination are two primary competing reaction mechanisms, and the former is dominant in the initial decomposition. Concerted ring breaking of condensed-phase HMX is not favored at high temperature. At lower temperature (1500 K), the most preferential initial decomposition pathway is N-N bond dissociation followed by the formation of NO(3) (O migration), although all three mechanisms are promoted by molecular vacancies. The promotion effect on concerted ring breaking is considerable at lower temperature. Products resulting from concerted ring breaking appear in the defective system but not in the perfect crystal. The mechanism of HONO elimination is less important at lower temperature. We also estimated the reaction rate constant and activation barriers of initial decomposition with different vacancy concentrations. Molecular vacancies accelerate the decomposition of condensed-phase HMX by increasing the reaction rate constant and reducing activation barriers.

Exploring Patterns of Soil Organic Matter Decomposition with Students and the Public Through the Global Decomposition Project (GDP)

NASA Astrophysics Data System (ADS)

Wood, J. H.; Natali, S.

2014-12-01

The Global Decomposition Project (GDP) is a program designed to introduce and educate students and the general public about soil organic matter and decomposition through a standardized protocol for collecting, reporting, and sharing data. This easy-to-use hands-on activity focuses on questions such as "How do environmental conditions control decomposition of organic matter in soil?" and "Why do some areas accumulate organic matter and others do not?" Soil organic matter is important to local ecosystems because it affects soil structure, regulates soil moisture and temperature, and provides energy and nutrients to soil organisms. It is also important globally because it stores a large amount of carbon, and when microbes "eat", or decompose organic matter they release greenhouse gasses such as carbon dioxide and methane into the atmosphere, which affects the earth's climate. The protocol describes a commonly used method to measure decomposition using a paper made of cellulose, a component of plant cell walls. Participants can receive pre-made cellulose decomposition bags, or make decomposition bags using instructions in the protocol and easily obtained materials (e.g., window screen and lignin-free paper). Individual results will be shared with all participants and the broader public through an online database. We will present decomposition bag results from a research site in Alaskan tundra, as well as from a middle-school-student led experiment in California. The GDP demonstrates how scientific methods can be extended to educate broader audiences, while at the same time, data collected by students and the public can provide new insight into global patterns of soil decomposition. The GDP provides a pathway for scientists and educators to interact and reach meaningful education and research goals.

A Key Enzyme of the NAD+ Salvage Pathway in Thermus thermophilus: Characterization of Nicotinamidase and the Impact of Its Gene Deletion at High Temperatures

PubMed Central

Taniguchi, Hironori; Sungwallek, Sathidaphorn; Chotchuang, Phatcharin; Okano, Kenji

2017-01-01

ABSTRACT NAD (NAD+) is a cofactor related to many cellular processes. This cofactor is known to be unstable, especially at high temperatures, where it chemically decomposes to nicotinamide and ADP-ribose. Bacteria, yeast, and higher organisms possess the salvage pathway for reconstructing NAD+ from these decomposition products; however, the importance of the salvage pathway for survival is not well elucidated, except for in pathogens lacking the NAD+ de novo synthesis pathway. Herein, we report the importance of the NAD+ salvage pathway in the thermophilic bacterium Thermus thermophilus HB8 at high temperatures. We identified the gene encoding nicotinamidase (TTHA0328), which catalyzes the first reaction of the NAD+ salvage pathway. This recombinant enzyme has a high catalytic activity against nicotinamide (Km of 17 μM, kcat of 50 s−1, kcat/Km of 3.0 × 103 s−1 · mM−1). Deletion of this gene abolished nicotinamide deamination activity in crude extracts of T. thermophilus and disrupted the NAD+ salvage pathway in T. thermophilus. Disruption of the salvage pathway led to the severe growth retardation at a higher temperature (80°C), owing to the drastic decrease in the intracellular concentrations of NAD+ and NADH. IMPORTANCE NAD+ and other nicotinamide cofactors are essential for cell metabolism. These molecules are unstable and decompose, even under the physiological conditions in most organisms. Thermophiles can survive at high temperatures where NAD+ decomposition is, in general, more rapid. This study emphasizes that NAD+ instability and its homeostasis can be one of the important factors for thermophile survival in extreme temperatures. PMID:28630126

A Key Enzyme of the NAD+ Salvage Pathway in Thermus thermophilus: Characterization of Nicotinamidase and the Impact of Its Gene Deletion at High Temperatures.

PubMed

Taniguchi, Hironori; Sungwallek, Sathidaphorn; Chotchuang, Phatcharin; Okano, Kenji; Honda, Kohsuke

2017-09-01

NAD (NAD + ) is a cofactor related to many cellular processes. This cofactor is known to be unstable, especially at high temperatures, where it chemically decomposes to nicotinamide and ADP-ribose. Bacteria, yeast, and higher organisms possess the salvage pathway for reconstructing NAD + from these decomposition products; however, the importance of the salvage pathway for survival is not well elucidated, except for in pathogens lacking the NAD + de novo synthesis pathway. Herein, we report the importance of the NAD + salvage pathway in the thermophilic bacterium Thermus thermophilus HB8 at high temperatures. We identified the gene encoding nicotinamidase (TTHA0328), which catalyzes the first reaction of the NAD + salvage pathway. This recombinant enzyme has a high catalytic activity against nicotinamide ( K m of 17 μM, k cat of 50 s -1 , k cat / K m of 3.0 × 10 3 s -1 · mM -1 ). Deletion of this gene abolished nicotinamide deamination activity in crude extracts of T. thermophilus and disrupted the NAD + salvage pathway in T. thermophilus Disruption of the salvage pathway led to the severe growth retardation at a higher temperature (80°C), owing to the drastic decrease in the intracellular concentrations of NAD + and NADH. IMPORTANCE NAD + and other nicotinamide cofactors are essential for cell metabolism. These molecules are unstable and decompose, even under the physiological conditions in most organisms. Thermophiles can survive at high temperatures where NAD + decomposition is, in general, more rapid. This study emphasizes that NAD + instability and its homeostasis can be one of the important factors for thermophile survival in extreme temperatures. Copyright © 2017 American Society for Microbiology.

Mechanistic investigation into sunlight-facilitated photodegradation of pyrene in seawater with oil dispersants.

PubMed

Fu, Jie; Gong, Yanyan; Cai, Zhengqing; O'Reilly, S E; Zhao, Dongye

2017-01-30

This study investigated the effects of 3 model oil dispersants (Corexit EC9500A, Corexit EC9527A and SPC 1000) on photodegradation of pyrene under simulated sunlight. Both Corexit dispersants enhanced photodegradation of pyrene, while SPC1000 slightly inhibited the reaction. Span 80 and Tween 85 were the key ingredients causing the effects, though the underlying mechanisms differed. Span 80 enriches pyrene in the upper layer of water column, whereas Tween 85 induces a photosensitization process. Two reactive oxygen species, 1 O 2 and O 2 - , were found responsible for pyrene photodegradation, though the presence of EC9500A suppressed the 1 O 2 pathway. In terms of photodegradation products, EC9500A enhanced generation of polyaromatic intermediates, i.e., phenaleno[1,9-cd][1,2]dioxine, 1-hydroxypyrene, and 1,8-pyrenequinone, but did not alter the classical photodegradation pathway. The Corexit dispersants were more prone to photochemical decomposition, with multiple by-products detected. The information aids in our understanding of the effects of dispersants on photochemical weathering of oil compositions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of Petri net based analysis techniques to signal transduction pathways.

PubMed

Sackmann, Andrea; Heiner, Monika; Koch, Ina

2006-11-02

Signal transduction pathways are usually modelled using classical quantitative methods, which are based on ordinary differential equations (ODEs). However, some difficulties are inherent in this approach. On the one hand, the kinetic parameters involved are often unknown and have to be estimated. With increasing size and complexity of signal transduction pathways, the estimation of missing kinetic data is not possible. On the other hand, ODEs based models do not support any explicit insights into possible (signal-) flows within the network. Moreover, a huge amount of qualitative data is available due to high-throughput techniques. In order to get information on the systems behaviour, qualitative analysis techniques have been developed. Applications of the known qualitative analysis methods concern mainly metabolic networks. Petri net theory provides a variety of established analysis techniques, which are also applicable to signal transduction models. In this context special properties have to be considered and new dedicated techniques have to be designed. We apply Petri net theory to model and analyse signal transduction pathways first qualitatively before continuing with quantitative analyses. This paper demonstrates how to build systematically a discrete model, which reflects provably the qualitative biological behaviour without any knowledge of kinetic parameters. The mating pheromone response pathway in Saccharomyces cerevisiae serves as case study. We propose an approach for model validation of signal transduction pathways based on the network structure only. For this purpose, we introduce the new notion of feasible t-invariants, which represent minimal self-contained subnets being active under a given input situation. Each of these subnets stands for a signal flow in the system. We define maximal common transition sets (MCT-sets), which can be used for t-invariant examination and net decomposition into smallest biologically meaningful functional units. The paper demonstrates how Petri net analysis techniques can promote a deeper understanding of signal transduction pathways. The new concepts of feasible t-invariants and MCT-sets have been proven to be useful for model validation and the interpretation of the biological system behaviour. Whereas MCT-sets provide a decomposition of the net into disjunctive subnets, feasible t-invariants describe subnets, which generally overlap. This work contributes to qualitative modelling and to the analysis of large biological networks by their fully automatic decomposition into biologically meaningful modules.

Application of Petri net based analysis techniques to signal transduction pathways

PubMed Central

Sackmann, Andrea; Heiner, Monika; Koch, Ina

2006-01-01

Background Signal transduction pathways are usually modelled using classical quantitative methods, which are based on ordinary differential equations (ODEs). However, some difficulties are inherent in this approach. On the one hand, the kinetic parameters involved are often unknown and have to be estimated. With increasing size and complexity of signal transduction pathways, the estimation of missing kinetic data is not possible. On the other hand, ODEs based models do not support any explicit insights into possible (signal-) flows within the network. Moreover, a huge amount of qualitative data is available due to high-throughput techniques. In order to get information on the systems behaviour, qualitative analysis techniques have been developed. Applications of the known qualitative analysis methods concern mainly metabolic networks. Petri net theory provides a variety of established analysis techniques, which are also applicable to signal transduction models. In this context special properties have to be considered and new dedicated techniques have to be designed. Methods We apply Petri net theory to model and analyse signal transduction pathways first qualitatively before continuing with quantitative analyses. This paper demonstrates how to build systematically a discrete model, which reflects provably the qualitative biological behaviour without any knowledge of kinetic parameters. The mating pheromone response pathway in Saccharomyces cerevisiae serves as case study. Results We propose an approach for model validation of signal transduction pathways based on the network structure only. For this purpose, we introduce the new notion of feasible t-invariants, which represent minimal self-contained subnets being active under a given input situation. Each of these subnets stands for a signal flow in the system. We define maximal common transition sets (MCT-sets), which can be used for t-invariant examination and net decomposition into smallest biologically meaningful functional units. Conclusion The paper demonstrates how Petri net analysis techniques can promote a deeper understanding of signal transduction pathways. The new concepts of feasible t-invariants and MCT-sets have been proven to be useful for model validation and the interpretation of the biological system behaviour. Whereas MCT-sets provide a decomposition of the net into disjunctive subnets, feasible t-invariants describe subnets, which generally overlap. This work contributes to qualitative modelling and to the analysis of large biological networks by their fully automatic decomposition into biologically meaningful modules. PMID:17081284

Ethylene dissociation on flat and stepped Ni(1 1 1): A combined STM and DFT study

NASA Astrophysics Data System (ADS)

Vang, Ronnie T.; Honkala, Karoliina; Dahl, Søren; Vestergaard, Ebbe K.; Schnadt, Joachim; Lægsgaard, Erik; Clausen, Bjerne S.; Nørskov, Jens K.; Besenbacher, Flemming

2006-01-01

The dissociative adsorption of ethylene (C 2H 4) on Ni(1 1 1) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (1 1 1) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges. DFT calculations were performed for several intermediate steps in the decomposition of ethylene on both Ni(1 1 1) and the stepped Ni(2 1 1) surface. In general the Ni(2 1 1) surface is found to have a higher reactivity than the Ni(1 1 1) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular the barrier for dissociation is lowered significantly more than the barrier for dehydrogenation, and this is of great importance for the bond-breaking selectivity of Ni surfaces. The influence of step edges was also probed by evaporating Ag onto the Ni(1 1 1) surface. STM shows that the room temperature evaporation leads to a step flow growth of Ag islands, and a subsequent annealing at 800 K causes the Ag atoms to completely wet the step edges of Ni(1 1 1). The blocking of the step edges is shown to prevent all decomposition of ethylene at room temperature, whereas the terrace site decomposition at 500 K is confirmed to be unaffected by the Ag atoms. Finally a high surface area NiAg alloy catalyst supported on MgAl 2O 4 was synthesized and tested in flow reactor measurements. The NiAg catalyst has a much lower activity for ethane hydrogenolysis than a similar Ni catalyst, which can be rationalized by the STM and DFT results.

Immobilization of Anions on Polymer Matrices for Gel Electrolytes with High Conductivity and Stability in Lithium Ion Batteries.

PubMed

Wang, Shih-Hong; Lin, Yong-Yi; Teng, Chiao-Yi; Chen, Yen-Ming; Kuo, Ping-Lin; Lee, Yuh-Lang; Hsieh, Chien-Te; Teng, Hsisheng

2016-06-15

This study reports on a high ionic-conductivity gel polymer electrolyte (GPE), which is supported by a TiO2 nanoparticle-decorated polymer framework comprising poly(acrylonitrile-co-vinyl acetate) blended with poly(methyl methacrylate), i.e. , PAVM: TiO2. High conductivity TiO2 is achieved by causing the PAVM:TiO2 polymer framework to swell in 1 M LiPF6 in carbonate solvent. Raman analysis results demonstrate that the poly(acrylonitrile) (PAN) segments and TiO2 nanoparticles strongly adsorb PF6(-) anions, thereby generating 3D percolative space-charge pathways surrounding the polymer framework for Li(+)-ion transport. The ionic conductivity of TiO2 is nearly 1 order of magnitude higher than that of commercial separator-supported liquid electrolyte (SLE). TiO2 has a high Li(+) transference number (0.7), indicating that most of the PF6(-) anions are stationary, which suppresses PF6(-) decomposition and substantially enlarges the voltage that can be applied to TiO2 (to 6.5 V vs Li/Li(+)). Immobilization of PF6(-) anions also leads to the formation of stable solid-electrolyte interface (SEI) layers in a full-cell graphite|electrolyte|LiFePO4 battery, which exhibits low SEI and overall resistances. The graphite|electrolyte|LiFePO4 battery delivers high capacity of 84 mAh g(-1) even at 20 C and presents 90% and 71% capacity retention after 100 and 1000 charge-discharge cycles, respectively. This study demonstrates a GPE architecture comprising 3D space charge pathways for Li(+) ions and suppresses anion decomposition to improve the stability and lifespan of the resulting LIBs.

Modular analysis of biological networks.

PubMed

Kaltenbach, Hans-Michael; Stelling, Jörg

2012-01-01

The analysis of complex biological networks has traditionally relied on decomposition into smaller, semi-autonomous units such as individual signaling pathways. With the increased scope of systems biology (models), rational approaches to modularization have become an important topic. With increasing acceptance of de facto modularity in biology, widely different definitions of what constitutes a module have sparked controversies. Here, we therefore review prominent classes of modular approaches based on formal network representations. Despite some promising research directions, several important theoretical challenges remain open on the way to formal, function-centered modular decompositions for dynamic biological networks.

Proteomic analysis reveals large amounts of decomposition enzymes and major metabolic pathways involved in algicidal process of Trametes versicolor F21a.

PubMed

Gao, Xueyan; Wang, Congyan; Dai, Wei; Ren, Shenrong; Tao, Fang; He, Xingbing; Han, Guomin; Wang, Wei

2017-06-20

A recent algicidal mode indicates that fungal mycelia can wrap and eliminate almost all co-cultivated algal cells within a short time span. However, the underlying molecular mechanism is rarely understood. We applied proteomic analysis to investigate the algicidal process of Trametes versicolor F21a and identified 3,754 fungal proteins. Of these, 30 fungal enzymes with endo- or exoglycosidase activities such as β-1,3-glucanase, α-galactosidase, α-glucosidase, alginate lyase and chondroitin lyase were significantly up-regulated. These proteins belong to Glycoside Hydrolases, Auxiliary Activities, Carbohydrate Esterases and Polysaccharide Lyases, suggesting that these enzymes may degrade lipopolysaccharides, peptidoglycans and alginic acid of algal cells. Additionally, peptidase, exonuclease, manganese peroxidase and cytochrome c peroxidase, which decompose proteins and DNA or convert other small molecules of algal cells, could be other major decomposition enzymes. Gene Ontology and KEGG pathway enrichment analysis demonstrated that pyruvate metabolism and tricarboxylic acid cycle pathways play a critical role in response to adverse environment via increasing energy production to synthesize lytic enzymes or uptake molecules. Carbon metabolism, selenocompound metabolism, sulfur assimilation and metabolism, as well as several amino acid biosynthesis pathways could play vital roles in the synthesis of nutrients required by fungal mycelia.

Hugoniot curve calculation of nitromethane decomposition mixtures: A reactive force field molecular dynamics approach

NASA Astrophysics Data System (ADS)

Guo, Feng; Zhang, Hong; Hu, Hai-Quan; Cheng, Xin-Lu; Zhang, Li-Yan

2015-11-01

We investigate the Hugoniot curve, shock-particle velocity relations, and Chapman-Jouguet conditions of the hot dense system through molecular dynamics (MD) simulations. The detailed pathways from crystal nitromethane to reacted state by shock compression are simulated. The phase transition of N2 and CO mixture is found at about 10 GPa, and the main reason is that the dissociation of the C-O bond and the formation of C-C bond start at 10.0-11.0 GPa. The unreacted state simulations of nitromethane are consistent with shock Hugoniot data. The complete pathway from unreacted to reacted state is discussed. Through chemical species analysis, we find that the C-N bond breaking is the main event of the shock-induced nitromethane decomposition. Project supported by the National Natural Science Foundation of China (Grant No. 11374217) and the Shandong Provincial Natural Science Foundation, China (Grant No. ZR2014BQ008).

MinePath: Mining for Phenotype Differential Sub-paths in Molecular Pathways

PubMed Central

Koumakis, Lefteris; Kartsaki, Evgenia; Chatzimina, Maria; Zervakis, Michalis; Vassou, Despoina; Marias, Kostas; Moustakis, Vassilis; Potamias, George

2016-01-01

Pathway analysis methodologies couple traditional gene expression analysis with knowledge encoded in established molecular pathway networks, offering a promising approach towards the biological interpretation of phenotype differentiating genes. Early pathway analysis methodologies, named as gene set analysis (GSA), view pathways just as plain lists of genes without taking into account either the underlying pathway network topology or the involved gene regulatory relations. These approaches, even if they achieve computational efficiency and simplicity, consider pathways that involve the same genes as equivalent in terms of their gene enrichment characteristics. Most recent pathway analysis approaches take into account the underlying gene regulatory relations by examining their consistency with gene expression profiles and computing a score for each profile. Even with this approach, assessing and scoring single-relations limits the ability to reveal key gene regulation mechanisms hidden in longer pathway sub-paths. We introduce MinePath, a pathway analysis methodology that addresses and overcomes the aforementioned problems. MinePath facilitates the decomposition of pathways into their constituent sub-paths. Decomposition leads to the transformation of single-relations to complex regulation sub-paths. Regulation sub-paths are then matched with gene expression sample profiles in order to evaluate their functional status and to assess phenotype differential power. Assessment of differential power supports the identification of the most discriminant profiles. In addition, MinePath assess the significance of the pathways as a whole, ranking them by their p-values. Comparison results with state-of-the-art pathway analysis systems are indicative for the soundness and reliability of the MinePath approach. In contrast with many pathway analysis tools, MinePath is a web-based system (www.minepath.org) offering dynamic and rich pathway visualization functionality, with the unique characteristic to color regulatory relations between genes and reveal their phenotype inclination. This unique characteristic makes MinePath a valuable tool for in silico molecular biology experimentation as it serves the biomedical researchers’ exploratory needs to reveal and interpret the regulatory mechanisms that underlie and putatively govern the expression of target phenotypes. PMID:27832067

MinePath: Mining for Phenotype Differential Sub-paths in Molecular Pathways.

PubMed

Koumakis, Lefteris; Kanterakis, Alexandros; Kartsaki, Evgenia; Chatzimina, Maria; Zervakis, Michalis; Tsiknakis, Manolis; Vassou, Despoina; Kafetzopoulos, Dimitris; Marias, Kostas; Moustakis, Vassilis; Potamias, George

2016-11-01

Pathway analysis methodologies couple traditional gene expression analysis with knowledge encoded in established molecular pathway networks, offering a promising approach towards the biological interpretation of phenotype differentiating genes. Early pathway analysis methodologies, named as gene set analysis (GSA), view pathways just as plain lists of genes without taking into account either the underlying pathway network topology or the involved gene regulatory relations. These approaches, even if they achieve computational efficiency and simplicity, consider pathways that involve the same genes as equivalent in terms of their gene enrichment characteristics. Most recent pathway analysis approaches take into account the underlying gene regulatory relations by examining their consistency with gene expression profiles and computing a score for each profile. Even with this approach, assessing and scoring single-relations limits the ability to reveal key gene regulation mechanisms hidden in longer pathway sub-paths. We introduce MinePath, a pathway analysis methodology that addresses and overcomes the aforementioned problems. MinePath facilitates the decomposition of pathways into their constituent sub-paths. Decomposition leads to the transformation of single-relations to complex regulation sub-paths. Regulation sub-paths are then matched with gene expression sample profiles in order to evaluate their functional status and to assess phenotype differential power. Assessment of differential power supports the identification of the most discriminant profiles. In addition, MinePath assess the significance of the pathways as a whole, ranking them by their p-values. Comparison results with state-of-the-art pathway analysis systems are indicative for the soundness and reliability of the MinePath approach. In contrast with many pathway analysis tools, MinePath is a web-based system (www.minepath.org) offering dynamic and rich pathway visualization functionality, with the unique characteristic to color regulatory relations between genes and reveal their phenotype inclination. This unique characteristic makes MinePath a valuable tool for in silico molecular biology experimentation as it serves the biomedical researchers' exploratory needs to reveal and interpret the regulatory mechanisms that underlie and putatively govern the expression of target phenotypes.

Development of a ReaxFF reactive force field for ammonium nitrate and application to shock compression and thermal decomposition.

PubMed

Shan, Tzu-Ray; van Duin, Adri C T; Thompson, Aidan P

2014-02-27

We have developed a new ReaxFF reactive force field parametrization for ammonium nitrate. Starting with an existing nitramine/TATB ReaxFF parametrization, we optimized it to reproduce electronic structure calculations for dissociation barriers, heats of formation, and crystal structure properties of ammonium nitrate phases. We have used it to predict the isothermal pressure-volume curve and the unreacted principal Hugoniot states. The predicted isothermal pressure-volume curve for phase IV solid ammonium nitrate agreed with electronic structure calculations and experimental data within 10% error for the considered range of compression. The predicted unreacted principal Hugoniot states were approximately 17% stiffer than experimental measurements. We then simulated thermal decomposition during heating to 2500 K. Thermal decomposition pathways agreed with experimental findings.

A DFT study of ethanol adsorption and decomposition on α-Al2O3(0 0 0 1) surface

NASA Astrophysics Data System (ADS)

Chiang, Hsin-Ni; Nachimuthu, Santhanamoorthi; Cheng, Ya-Chin; Damayanti, Nur Pradani; Jiang, Jyh-Chiang

2016-02-01

Ethanol adsorption and decomposition on the clean α-Al2O3(0 0 0 1) surface have been systematically investigated by density functional theory calculations. The nature of the surface-ethanol bonding has studied through the density of states (DOS) and the electron density difference (EDD) contour plots. The DOS patterns confirm that the lone pair electrons of EtOH are involved in the formation of a surface Alsbnd O dative bond and the EDD plots provide evidences for the bond weakening/forming, which are consistent with the DOS analysis. Our ethanol decomposition results indicate that ethanol dehydration to ethylene (CH3CH2OH(a) → C2H4(g) + OH(a) + H(a)), is the main reaction pathway with the energy barrier of 1.46 eV. Although the cleavage of the hydroxyl group of ethanol has lower energy barrier, the further decomposition of ethoxy owns much higher energy barrier.

Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

DOE PAGES

Kelly, Thomas G.; Ren, Hui; Chen, Jingguang G.

2015-03-27

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC(0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to producemore » carbon monoxide and methane. In addition, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.« less

In Silico Alkaline Hydrolysis of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Density Functional Theory Investigation.

PubMed

Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Shukla, Manoj K; Okovytyy, Sergiy I; Hovorun, Dmytro; Leszczynski, Jerzy

2016-09-20

HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), an energetic material used in military applications, may be released to the environment during manufacturing, transportation, storage, training, and disposal. A detailed investigation of a possible mechanism of alkaline hydrolysis, as one of the most promising methods for HMX remediation, was performed by computational study at PCM(Pauling)/M06-2X/6-311++G(d,p) level. Obtained results suggest that HMX hydrolysis at pH 10 represents a highly exothermic multistep process involving initial deprotonation and nitrite elimination, hydroxide attachment accompanied by cycle cleavage, and further decomposition of cycle-opened intermediate to the products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of HMX hydrolysis such as nitrite, 4-nitro-2,4-diazabutanal, formaldehyde, nitrous oxide, formate, and ammonia correspond to experimentally observed species. Based on computed reaction pathways for HMX decomposition by alkaline hydrolysis, the kinetics of the entire process was modeled. Very low efficiency of this reaction at pH 10 was observed. Computations predict significant increases (orders of magnitude) of the hydrolysis rate for hydrolysis reactions undertaken at pH 11, 12, and 13.

Ab initio kinetics of gas phase decomposition reactions.

PubMed

Sharia, Onise; Kuklja, Maija M

2010-12-09

The thermal and kinetic aspects of gas phase decomposition reactions can be extremely complex due to a large number of parameters, a variety of possible intermediates, and an overlap in thermal decomposition traces. The experimental determination of the activation energies is particularly difficult when several possible reaction pathways coexist in the thermal decomposition. Ab initio calculations intended to provide an interpretation of the experiment are often of little help if they produce only the activation barriers and ignore the kinetics of the decomposition process. To overcome this ambiguity, a theoretical study of a complete picture of gas phase thermo-decomposition, including reaction energies, activation barriers, and reaction rates, is illustrated with the example of the β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) molecule by means of quantum-chemical calculations. We study three types of major decomposition reactions characteristic of nitramines: the HONO elimination, the NONO rearrangement, and the N-NO(2) homolysis. The reaction rates were determined using the conventional transition state theory for the HONO and NONO decompositions and the variational transition state theory for the N-NO(2) homolysis. Our calculations show that the HMX decomposition process is more complex than it was previously believed to be and is defined by a combination of reactions at any given temperature. At all temperatures, the direct N-NO(2) homolysis prevails with the activation barrier at 38.1 kcal/mol. The nitro-nitrite isomerization and the HONO elimination, with the activation barriers at 46.3 and 39.4 kcal/mol, respectively, are slow reactions at all temperatures. The obtained conclusions provide a consistent interpretation for the reported experimental data.

On the Reaction Mechanism of Acetaldehyde Decomposition on Mo(110)

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

Mei, Donghai; Karim, Ayman M.; Wang, Yong

2012-02-16

The strong Mo-O bond strength provides promising reactivity of Mo-based catalysts for the deoxygenation of biomass-derived oxygenates. Combining the novel dimer saddle point searching method with periodic spin-polarized density functional theory calculations, we investigated the reaction pathways of a acetaldehyde decomposition on the clean Mo(110) surface. Two reaction pathways were identified, a selective deoxygenation and a nonselective fragmentation pathways. We found that acetaldehyde preferentially adsorbs at the pseudo 3-fold hollow site in the η2(C,O) configuration on Mo(110). Among four possible bond (β-C-H, γ-C-H, C-O and C-C) cleavages, the initial decomposition of the adsorbed acetaldehyde produces either ethylidene via the C-Omore » bond scission or acetyl via the β-C-H bond scission while the C-C and the γ-C-H bond cleavages of acetaldehyde leading to the formation of methyl (and formyl) and formylmethyl are unlikely. Further dehydrogenations of ethylidene into either ethylidyne or vinyl are competing and very facile with low activation barriers of 0.24 and 0.31 eV, respectively. Concurrently, the formed acetyl would deoxygenate into ethylidyne via the C-O cleavage rather than breaking the C-C or the C-H bonds. The selective deoxygenation of acetaldehyde forming ethylene is inhibited by relatively weaker hydrogenation capability of the Mo(110) surface. Instead, the nonselective pathway via vinyl and vinylidene dehydrogenations to ethynyl as the final hydrocarbon fragment is kinetically favorable. On the other hand, the strong interaction between ethylene and the Mo(110) surface also leads to ethylene decomposition instead of desorption into the gas phase. This work was financially supported by the National Advanced Biofuels Consortium (NABC). Computing time was granted by a user project (emsl42292) at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). This work was financially supported by the National Advanced Biofuels Consortium (NABC). Computing time was granted by a user project (emsl42292) at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). The EMSL is a U.S. Department of Energy (DOE) national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and supported by the DOE Office of Biological and Environmental Research. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Management intensity alters decomposition via biological pathways

USGS Publications Warehouse

Wickings, Kyle; Grandy, A. Stuart; Reed, Sasha; Cleveland, Cory

2011-01-01

Current conceptual models predict that changes in plant litter chemistry during decomposition are primarily regulated by both initial litter chemistry and the stage-or extent-of mass loss. Far less is known about how variations in decomposer community structure (e.g., resulting from different ecosystem management types) could influence litter chemistry during decomposition. Given the recent agricultural intensification occurring globally and the importance of litter chemistry in regulating soil organic matter storage, our objectives were to determine the potential effects of agricultural management on plant litter chemistry and decomposition rates, and to investigate possible links between ecosystem management, litter chemistry and decomposition, and decomposer community composition and activity. We measured decomposition rates, changes in litter chemistry, extracellular enzyme activity, microarthropod communities, and bacterial versus fungal relative abundance in replicated conventional-till, no-till, and old field agricultural sites for both corn and grass litter. After one growing season, litter decomposition under conventional-till was 20% greater than in old field communities. However, decomposition rates in no-till were not significantly different from those in old field or conventional-till sites. After decomposition, grass residue in both conventional- and no-till systems was enriched in total polysaccharides relative to initial litter, while grass litter decomposed in old fields was enriched in nitrogen-bearing compounds and lipids. These differences corresponded with differences in decomposer communities, which also exhibited strong responses to both litter and management type. Overall, our results indicate that agricultural intensification can increase litter decomposition rates, alter decomposer communities, and influence litter chemistry in ways that could have important and long-term effects on soil organic matter dynamics. We suggest that future efforts to more accurately predict soil carbon dynamics under different management regimes may need to explicitly consider how changes in litter chemistry during decomposition are influenced by the specific metabolic capabilities of the extant decomposer communities.

Modeling diffusion control on organic matter decomposition in unsaturated soil pore space

NASA Astrophysics Data System (ADS)

Vogel, Laure; Pot, Valérie; Garnier, Patricia; Vieublé-Gonod, Laure; Nunan, Naoise; Raynaud, Xavier; Chenu, Claire

2014-05-01

Soil Organic Matter decomposition is affected by soil structure and water content, but field and laboratory studies about this issue conclude to highly variable outcomes. Variability could be explained by the discrepancy between the scale at which key processes occur and the measurements scale. We think that physical and biological interactions driving carbon transformation dynamics can be best understood at the pore scale. Because of the spatial disconnection between carbon sources and decomposers, the latter rely on nutrient transport unless they can actively move. In hydrostatic case, diffusion in soil pore space is thus thought to regulate biological activity. In unsaturated conditions, the heterogeneous distribution of water modifies diffusion pathways and rates, thus affects diffusion control on decomposition. Innovative imaging and modeling tools offer new means to address these effects. We have developed a new model based on the association between a 3D Lattice-Boltzmann Model and an adimensional decomposition module. We designed scenarios to study the impact of physical (geometry, saturation, decomposers position) and biological properties on decomposition. The model was applied on porous media with various morphologies. We selected three cubic images of 100 voxels side from µCT-scanned images of an undisturbed soil sample at 68µm resolution. We used LBM to perform phase separation and obtained water phase distributions at equilibrium for different saturation indices. We then simulated the diffusion of a simple soluble substrate (glucose) and its consumption by bacteria. The same mass of glucose was added as a pulse at the beginning of all simulations. Bacteria were placed in few voxels either regularly spaced or concentrated close to or far from the glucose source. We modulated physiological features of decomposers in order to weight them against abiotic conditions. We could evidence several effects creating unequal substrate access conditions for decomposers, hence inducing contrasted decomposition kinetics: position of bacteria relative to the substrate diffusion pathways, diffusion rate and hydraulic connectivity between bacteria and substrate source, local substrate enrichment due to restricted mass transfer. Physiological characteristics had a strong impact on decomposition only when glucose diffused easily but not when diffusion limitation prevailed. This suggests that carbon dynamics should not be considered to derive from decomposers' physiology alone but rather from the interactions of biological and physical processes at the microscale.

Ab initio molecular dynamics study on the initial chemical events in nitramines: thermal decomposition of CL-20.

PubMed

Isayev, Olexandr; Gorb, Leonid; Qasim, Mo; Leszczynski, Jerzy

2008-09-04

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane or HNIW) is a high-energy nitramine explosive. To improve atomistic understanding of the thermal decomposition of CL-20 gas and solid phases, we performed a series of ab initio molecular dynamics simulations. We found that during unimolecular decomposition, unlike other nitramines (e.g., RDX, HMX), CL-20 has only one distinct initial reaction channelhomolysis of the N-NO2 bond. We did not observe any HONO elimination reaction during unimolecular decomposition, whereas the ring-breaking reaction was followed by NO 2 fission. Therefore, in spite of limited sampling, that provides a mostly qualitative picture, we proposed here a scheme of unimolecular decomposition of CL-20. The averaged product population over all trajectories was estimated at four HCN, two to four NO2, two to four NO, one CO, and one OH molecule per one CL-20 molecule. Our simulations provide a detailed description of the chemical processes in the initial stages of thermal decomposition of condensed CL-20, allowing elucidation of key features of such processes as composition of primary reaction products, reaction timing, and Arrhenius behavior of the system. The primary reactions leading to NO2, NO, N 2O, and N2 occur at very early stages. We also estimated potential activation barriers for the formation of NO2, which essentially determines overall decomposition kinetics and effective rate constants for NO2 and N2. The calculated solid-phase decomposition pathways correlate with available condensed-phase experimental data.

Dissolved Organic Carbon and Disinfection By-Product Precursor Release from Managed Peat Soils

USGS Publications Warehouse

Fleck, J.A.; Bossio, D.A.; Fujii, R.

2004-01-01

A wetland restoration demonstration project examined the effects of a permanently flooded wetland on subsidence of peat soils. The project, started in 1997, was done on Twitchell Island, in the Sacramento-San Joaquin Delta of California. Conversion of agricultural land to a wetland has changed many of the biogeochemical processes controlling dissolved organic carbon (DOC) release from the peat soils, relative to the previous land use. Dissolved organic C in delta waters is a concern because it reacts with chlorine, added as a disinfectant in municipal drinking waters, to form carcinogenic disinfection byproducts (DBPs), including trihalomethanes (THMs) and haloacetic acids (HAAs). This study explores the effects of peat soil biogeochemistry on DOC and DBP release under agricultural and wetland management. Results indicate that organic matter source, extent of soil organic matter decomposition, and decomposition pathways all are factors in THM formation. The results show that historical management practices dominate the release of DOC and THM precursors. However, within-site differences indicate that recent management decisions can contribute to changes in DOC quality and THM precursor formation. Not all aromatic forms of carbon are highly reactive and certain environmental conditions produce the specific carbon structures that form THMs. Both HAA and THM precursors are elevated in the DOC released under wetland conditions. The findings of this study emphasize the need to further investigate the roles of organic matter sources, microbial decomposition pathways, and decomposition status of soil organic matter in the release of DOC and DBP precursors from delta soils under varying land-use practices.

Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

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

Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

2013-01-01

Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atomsmore » of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.« less

Probing the thermal stability and the decomposition mechanism of a magnesium-fullerene polymer via X-ray Raman spectroscopy, X-ray diffraction and molecular dynamics simulations.

PubMed

Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo

2016-02-21

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Micromorphological aspects of forensic geopedology: time-dependent markers of decomposition and permanence in soil in experimental burials

NASA Astrophysics Data System (ADS)

Zangarini, Sara; Cattaneo, Cristina; Trombino, Luca

2014-05-01

The importance of the role played by soil scientists grows up in the modern forensic sciences, in particular when buried human remains strongly decomposed or skeletonized are found in different environment situations. An interdisciplinary team, formed by earth and legal medicine researchers from the University of Milan is working on several sets of experimental burial of pigs in different soil types and for different times of burial, in order to get new evidences on environmental responses to the burial, focusing specifically on geopedological and micropedological aspects. The present work is aimed at the micromorphological (petrographic microscope) and ultramicroscopic (SEM) cross characterization of bone tissue in buried remains, in order to describe bone alteration pathways due both to decomposition and to permanence in soil. These methods allow identifying in the tissues of analysed bones: - Unusual concentrations of metal oxides (i.e. Fe, Mn), in the form of violet-blue colorations (in XPL), which seem to be related to chemical conditions in the burial area; their presence could be a method to discriminate permanence in soil rather than a different environment of decomposition. - Magnesium phosphate (i.e. Mg3(PO4)2 ) crystallizations, usually noticed in bones buried from 7 to 103 weeks; their presence seems to be related to the decomposition both of the bones themselves and of soft tissues. - The presence of significant sulphur levels (i.e. SO3) in bones buried for over 7 weeks, which seem to be related to the transport and fixation of soft tissues decomposition fluids. These results point out that micromorphological techniques coupled with spatially resolved chemical analyses allow identifying both indicators of the permanence of the remains into the soil (i.e. metal oxides concentrations) and time-dependent markers of decomposition (i.e. significant sulphur levels and magnesium phosphate) in order to determine PMI (post-mortem-interval) and TSB (time-since-burial). Further studies and new experiments are in progress in order to better clarify the bone alteration pathways on different skeletal districts and in different kind of soils.

Decomposition reactions of (hydroxyalkyl) nitrosoureas and related compounds: possible relationship to carcinogenicity.

PubMed

Singer, S S

1985-08-01

(Hydroxyalkyl)nitrosoureas and the related cyclic carbamates N-nitrosooxazolidones are potent carcinogens. The decompositions of four such compounds, 1-nitroso-1-(2-hydroxyethyl)urea (I), 3-nitrosooxazolid-2-one (II), 1-nitroso-1-(2-hydroxypropyl)urea (III), and 5-methyl-3-nitrosooxazolid-2-one (IV), in aqueous buffers at physiological pH were studied to determine if any obvious differences in decomposition pathways could account for the variety of tumors obtained from these four compounds. The products predicted by the literature mechanisms for nitrosourea and nitrosooxazolidone decompositions (which were derived from experiments at pH 10-12) were indeed the products formed, including glycols, active carbonyl compounds, epoxides, and, from the oxazolidones, cyclic carbonates. Furthermore, it was shown that in pH 6.4-7.4 buffer epoxides were stable reaction products. However, in the presence of hepatocytes, most of the epoxide was converted to glycol. The analytical methods developed were then applied to the analysis of the decomposition products of some related dialkylnitrosoureas, and similar results were obtained. The formation of chemically reactive secondary products and the possible relevance of these results to carcinogenesis studies are discussed.

Vacancy-induced initial decomposition of condensed phase NTO via bimolecular hydrogen transfer mechanisms at high pressure: a DFT-D study.

PubMed

Liu, Zhichao; Wu, Qiong; Zhu, Weihua; Xiao, Heming

2015-04-28

Density functional theory with dispersion-correction (DFT-D) was employed to study the effects of vacancy and pressure on the structure and initial decomposition of crystalline 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (β-NTO), a high-energy insensitive explosive. A comparative analysis of the chemical behaviors of NTO in the ideal bulk crystal and vacancy-containing crystals under applied hydrostatic compression was considered. Our calculated formation energy, vacancy interaction energy, electron density difference, and frontier orbitals reveal that the stability of NTO can be effectively manipulated by changing the molecular environment. Bimolecular hydrogen transfer is suggested to be a potential initial chemical reaction in the vacancy-containing NTO solid at 50 GPa, which is prior to the C-NO2 bond dissociation as its initiation decomposition in the gas phase. The vacancy defects introduced into the ideal bulk NTO crystal can produce a localized site, where the initiation decomposition is preferentially accelerated and then promotes further decompositions. Our results may shed some light on the influence of the molecular environments on the initial pathways in molecular explosives.

Study on microstructural changes in thermally-aged stainless steel weld-overlay cladding of nuclear reactor pressure vessels by atom probe tomography

NASA Astrophysics Data System (ADS)

Takeuchi, T.; Kameda, J.; Nagai, Y.; Toyama, T.; Nishiyama, Y.; Onizawa, K.

2011-08-01

The effect of thermal aging on microstructural changes was investigated in stainless steel weld-overlay cladding composed of 90% austenite and 10% δ-ferrite phases using atom probe tomography (APT). In as-received materials subjected to cooling process after post-welding heat treatments (PWHT), a slight fluctuation of the Cr concentration was already observed due to spinodal decomposition in the ferrite phase but not in the austenitic phase. Thermal aging at 400 °C for 10,000 h caused not only an increase in the amplitude of spinodal decomposition but also the precipitation of G phases with composition ratios of Ni:Si:Mn = 16:7:6 in the ferrite phase. The chemical compositions of M 23C 6 type carbides seemed to be formed at the austenite/ferrite interface were analyzed. The analyses of the magnitude of the spinodal decomposition and the hardness implied that the spinodal decomposition was the main cause of the hardening.

Effects of electron acceptors on soluble reactive phosphorus in the overlying water during algal decomposition.

PubMed

Wang, Jinzhi; Jiang, Xia; Zheng, Binghui; Niu, Yuan; Wang, Kun; Wang, Wenwen; Kardol, Paul

2015-12-01

Endogenous phosphorus (P) release from sediments is an important factor to cause eutrophication and, hence, algal bloom in lakes in China. Algal decomposition depletes dissolved oxygen (DO) and causes anaerobic conditions and therefore increases P release from sediments. As sediment P release is dependent on the iron (Fe) cycle, electron acceptors (e.g., NO3 (-), SO4 (2-), and Mn(4+)) can be utilized to suppress the reduction of Fe(3+) under anaerobic conditions and, as such, have the potential to impair the release of sediment P. Here, we used a laboratory experiment to test the effects of FeCl3, MnO2, and KNO3 on soluble reactive phosphorus (SRP) concentration and related chemical variables in the overlying water column during algal decomposition at different algal densities. Results showed that algal decomposition significantly depleted DO and thereby increased sediment Fe-bound P release. Compared with the control, addition of FeCl3 significantly decreased water SRP concentration through inhibiting sediment P release. Compared with FeCl3, addition of MnO2 has less potential to suppress sediment P release during algal decomposition. Algal decomposition has the potential for NO3 (-) removal from aquatic ecosystem through denitrification and by that alleviates the suppressing role of NO3 (-) on sediment P release. Our results indicated that FeCl3 and MnO2 could be efficient in reducing sediment P release during algal decomposition, with the strongest effect found for FeCl3; large amounts of NO3 (-) were removed from the aquatic ecosystem through denitrification during algal decomposition. Moreover, the amounts of NO3 (-) removal increased with increasing algal density.

Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

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

Dreger, Zbigniew A.; Tao, Yuchuan; Gupta, Yogendra M.

The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes placemore » along an isobar, whereas the α’-ε transition pressure decreases with increasing temperature, and (iv) melting/decomposition temperatures increase rapidly with pressure, with an increase in the slope at the onset of the α’-ε transition. Our results differ from the recently reported HP-HT phase diagram for nonhydrostatically compressed polycrystalline FOX-7. In addition, the observed interplay between melting and decomposition suggests the suppression of melting with pressure. Our FTIR measurements at different pressures to 3.5 GPa showed similar decomposition products, suggesting similar decomposition pathways irrespective of the pressure. Lastly, the present results provide new insights into the structural and chemical stability of an important insensitive high explosive (IHE) crystal under well-defined HP-HT conditions.« less

Phase diagram and decomposition of 1,1-diamino-2,2-dinitroethene single crystals at high pressures and temperatures

DOE PAGES

Dreger, Zbigniew A.; Tao, Yuchuan; Gupta, Yogendra M.

2016-05-10

The high pressure-high temperature (HP-HT) phase diagram and decomposition of FOX-7, central to understanding its stability and reactivity, were determined using optical spectroscopy and imaging measurements in hydrostatically compressed and heated single crystals. Boundaries between various FOX-7 phases (α, α’, β, γ, and ε) and melting/decomposition curves were established up to 10 GPa and 750 K. Main findings are: (i) a triple point is observed between α, β, and γ phases ~ 0.6 GPa and ~ 535 K, (ii) previously suggested δ phase is not a new phase but is partly decomposed γ phase, (iii) the α-α’ transition takes placemore » along an isobar, whereas the α’-ε transition pressure decreases with increasing temperature, and (iv) melting/decomposition temperatures increase rapidly with pressure, with an increase in the slope at the onset of the α’-ε transition. Our results differ from the recently reported HP-HT phase diagram for nonhydrostatically compressed polycrystalline FOX-7. In addition, the observed interplay between melting and decomposition suggests the suppression of melting with pressure. Our FTIR measurements at different pressures to 3.5 GPa showed similar decomposition products, suggesting similar decomposition pathways irrespective of the pressure. Lastly, the present results provide new insights into the structural and chemical stability of an important insensitive high explosive (IHE) crystal under well-defined HP-HT conditions.« less

Methanol decomposition reactions over a boron-doped graphene supported Ru-Pt catalyst.

PubMed

Damte, Jemal Yimer; Lyu, Shang-Lin; Leggesse, Ermias Girma; Jiang, Jyh Chiang

2018-04-04

The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.

Fungal-to-bacterial dominance of soil detrital food-webs: Consequences for biogeochemistry

NASA Astrophysics Data System (ADS)

Rousk, Johannes; Frey, Serita

2015-04-01

Resolving fungal and bacterial groups within the microbial decomposer community is thought to capture disparate microbial life strategies, associating bacteria with an r-selected strategy for carbon (C) and nutrient use, and fungi with a K-selected strategy. Additionally, food-web models have established a widely held belief that the bacterial decomposer pathway in soil supports high turnover rates of easily available substrates, while the slower fungal pathway supports the decomposition of more complex organic material, thus characterising the biogeochemistry of the ecosystem. Three field-experiments to generate gradients of SOC-quality were assessed. (1) the Detritus Input, Removal, and Trenching - DIRT - experiment in a temperate forest in mixed hardwood stands at Harvard Forest LTER, US. There, experimentally adjusted litter input and root input had affected the SOC quality during 23 years. (2) field-application of 14-C labelled glucose to grassland soils, sampled over the course of 13 months to generate an age-gradient of SOM (1 day - 13 months). (3) The Park Grass Experiment at Rothamsted, UK, where 150-years continuous N-fertilisation (0, 50, 100, 150 kg N ha-1 y-1) has affected the quality of SOM in grassland soils. A combination of carbon stable and radio isotope studies, fungal and bacterial growth and biomass measurements, and C and N mineralisation (15N pool dilution) assays were used to investigate how SOC-quality influenced fungal and bacterial food-web pathways and the implications this had for C and nutrient turnover. There was no support that decomposer food-webs dominated by bacteria support high turnover rates of easily available substrates, while slower fungal-dominated decomposition pathways support the decomposition of more complex organic material. Rather, an association between high quality SOC and fungi emerges from the results. This suggests that we need to revise our basic understanding for soil microbial communities and the processes they regulate in soil.

Jellyfish (Cyanea nozakii) decomposition and its potential influence on marine environments studied via simulation experiments.

PubMed

Qu, Chang-Feng; Song, Jin-Ming; Li, Ning; Li, Xue-Gang; Yuan, Hua-Mao; Duan, Li-Qin; Ma, Qing-Xia

2015-08-15

A growing body of evidence suggests that the jellyfish population in Chinese seas is increasing, and decomposition of jellyfish strongly influences the marine ecosystem. This study investigated the change in water quality during Cyanea nozakii decomposition using simulation experiments. The results demonstrated that the amount of dissolved nutrients released by jellyfish was greater than the amount of particulate nutrients. NH4(+) was predominant in the dissolved matter, whereas the particulate matter was dominated by organic nitrogen and inorganic phosphorus. The high N/P ratios demonstrated that jellyfish decomposition may result in high nitrogen loads. The inorganic nutrients released by C. nozakii decomposition were important for primary production. Jellyfish decomposition caused decreases in the pH and oxygen consumption associated with acidification and hypoxia or anoxia; however, sediments partially mitigated the changes in the pH and oxygen. These results imply that jellyfish decomposition can result in potentially detrimental effects on marine environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ab initio calculations of the effects of H+ and NH4+ on the initial decomposition of HMX.

PubMed

Wang, Luoxin; Tuo, Xinlin; Yi, Changhai; Wang, Xiaogong

2008-10-01

In this work, the effects of H(+) and NH(4)(+) on the initial decomposition of HMX were investigated on the basis of the B3P86/6-31G** and B3LYP/6-31G* calculations. Three initial decomposition pathways including the N-NO(2) bond fission, HONO elimination and C-N bond dissociation were considered for the complexes formed by HMX with H(+) (PHMX1 and PHMX2) or with NH(4)(+) (AHMX). We found that H(+) and NH(4)(+) did not evidently induce the HMX to trigger the N-NO(2) heterolysis because the energy barrier of N-NO(2) heterolysis was found to be higher than the bond dissociation energy of N-NO(2) homolytic cleavage. Meanwhile, the transition state barriers of the HONO elimination from the complexes were found to be similar to that from the isolated HMX, which means that the HONO elimination reaction of HMX was not affected by the H(+) and NH(4)(+). As for the ring-opening reaction of HMX due to the C-N bond dissociation, the calculated potential energy profile showed that the energy of the complex (AHMX) went uphill along the C-N bond length and no transition state existed on the curve. However, the transition state energy barriers of C-N bond dissociation were calculated to be only 5.0 kcal/mol and 5.5 kcal/mol for the PHMX1 and PHMX2 complexes, respectively, which were much lower than the C-N bond dissociation energy of isolated HMX. Moreover, among the three initial decomposition reactions, the C-N bond dissociation was also the most energetically favorable pathway for the PHMX1 and PHMX2. Our calculation results showed that the H(+) can significantly promote the initial thermal decomposition of C-N bond of HMX, which, however, is influenced by NH(4)(+) slightly.

Factors controlling the abiotic photo-degradation of monomethylmercury in surface waters

NASA Astrophysics Data System (ADS)

Black, Frank J.; Poulin, Brett A.; Flegal, A. Russell

2012-05-01

Photo-decomposition is among the most important mechanisms responsible for degrading monomethylmercury (MMHg) in aquatic systems, but this process is not fully understood. We investigated the relative importance of different factors in controlling the rate of MMHg photo-decomposition in surface waters in experiments using DOM isolated from natural waters. We found no evidence of net abiotic production of MMHg in any dark or light exposed treatments. The average (mean ± s.d.) MMHg photo-decomposition rate constant for all light exposed samples using DOM concentrated from three coastal wetlands was 0.0099 ± 0.0020 E-1m2 (range of 0.006-0.015 E-1m2) when expressed in photon flux from 330-700 nm. This was roughly 3-fold higher than the average MMHg photo-decomposition rate constant in coastal seawater of 0.0032 ± 0.0010 E-1m2. MMHg photo-degradation was highly wavelength dependent. The ratio of MMHg photo-decomposition rate constants, with respect to photon flux, was 400:37:1 for UVB:UVA:PAR. However, when integrated across the entire water column over which MMHg photo-demethylation occurs, PAR was responsible for photo-degrading more MMHg than UVB and UVA combined in the three wetland sites because of the more rapid attenuation of UV light with depth. MMHg half-lives in the wetlands were calculated for the upper 250 cm where photo-degradation occurred, and ranged from 7.6 to 20 days under typical summer sunlight conditions at 37°N. Rates of MMHg photo-decomposition decreased with increasing salinity, and were 27% higher at a salinity of 5 than those at a salinity of 25. This difference could not be accounted for by changes in the complexation of MMHg by DOM and chloride. Differences in MMHg photo-degradation rate constants of up to 18% were measured between treatments using DOM concentrated from three different wetlands. Surprisingly, increasing DOM concentration from 1.5 to 11.3 mg OC L-1 had only a small (6%) effect on MMHg photo-decomposition, which was much smaller than the 34% decrease predicted due to the attenuation of light at the higher DOM levels. This suggests that DOM plays an important role in MMHg photo-decomposition apart from mediating light levels and MMHg complexation. Experiments employing various scavengers implied that singlet oxygen and hydroxyl radicals were not involved in the photo-degradation of MMHg in the natural waters used. Varying concentrations of Fe, Cu, and Mn had only small (⩽11%) effects on rates of MMHg photo-decomposition, and relatively high rates were measured in high purity water with no trace metals or DOM. These results demonstrate that MMHg photo-decomposition can occur via pathways not involving Fe, the photo-Fenton reaction, nitrate photolysis, or thiol complexation. Taken with previous studies, multiple reaction pathways appear to exist, and their importance varies as a function of water chemistry and light wavelength.

Decomposition rate of Rhizopora stylosa litter in Tanjung Rejo Village, Deli Serdang Regency, North Sumatera Province

NASA Astrophysics Data System (ADS)

Rambey, R.; Delvian; Sianturi, S. D.

2018-02-01

Research on the decomposition rate of Rhizopora stylosa litter in Tanjung Rejo village, Deli Serdang Regency, North Sumatera Province was conducted from September 2016 to May 2017. The objectives of this research were (1) to measure the decomposition rate of Rhizophora stylosa litter and (2) to determine the type of functional fungi in decomposition of litter. R. stylosa litter decomposition is characterized by a reduction in litter weight per observation period. Decomposition rate tended to increase every week, which was from 0.238 in the seventh day and reached 0.302 on the fiftysixthth day. The decomposition rate of R. stylosa litter of leaf was high with the value of k per day > 0,01 caused by macrobentos and fungi, and also the decomposition of R. stylosa litter conducted in the pond area which is classified far from the coast. Therefore, to enable the high population of fungi which affect the decomposition rate of the litter. The types of fungi decomposers were: Aspergillus sp.-1, Aspergillus sp.-2, Aspergillus sp.-3, Rhizophus sp.-1., Rhizophus sp.-2, Penicillium sp., Syncephalastrum sp. and Fusarium sp.

Potential role of gas hydrate decomposition in generating submarine slope failures: Chapter 12

USGS Publications Warehouse

Pauli, Charles K.; Ussler, William III; Dillon, William P.; Max, Michael D.

2003-01-01

Gas hydrate decomposition is hypothesized to be a factor in generating weakness in continental margin sediments that may help explain some of the observed patterns of continental margin sediment instability. The processes associated with formation and decomposition of gas hydrate can cause the strengthening of sediments in which gas hydrate grow and the weakening of sediments in which gas hydrate decomposes. The weakened sediments may form horizons along which the potential for sediment failure is increased. While a causal relationship between slope failures and gas hydrate decomposition has not been proven, a number of empirical observations support their potential connection.

A vacuum ultraviolet photoionization study on the thermal decomposition of ammonium perchlorate

DOE PAGES

Gobi, Sandor; Zhao, Long; Xu, Bo; ...

2017-11-14

Pyrolysis products of ammonium perchlorate (NH 4ClO 4) at 483 K were monitored on line and in situ via single photon photoionization reflectron time-of-flight spectrometry (PI-ReTOF-MS) in the photon energy range of 9.00–17.50 eV. The photoionization efficiency curves (PIE) of the subliming product molecules were collected and allowed for detection of three class of products containing chlorine, nitrogen, and oxygen including atoms and free radicals. The results found suggest a new insight into possible low-temperature decomposition pathways of NH 4ClO 4.

A vacuum ultraviolet photoionization study on the thermal decomposition of ammonium perchlorate

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

Gobi, Sandor; Zhao, Long; Xu, Bo

Pyrolysis products of ammonium perchlorate (NH 4ClO 4) at 483 K were monitored on line and in situ via single photon photoionization reflectron time-of-flight spectrometry (PI-ReTOF-MS) in the photon energy range of 9.00–17.50 eV. The photoionization efficiency curves (PIE) of the subliming product molecules were collected and allowed for detection of three class of products containing chlorine, nitrogen, and oxygen including atoms and free radicals. The results found suggest a new insight into possible low-temperature decomposition pathways of NH 4ClO 4.

A vacuum ultraviolet photoionization study on the thermal decomposition of ammonium perchlorate

NASA Astrophysics Data System (ADS)

Góbi, Sándor; Zhao, Long; Xu, Bo; Ablikim, Utuq; Ahmed, Musahid; Kaiser, Ralf I.

2018-01-01

Pyrolysis products of ammonium perchlorate (NH4ClO4) at 483 K were monitored on line and in situ via single photon photoionization reflectron time-of-flight spectrometry (PI-ReTOF-MS) in the photon energy range of 9.00-17.50 eV. The photoionization efficiency curves (PIE) of the subliming product molecules were collected and allowed for detection of three class of products containing chlorine, nitrogen, and oxygen including atoms and free radicals. These results suggest a new insight into possible low-temperature decomposition pathways of NH4ClO4.

Mode Analyses of Gyrokinetic Simulations of Plasma Microturbulence

NASA Astrophysics Data System (ADS)

Hatch, David R.

This thesis presents analysis of the excitation and role of damped modes in gyrokinetic simulations of plasma microturbulence. In order to address this question, mode decompositions are used to analyze gyrokinetic simulation data. A mode decomposition can be constructed by projecting a nonlinearly evolved gyrokinetic distribution function onto a set of linear eigenmodes, or alternatively by constructing a proper orthogonal decomposition of the distribution function. POD decompositions are used to examine the role of damped modes in saturating ion temperature gradient driven turbulence. In order to identify the contribution of different modes to the energy sources and sinks, numerical diagnostics for a gyrokinetic energy quantity were developed for the GENE code. The use of these energy diagnostics in conjunction with POD mode decompositions demonstrates that ITG turbulence saturates largely through dissipation by damped modes at the same perpendicular spatial scales as those of the driving instabilities. This defines a picture of turbulent saturation that is very different from both traditional hydrodynamic scenarios and also many common theories for the saturation of plasma turbulence. POD mode decompositions are also used to examine the role of subdominant modes in causing magnetic stochasticity in electromagnetic gyrokinetic simulations. It is shown that the magnetic stochasticity, which appears to be ubiquitous in electromagnetic microturbulence, is caused largely by subdominant modes with tearing parity. The application of higher-order singular value decomposition (HOSVD) to the full distribution function from gyrokinetic simulations is presented. This is an effort to demonstrate the ability to characterize and extract insight from a very large, complex, and high-dimensional data-set - the 5-D (plus time) gyrokinetic distribution function.

Effects of water flow regulation on ecosystem functioning in a Mediterranean river network assessed by wood decomposition.

PubMed

Abril, Meritxell; Muñoz, Isabel; Casas-Ruiz, Joan P; Gómez-Gener, Lluís; Barceló, Milagros; Oliva, Francesc; Menéndez, Margarita

2015-06-01

Mediterranean rivers are extensively modified by flow regulation practises along their courses. An important part of the river impoundment in this area is related to the presence of small dams constructed mainly for water abstraction purposes. These projects drastically modified the ecosystem morphology, transforming lotic into lentic reaches and increasing their alternation along the river. Hydro-morphologial differences between these reaches indicate that flow regulation can trigger important changes in the ecosystem functioning. Decomposition of organic matter is an integrative process and this complexity makes it a good indicator of changes in the ecosystem. The aim of this study was to assess the effect caused by flow regulation on ecosystem functioning at the river network scale, using wood decomposition as a functional indicator. We studied the mass loss from wood sticks during three months in different lotic and lentic reaches located along a Mediterranean river basin, in both winter and summer. Additionally, we identified the environmental factors affecting decomposition rates along the river orders. The results revealed differences in decomposition rates between sites in both seasons that were principally related to the differences between stream orders. The rates were mainly related to temperature, nutrient concentrations (NO2(-), NO3(2-)) and water residence time. High-order streams with higher temperature and nutrient concentrations exhibited higher decomposition rates compared with low-order streams. The effect of the flow regulation on the decomposition rates only appeared to be significant in high orders, especially in winter, when the hydrological characteristics of lotic and lentic habitats widely varied. Lotic reaches with lower water residence time exhibited greater decomposition rates compared with lentic reaches probably due to more physical abrasion and differences in the microbial assemblages. Overall, our study revealed that in high orders the reduction of flow caused by flow regulation affects the wood decomposition indicating changes in ecosystem functioning. Copyright © 2015 Elsevier B.V. All rights reserved.

What Role Does Photodegradation Play in Influencing Plant Litter Decomposition and Biogeochemistry in Coastal Marsh Ecosystems?

NASA Astrophysics Data System (ADS)

Tobler, M.; White, D. A.; Abbene, M. L.; Burst, S. L.; McCulley, R. L.; Barnes, P. W.

2016-02-01

Decomposition is a crucial component of global biogeochemical cycles that influences the fate and residence time of carbon and nutrients in organic matter pools, yet the processes controlling litter decomposition in coastal marshes are not fully understood. We conducted a series of field studies to examine what role photodegradation, a process driven in part by solar UV radiation (280-400 nm), plays in the decomposition of the standing dead litter of Sagittaria lancifolia and Spartina patens, two common species in marshes of intermediate salinity in southern Louisiana, USA. Results indicate that the exclusion of solar UV significantly altered litter mass loss, but the magnitude and direction of these effects varied depending on species, height of the litter above the water surface and the stage of decomposition. Over one growing season, S. lancifolia litter exposed to ambient solar UV had significantly less mass loss compared to litter exposed to attenuated UV over the initial phase of decomposition (0-5 months; ANOVA P=0.004) then treatment effects switched in the latter phase of the study (5-7 months; ANOVA P<0.001). Similar results were found in S. patens over an 11-month period. UV exposure reduced total C, N and lignin by 24-33% in remaining tissue with treatment differences most pronounced in S. patens. Phospholipid fatty-acid analysis (PFLA) indicated that UV also significantly altered microbial (bacterial) biomass and bacteria:fungi ratios of decomposing litter. These findings, and others, indicate that solar UV can have positive and negative net effects on litter decomposition in marsh plants with inhibition of biotic (microbial) processes occurring early in the decomposition process then shifting to enhancement of decomposition via abiotic (photodegradation) processes later in decomposition. Photodegradation of standing litter represents a potentially significant pathway of C and N loss from these coastal wetland ecosystems.

Multivariate modelling of endophenotypes associated with the metabolic syndrome in Chinese twins.

PubMed

Pang, Z; Zhang, D; Li, S; Duan, H; Hjelmborg, J; Kruse, T A; Kyvik, K O; Christensen, K; Tan, Q

2010-12-01

The common genetic and environmental effects on endophenotypes related to the metabolic syndrome have been investigated using bivariate and multivariate twin models. This paper extends the pairwise analysis approach by introducing independent and common pathway models to Chinese twin data. The aim was to explore the common genetic architecture in the development of these phenotypes in the Chinese population. Three multivariate models including the full saturated Cholesky decomposition model, the common factor independent pathway model and the common factor common pathway model were fitted to 695 pairs of Chinese twins representing six phenotypes including BMI, total cholesterol, total triacylglycerol, fasting glucose, HDL and LDL. Performances of the nested models were compared with that of the full Cholesky model. Cross-phenotype correlation coefficients gave clear indication of common genetic or environmental backgrounds in the phenotypes. Decomposition of phenotypic correlation by the Cholesky model revealed that the observed phenotypic correlation among lipid phenotypes had genetic and unique environmental backgrounds. Both pathway models suggest a common genetic architecture for lipid phenotypes, which is distinct from that of the non-lipid phenotypes. The declining performance with model restriction indicates biological heterogeneity in development among some of these phenotypes. Our multivariate analyses revealed common genetic and environmental backgrounds for the studied lipid phenotypes in Chinese twins. Model performance showed that physiologically distinct endophenotypes may follow different genetic regulations.

In situ carbon turnover dynamics and the role of soil microorganisms therein: a climate warming study in an Alpine ecosystem.

PubMed

Djukic, Ika; Zehetner, Franz; Watzinger, Andrea; Horacek, Micha; Gerzabek, Martin H

2013-01-01

Litter decomposition represents one of the largest fluxes in the global terrestrial carbon cycle. The aim of this study was to improve our understanding of the factors governing decomposition in alpine ecosystems and how their responses to changing environmental conditions change over time. Our study area stretches over an elevation gradient of 1000 m on the Hochschwab massif in the Northern Limestone Alps of Austria. We used high-to-low elevation soil translocation to simulate the combined effects of changing climatic conditions, shifting vegetation zones, and altered snow cover regimes. In original and translocated soils, we conducted in situ decomposition experiments with maize litter and studied carbon turnover dynamics as well as temporal response patterns of the pathways of carbon during microbial decomposition over a 2-year incubation period. A simulated mean annual soil warming (through down-slope translocation) of 1.5 and 2.7 °C, respectively, resulted in a significantly accelerated turnover of added maize carbon. Changes in substrate quantity and quality in the course of the decomposition appeared to have less influence on the microbial community composition and its substrate utilization than the prevailing environmental/site conditions, to which the microbial community adapted quickly upon change. In general, microbial community composition and function significantly affected substrate decomposition rates only in the later stage of decomposition when the differentiation in substrate use among the microbial groups became more evident. Our study demonstrated that rising temperatures in alpine ecosystems may accelerate decomposition of litter carbon and also lead to a rapid adaptation of the microbial communities to the new environmental conditions. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Experimental study of decomposition of aqueous nitrosyl thiocyanate.

PubMed

Rayson, Mark S; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-08-15

This study has examined the kinetics of the decomposition of nitrosyl thiocyanate (ONSCN) by stopped flow UV-vis spectrophotometry, with the reaction products identified and quantified by infrared spectroscopy, membrane inlet mass spectrometry, ion chromatography, and CN(-) ion selective electrode. The reaction results in the formation of nitric oxide and thiocyanogen, the latter decomposing to sulfate and hydrogen cyanide in aqueous solution. The rate of consumption of ONSCN depends strongly on the concentration of SCN(-) ions and is inhibited by nitric oxide. We have developed a reaction mechanism that comprises three parallel pathways for the decomposition of ONSCN. At high thiocyanate concentrations, two reaction pathways operate including a second order reaction to generate NO and (SCN)(2) and a reversible reaction between ONSCN and SCN(-) producing NO and (SCN)(2)(-), with the rate limiting step corresponding to the consumption of (SCN)(2)(-) by reaction with ONSCN. The third reaction pathway, which becomes significant at low thiocyanate concentrations, involves formation of a previously unreported species, ONOSCN, via a reaction between ONSCN and HOSCN, the latter constituting an intermediate in the hydrolysis of (SCN)(2). ONOSCN contributes to the formation of NO via homolysis of the O-NO bond and subsequent dimerization and hydrolysis of OSCN. Fitting the chemical reactions of the model to the experimental measurements, which covered a wide range of reactant concentrations, afforded estimation of all relevant kinetic parameters and provided an excellent match. The reaction mechanism developed in this contribution may be applied to predict the rates of NO formation from ONSCN during the synthesis of azo dyes, the gassing of explosive emulsions, or nitrosation reactions occurring in the human body. © 2011 American Chemical Society

Initial decomposition of the condensed-phase β-HMX under shock waves: molecular dynamics simulations.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Ji, Guang-Fu; Chen, Xiang-Rong; Zhao, Feng; Wei, Dong-Qing

2012-11-26

We have performed quantum-based multiscale simulations to study the initial chemical processes of condensed-phase octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) under shock wave loading. A self-consistent charge density-functional tight-binding (SCC-DFTB) method was employed. The results show that the initial decomposition of shocked HMX is triggered by the N-NO(2) bond breaking under the low velocity impact (8 km/s). As the shock velocity increases (11 km/s), the homolytic cleavage of the N-NO(2) bond is suppressed under high pressure, the C-H bond dissociation becomes the primary pathway for HMX decomposition in its early stages. It is accompanied by a five-membered ring formation and hydrogen transfer from the CH(2) group to the -NO(2) group. Our simulations suggest that the initial chemical processes of shocked HMX are dependent on the impact velocity, which gain new insights into the initial decomposition mechanism of HMX upon shock loading at the atomistic level, and have important implications for understanding and development of energetic materials.

Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation.

PubMed

Pfeifle, Mark; Ma, Yong-Tao; Jasper, Ahren W; Harding, Lawrence B; Hase, William L; Klippenstein, Stephen J

2018-05-07

Ozonolysis produces chemically activated carbonyl oxides (Criegee intermediates, CIs) that are either stabilized or decompose directly. This branching has an important impact on atmospheric chemistry. Prior theoretical studies have employed statistical models for energy partitioning to the CI arising from dissociation of the initially formed primary ozonide (POZ). Here, we used direct dynamics simulations to explore this partitioning for decomposition of c-C 2 H 4 O 3 , the POZ in ethylene ozonolysis. A priori estimates for the overall stabilization probability were then obtained by coupling the direct dynamics results with master equation simulations. Trajectories were initiated at the concerted cycloreversion transition state, as well as the second transition state of a stepwise dissociation pathway, both leading to a CI (H 2 COO) and formaldehyde (H 2 CO). The resulting CI energy distributions were incorporated in master equation simulations of CI decomposition to obtain channel-specific stabilized CI (sCI) yields. Master equation simulations of POZ formation and decomposition, based on new high-level electronic structure calculations, were used to predict yields for the different POZ decomposition channels. A non-negligible contribution of stepwise POZ dissociation was found, and new mechanistic aspects of this pathway were elucidated. By combining the trajectory-based channel-specific sCI yields with the channel branching fractions, an overall sCI yield of (48 ± 5)% was obtained. Non-statistical energy release was shown to measurably affect sCI formation, with statistical models predicting significantly lower overall sCI yields (∼30%). Within the range of experimental literature values (35%-54%), our trajectory-based calculations favor those clustered at the upper end of the spectrum.

Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation

NASA Astrophysics Data System (ADS)

Pfeifle, Mark; Ma, Yong-Tao; Jasper, Ahren W.; Harding, Lawrence B.; Hase, William L.; Klippenstein, Stephen J.

2018-05-01

Ozonolysis produces chemically activated carbonyl oxides (Criegee intermediates, CIs) that are either stabilized or decompose directly. This branching has an important impact on atmospheric chemistry. Prior theoretical studies have employed statistical models for energy partitioning to the CI arising from dissociation of the initially formed primary ozonide (POZ). Here, we used direct dynamics simulations to explore this partitioning for decomposition of c-C2H4O3, the POZ in ethylene ozonolysis. A priori estimates for the overall stabilization probability were then obtained by coupling the direct dynamics results with master equation simulations. Trajectories were initiated at the concerted cycloreversion transition state, as well as the second transition state of a stepwise dissociation pathway, both leading to a CI (H2COO) and formaldehyde (H2CO). The resulting CI energy distributions were incorporated in master equation simulations of CI decomposition to obtain channel-specific stabilized CI (sCI) yields. Master equation simulations of POZ formation and decomposition, based on new high-level electronic structure calculations, were used to predict yields for the different POZ decomposition channels. A non-negligible contribution of stepwise POZ dissociation was found, and new mechanistic aspects of this pathway were elucidated. By combining the trajectory-based channel-specific sCI yields with the channel branching fractions, an overall sCI yield of (48 ± 5)% was obtained. Non-statistical energy release was shown to measurably affect sCI formation, with statistical models predicting significantly lower overall sCI yields (˜30%). Within the range of experimental literature values (35%-54%), our trajectory-based calculations favor those clustered at the upper end of the spectrum.

SURFACTANT TEMPLATED SOL-GEL SYNTHESIS OF MESOPOROUS TIO2 PHOTOCATALYSTS AND THEIR APPLICATION IN THE DESTRUCTION OF CYANOBACTERIAL TOXINS

EPA Science Inventory

In the symposium, we will present the synthesis and properties of the mesoporous TIO₂ films and membranes and fundamental and systematic study on the decomposition pathway of such biological toxins.

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

Antonov, Ivan O.; Zador, Judit; Rotavera, Brandon

Here, we report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10–2000 Torr and T = 400–700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O 2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO 2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely ofmore » central importance in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O 2 and QOOH + O 2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH.« less

Gaseous species as reaction tracers in the solvothermal synthesis of the zinc oxide terephthalate MOF-5.

PubMed

Hausdorf, Steffen; Baitalow, Felix; Seidel, Jürgen; Mertens, Florian O R L

2007-05-24

Gaseous species emitted during the zinc oxide/zinc hydroxide 1,4-benzenedicarboxylate metal organic framework synthesis (MOF-5, MOF-69c) have been used to investigate the reaction scheme that leads to the framework creation. Changes of the gas-phase composition over time indicate that the decomposition of the solvent diethylformamide occurs at least via two competing reaction pathways that can be linked to the reaction's overall water and pH management. From isotope exchange experiments, we deduce that one of the decomposition pathways leads to the removal of water from the reaction mixture, which sets the conditions when the synthesis of an oxide-based (MOF-5) instead of an hydroxide-based MOF (MOF-69c) occurs. A quantitative account of most reactants and byproducts before and after the MOF-5/MOF-69c synthesis is presented. From the investigation of the reaction intermediates and byproducts, we derive a proposal of a basic reaction scheme for the standard synthesis zinc oxide carboxylate MOFs.

Thermal decomposition pathway of undoped and doped zinc layered gallate nanohybrid with Fe 3+, Co 2+ and Ni 2+ to produce mesoporous and high pore volume carbon material

NASA Astrophysics Data System (ADS)

Ghotbi, Mohammad Yeganeh; bin Hussein, Mohd Zobir; Yahaya, Asmah Hj; Abd Rahman, Mohd Zaki

2009-12-01

A series of brucite-like materials, undoped and doped zinc layered hydroxide nitrate with 2% (molar) Fe 3+, Co 2+ and Ni 2+ were synthesized. Organic-inorganic nanohybrid material with gallate anion as a guest, and zinc hydroxide nitrate, as an inorganic layered host was prepared by the ion-exchange method. The nanohybrid materials were heat-treated at various temperatures, 400-700 °C. X-ray diffraction, thermal analysis and also Fourier transform infrared results showed that incorporation of the doping agents within the zinc layered hydroxide salt layers has enhanced the heat-resistivity of the nanohybrid materials in the thermal decomposition pathway. Porous carbon materials can be obtained from the heat-treating the nanohybrids at 600 and 700 °C. Calcination of the nanohybrids at 700 °C under nitrogen atmosphere produces mesoporous and high pore volume carbon materials.

Stability of nicotinate and dodecyl sulfate in a Lewis acidic ionic liquid for aluminum electroplating and characterization of their degradation products.

PubMed

Kosmus, Patrick; Steiner, Oliver; Goessler, Walter; Gollas, Bernhard; Fauler, Gisela

2016-04-01

Plating bath additives are essential for optimization of the morphology of electroplated layers. The ionic liquid 1-ethyl-3-methylimidazolium (EMIM) chloride plus 1.5 mol equivalents of AlCl3 has great potential for electroplating of aluminum. In this study, the chemical and electrochemical stability of the additives EMIM-nicotinate and sodium dodecyl sulfate and their effect on the stability of EMIM was investigated and analyzed. Nicotinate and its electrochemical decomposition product β-picoline could be detected and we show with a single HPLC-UV-MS method that EMIM is not affected by the decomposition of this additive. An adapted standard HPLC-UV-MS method together with GC-MS and ion chromatography was used to analyze the decomposition products of SDS and possible realkylation products of EMIM. Several volatile medium and short chain-length alkanes as well as sulfate ions have been found as decomposition products of SDS. Alkenium ions formed as intermediates during the decomposition of SDS realkylate EMIM to produce mono- up to pentasubstituted alkyl-imidazoles. A reaction pathway involving Wagner-Meerwein rearrangements and Friedel-Crafts alkylations has been suggested to account for the formation of the detected products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal decomposition of the amino acids glycine, cysteine, aspartic acid, asparagine, glutamic acid, glutamine, arginine and histidine.

PubMed

Weiss, Ingrid M; Muth, Christina; Drumm, Robert; Kirchner, Helmut O K

2018-01-01

The pathways of thermal instability of amino acids have been unknown. New mass spectrometric data allow unequivocal quantitative identification of the decomposition products. Calorimetry, thermogravimetry and mass spectrometry were used to follow the thermal decomposition of the eight amino acids G, C, D, N, E, Q, R and H between 185 °C and 280 °C. Endothermic heats of decomposition between 72 and 151 kJ/mol are needed to form 12 to 70% volatile products. This process is neither melting nor sublimation. With exception of cysteine they emit mainly H 2 O, some NH 3 and no CO 2 . Cysteine produces CO 2 and little else. The reactions are described by polynomials, AA→ a NH 3 + b H 2 O+ c CO 2 + d H 2 S+ e residue, with integer or half integer coefficients. The solid monomolecular residues are rich in peptide bonds. Eight of the 20 standard amino acids decompose at well-defined, characteristic temperatures, in contrast to commonly accepted knowledge. Products of decomposition are simple. The novel quantitative results emphasize the impact of water and cyclic condensates with peptide bonds and put constraints on hypotheses of the origin, state and stability of amino acids in the range between 200 °C and 300 °C.

Functional evaluation of pollutant transformation in sediment from combined sewer system.

PubMed

Shi, Xuan; Ngo, Huu Hao; Sang, Langtao; Jin, Pengkang; Wang, Xiaochang C; Wang, Guanghua

2018-07-01

In this study, a pilot combined sewer system was constructed to characterize the pollutant transformation in sewer sediment. The results showed that particulate contaminants deposited from sewage could be transformed into dissolved matter by distinct pollutant transformation pathways. Although the oxidation-reduction potential (ORP) was varied from -80 mV to -340 mV in different region of the sediment, the fermentation was the dominant process in all regions of the sediment, which induced hydrolysis and decomposition of particulate contaminants. As a result, the accumulation of dissolved organic matter and the variation of ORP values along the sediment depth led to the depth-dependent reproduction characteristics of methanogens and sulfate-reducing bacteria, which were existed in the middle and deep layer of the sediment respectively. However, the diversity of nitrifying and polyphosphate-accumulating bacteria was low in sewer sediment and those microbial communities showed a non-significant correlation with nitrogen and phosphorus contaminants, which indicated that the enrichment of nitrogen and phosphorus contaminants was mainly caused by physical deposition process. Thus, this study proposed a promising pathway to evaluate pollutant transformation and can help provide theoretical foundation for urban sewer improvement. Copyright © 2018 Elsevier Ltd. All rights reserved.

Soil Properties, Nutrient Dynamics, and Soil Enzyme Activities Associated with Garlic Stalk Decomposition under Various Conditions

PubMed Central

Han, Xu; Cheng, Zhihui; Meng, Huanwen

2012-01-01

The garlic stalk is a byproduct of garlic production and normally abandoned or burned, both of which cause environmental pollution. It is therefore appropriate to determine the conditions of efficient decomposition, and equally appropriate to determine the impact of this decomposition on soil properties. In this study, the soil properties, enzyme activities and nutrient dynamics associated with the decomposition of garlic stalk at different temperatures, concentrations and durations were investigated. Stalk decomposition significantly increased the values of soil pH and electrical conductivity. In addition, total nitrogen and organic carbon concentration were significantly increased by decomposing stalks at 40°C, with a 5∶100 ratio and for 10 or 60 days. The highest activities of sucrase, urease and alkaline phosphatase in soil were detected when stalk decomposition was performed at the lowest temperature (10°C), highest concentration (5∶100), and shortest duration (10 or 20 days). The evidence presented here suggests that garlic stalk decomposition improves the quality of soil by altering the value of soil pH and electrical conductivity and by changing nutrient dynamics and soil enzyme activity, compared to the soil decomposition without garlic stalks. PMID:23226411

Detection of decomposition volatile organic compounds in soil following removal of remains from a surface deposition site.

PubMed

Perrault, Katelynn A; Stefanuto, Pierre-Hugues; Stuart, Barbara H; Rai, Tapan; Focant, Jean-François; Forbes, Shari L

2015-09-01

Cadaver-detection dogs use volatile organic compounds (VOCs) to search for human remains including those deposited on or beneath soil. Soil can act as a sink for VOCs, causing loading of decomposition VOCs in the soil following soft tissue decomposition. The objective of this study was to chemically profile decomposition VOCs from surface decomposition sites after remains were removed from their primary location. Pig carcasses were used as human analogues and were deposited on a soil surface to decompose for 3 months. The remains were then removed from each site and VOCs were collected from the soil for 7 months thereafter and analyzed by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS). Decomposition VOCs diminished within 6 weeks and hydrocarbons were the most persistent compound class. Decomposition VOCs could still be detected in the soil after 7 months using Principal Component Analysis. This study demonstrated that the decomposition VOC profile, while detectable by GC×GC-TOFMS in the soil, was considerably reduced and altered in composition upon removal of remains. Chemical reference data is provided by this study for future investigations of canine alert behavior in scenarios involving scattered or scavenged remains.

Theoretical Study of Decomposition Pathways for HArF and HKrF

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Donchan (Technical Monitor)

2002-01-01

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Acid-catalyzed oxidation of 2,4-dichlorophenoxyacetic acid by ammonium nitrate in aqueous solution

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

Leavitt, D.D.; Abraham, M.A.

1990-04-01

2,4-Dichlorophenoxyacetic acid (2,4-D) was oxidized to CO{sub 2} and water by homogeneous, liquid-phase reaction with ammonium nitrate at temperatures between 250 and 450{degree}F and pressures below 100 psi. N{sub 2} and N{sub 2}O were produced from the thermal decomposition of the ammonium nitrate oxidant. An unexpected maximum in conversion was observed at an intermediate reaction temperature, which was consistent with rapid thermal decomposition of the NH{sub 4}NO{sub 3} oxidant. Postulated reaction pathways consisting of simultaneous oxidation of 2,4-D and decomposition of the oxidant allowed estimation of kinetic constants from best-fit analysis of the data. The proposed reaction model provided amore » mathematical description of 2,4-D conversion, which allowed extrapolation of the results to reaction conditions and reactor configurations that were not experimentally investigated.« less

Increased site fertility and litter decomposition rate in high-pollution sites in the San Bernardino Mountains

Treesearch

Mark E. Fenn

1991-01-01

Some possible factors causing enhanced litter decomposition in high-pollution sites in the San Bernardino Mountains of southern California were investigated. Nitrogen concentration of soil, as well as foliage and litter of ponderosa pine (Pinus ponderosa Laws.) and Jeffrey pine (Pinus jeffreyi Grev. & Balf.) were greater in...

Does cattle grazing of dual-purpose wheat accelerate the rate of stubble decomposition and nutrients released

USDA-ARS?s Scientific Manuscript database

Decomposition and nutrient release of winter annual forages in integrated crop-livestock systems could be affected by the resultant alterations in structure and quality of residues caused by grazing, but little information is available to test this hypothesis. Information on residue dynamics is need...

High temperature phase decomposition in Ti{sub x}Zr{sub y}Al{sub z}N

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

Lind, Hans; Pilemalm, Robert; Rogström, Lina

2014-12-15

Through a combination of theoretical and experimental observations we study the high temperature decomposition behavior of c-(Ti{sub x}Zr{sub y}Al{sub z}N) alloys. We show that for most concentrations the high formation energy of (ZrAl)N causes a strong tendency for spinodal decomposition between ZrN and AlN while other decompositions tendencies are suppressed. In addition we observe that entropic effects due to configurational disorder favor a formation of a stable Zr-rich (TiZr)N phase with increasing temperature. Our calculations also predict that at high temperatures a Zr rich (TiZrAl)N disordered phase should become more resistant against the spinodal decomposition despite its high and positivemore » formation energy due to the specific topology of the free energy surface at the relevant concentrations. Our experimental observations confirm this prediction by showing strong tendency towards decomposition in a Zr-poor sample while a Zr-rich alloy shows a greatly reduced decomposition rate, which is mostly attributable to binodal decomposition processes. This result highlights the importance of considering the second derivative of the free energy, in addition to its absolute value in predicting decomposition trends of thermodynamically unstable alloys.« less

First-principles calculated decomposition pathways for LiBH 4 nanoclusters

DOE PAGES

Huang, Zhi -Quan; Chen, Wei -Chih; Chuang, Feng -Chuan; ...

2016-05-18

Here, we analyze thermodynamic stability and decomposition pathways of LiBH 4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH 4) n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li) n, (B) n, (LiB) n, (LiH) n, and Li 2B nH n; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathwaysmore » markedly differ from those in bulk LiBH 4. While experiments have found that the bulk material decomposes into LiH and B, with Li 2B 12H 12 as a kinetically inhibited intermediate phase, (LiBH 4) n nanoclusters with n ≤ 12 are predicted to decompose into mixed Li nB n clusters via a series of intermediate clusters of Li nB nH m (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.« less

Electron Paramagnetic Resonance Spectroscopic Study on Nonequilibrium Reaction Pathways in the Photolysis of Solid Nitromethane (CH3NO2) and D3-Nitromethane (CD3NO2).

PubMed

Tsegaw, Yetsedaw Andargie; Sander, Wolfram; Kaiser, Ralf I

2016-03-10

Thin films of nitromethane (CH3NO2) along with its isotopically labeled counterpart D3-nitromethane (CD3NO2) were photolyzed at discrete wavelength between 266 nm (4.7 eV) and 121 nm (10.2 eV) to explore the underlying mechanisms involved in the decomposition of model compounds of energetic materials in the condensed phase at 5 K. The chemical modifications of the ices were traced in situ via electron paramagnetic resonance, thus focusing on the detection of (hitherto elusive) reaction intermediates and products with unpaired electrons. These studies revealed the formation of two carbon-centered radicals [methyl (CH3), nitromethyl (CH2NO2)], one oxygen-centered radical [methoxy (CH3O)], two nitrogen-centered radicals [nitrogen monoxide (NO), nitrogen dioxide (NO2)], as well as atomic hydrogen (H). The decomposition products of these channels and the carbon-centered nitromethyl (CH2NO2) radical in particular represent crucial reaction intermediates leading via sequential molecular mass growth processes in the exposed nitromethane samples to complex organic molecules as predicted previously by dynamics calculations. The detection of the nitromethyl (CH2NO2) radical along with atomic hydrogen (H) demonstrated the existence of a high-energy decomposition pathway, which is closed under collisionless conditions in the gas phase.

Thermal decomposition behavior of nano/micro bimodal feedstock with different solids loading

NASA Astrophysics Data System (ADS)

Oh, Joo Won; Lee, Won Sik; Park, Seong Jin

2018-01-01

Debinding is one of the most critical processes for powder injection molding. The parts in debinding process are vulnerable to defect formation, and long processing time of debinding decreases production rate of whole process. In order to determine the optimal condition for debinding process, decomposition behavior of feedstock should be understood. Since nano powder affects the decomposition behavior of feedstock, nano powder effect needs to be investigated for nano/micro bimodal feedstock. In this research, nano powder effect on decomposition behavior of nano/micro bimodal feedstock has been studied. Bimodal powders were fabricated with different ratios of nano powder, and the critical solids loading of each powder was measured by torque rheometer. Three different feedstocks were fabricated for each powder depending on solids loading condition. Thermogravimetric analysis (TGA) experiment was carried out to analyze the thermal decomposition behavior of the feedstocks, and decomposition activation energy was calculated. The result indicated nano powder showed limited effect on feedstocks in lower solids loading condition than optimal range. Whereas, it highly influenced the decomposition behavior in optimal solids loading condition by causing polymer chain scission with high viscosity.

Influence of density and environmental factors on decomposition kinetics of amorphous polylactide - Reactive molecular dynamics studies.

PubMed

Mlyniec, A; Ekiert, M; Morawska-Chochol, A; Uhl, T

2016-06-01

In this work, we investigate the influence of the surrounding environment and the initial density on the decomposition kinetics of polylactide (PLA). The decomposition of the amorphous PLA was investigated by means of reactive molecular dynamics simulations. A computational model simulates the decomposition of PLA polymer inside the bulk, due to the assumed lack of removal of reaction products from the polymer matrix. We tracked the temperature dependency of the water and carbon monoxide production to extract the activation energy of thermal decomposition of PLA. We found that an increased density results in decreased activation energy of decomposition by about 50%. Moreover, initiation of decomposition of the amorphous PLA is followed by a rapid decline in activation energy caused by reaction products which accelerates the hydrolysis of esters. The addition of water molecules decreases initial energy of activation as well as accelerates the decomposition process. Additionally, we have investigated the dependency of density on external loading. Comparison of pressures needed to obtain assumed densities shows that this relationship is bilinear and the slope changes around a density equal to 1.3g/cm(3). The conducted analyses provide an insight into the thermal decomposition process of the amorphous phase of PLA, which is particularly susceptible to decomposition in amorphous and semi-crystalline PLA polymers. Copyright © 2016 Elsevier Inc. All rights reserved.

Acid and alkali effects on the decomposition of HMX molecule: a computational study.

PubMed

Zhang, Chaoyang; Li, Yuzhen; Xiong, Ying; Wang, Xiaolin; Zhou, Mingfei

2011-11-03

The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).

HYDROLOGIC FLOWPATHS INFLUENCE INORGANIC AND ORGANIC NUTRIENT LEACHING IN A FOREST SOIL

EPA Science Inventory

Hydrologic pathways through soil affect element leaching by determining the relative importance of biogeochemical processes such as sorption and decomposition. We used stable hydrogen isotopes of water (δD) to examine the influence of flowpaths on soil solution chemistry in a mat...

Methods for estimating litter decomposition. Chapter 8

Treesearch

Noah J. Karberg; Neal A. Scott; Christian P. Giardina

2008-01-01

Litterfall in terrestrial ecosystems represents the primary pathway for nutrient return to soil. Heterotrophic metabolism, facilitated through comminution by small insects and leaching during precipitation events, results in the release of plant litter carbon as CO2 into the atmosphere. The balance between litter inputs and heterotrophic litter...

Engineering of the glycerol decomposition pathway and cofactor regulation in an industrial yeast improves ethanol production.

PubMed

Zhang, Liang; Tang, Yan; Guo, Zhongpeng; Shi, Guiyang

2013-10-01

Glycerol is a major by-product of industrial ethanol production and its formation consumes up to 4 % of the sugar substrate. This study modified the glycerol decomposition pathway of an industrial strain of Saccharomyces cerevisiae to optimize the consumption of substrate and yield of ethanol. This study is the first to couple glycerol degradation with ethanol formation, to the best of our knowledge. The recombinant strain overexpressing GCY1 and DAK1, encoding glycerol dehydrogenase and dihydroxyacetone kinase, respectively, in glycerol degradation pathway, exhibited a moderate increase in ethanol yield (2.9 %) and decrease in glycerol yield (24.9 %) compared to the wild type with the initial glucose concentration of 15 % under anaerobic conditions. However, when the mhpF gene, encoding acetylating NAD⁺-dependent acetaldehyde dehydrogenase from Escherichia coli, was co-expressed in the aforementioned recombinant strain, a further increase in ethanol yield by 5.5 % and decrease in glycerol yield by 48 % were observed for the resultant recombinant strain GDMS1 when acetic acid was added into the medium prior to inoculation compared to the wild type. The process outlined in this study which enhances glycerol consumption and cofactor regulation in an industrial yeast is a promising metabolic engineering strategy to increase ethanol production by reducing the formation of glycerol.

Mathematical methods to analysis of topology, functional variability and evolution of metabolic systems based on different decomposition concepts.

PubMed

Mrabet, Yassine; Semmar, Nabil

2010-05-01

Complexity of metabolic systems can be undertaken at different scales (metabolites, metabolic pathways, metabolic network map, biological population) and under different aspects (structural, functional, evolutive). To analyse such a complexity, metabolic systems need to be decomposed into different components according to different concepts. Four concepts are presented here consisting in considering metabolic systems as sets of metabolites, chemical reactions, metabolic pathways or successive processes. From a metabolomic dataset, such decompositions are performed using different mathematical methods including correlation, stiochiometric, ordination, classification, combinatorial and kinetic analyses. Correlation analysis detects and quantifies affinities/oppositions between metabolites. Stoichiometric analysis aims to identify the organisation of a metabolic network into different metabolic pathways on the hand, and to quantify/optimize the metabolic flux distribution through the different chemical reactions of the system. Ordination and classification analyses help to identify different metabolic trends and their associated metabolites in order to highlight chemical polymorphism representing different variability poles of the metabolic system. Then, metabolic processes/correlations responsible for such a polymorphism can be extracted in silico by combining metabolic profiles representative of different metabolic trends according to a weighting bootstrap approach. Finally evolution of metabolic processes in time can be analysed by different kinetic/dynamic modelling approaches.

Using Learning Decomposition and Bootstrapping with Randomization to Compare the Impact of Different Educational Interventions on Learning

ERIC Educational Resources Information Center

Feng, Mingyu; Beck, Joseph E.; Heffernan, Neil T.

2009-01-01

A basic question of instructional interventions is how effective it is in promoting student learning. This paper presents a study to determine the relative efficacy of different instructional strategies by applying an educational data mining technique, learning decomposition. We use logistic regression to determine how much learning is caused by…

Transformation among Aromatic Iodinated Disinfection Byproducts in the Presence of Monochloramine: From Monoiodophenol to Triiodophenol and Diiodonitrophenol.

PubMed

Gong, Tingting; Tao, Yuxian; Zhang, Xiangru; Hu, Shaoyang; Yin, Jinbao; Xian, Qiming; Ma, Jian; Xu, Bin

2017-09-19

Aromatic iodinated disinfection byproducts (DBPs) are a newly identified category of highly toxic DBPs. Among the identified aromatic iodinated DBPs, 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol have shown relatively widespread occurrence and high toxicity. In this study, we found that 4-iodophenol underwent transformation to form 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol in the presence of monochloramine. The transformation pathways were investigated, the decomposition kinetics of 4-iodophenol and the formation of 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol were studied, the factors affecting the transformation were examined, the toxicity change during the transformation was evaluated, and the occurrence of the proposed transformation pathways during chloramination of source water was verified. The results revealed that 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol, which could account for 71.0% of iodine in the transformed 4-iodophenol, were important iodinated transformation products of 4-iodophenol in the presence of monochloramine. The transformation pathways of 4-iodophenol in the presence of monochloramine were proposed and verified. The decomposition of 4-iodophenol in the presence of monochloramine followed a pseudo-second-order decay. Various factors including monochloramine dose, pH, temperature, nitrite concentration, and free chlorine contact time (before chloramination) affected the transformation. The cytotoxicity of the chloraminated 4-iodophenol samples increased continuously with contact time. The proposed transformation pathways occurred during chloramination of source water.

A new conceptual model on the fate and controls of fresh and pyrolized plant litter decomposition

USDA-ARS?s Scientific Manuscript database

The leaching of dissolved organic matter (DOM) from fresh and pyrolyzed aboveground plant inputs to the soil is a major pathway by which decomposing aboveground plant material contributes to soil organic matter formation. Understanding how aboveground plant input chemical traits control the partiti...

INTERACTIONS BETWEEN PHOTOCHEMICAL AND MICROBIAL DECOMPOSITION IN MODIFYING THE BIOLOGICAL AVAILABILITY AND OPTICAL PROPERTIES OF ESTUARINE DISSOLVED ORGANIC MATTER

EPA Science Inventory

Direct photodecomposition and photochemically-mediated bacterial degradation (via photochemical modification of otherwise refractory DOM into biologically labile forms) provide
important pathways for the loss of dissolved organic matter in coastal waters. Here we report
lab...

COLBALT-MEDIATED ACTIVATION OF PEROXYMONOSULFATE AND SULFATE RADICAL ATTACK ON PHENOLIC COMPOUNDS, IMPLICATIONS OF CHLORIDE IONS

EPA Science Inventory

This study reports on the sulfate radical pathway of room temperature degradation of two phenolic compounds in water. The radicals were produced by the cobalt-mediated decomposition of peroxymonosulfate (Oxone) in an aqueous homogeneous system. The major intermediates formed from...

Prolonged respiratory symptoms caused by thermal degradation products of freons.

PubMed

Piirilä, Päivi; Espo, Timo; Pfäffli, Pirkko; Riihimäki, Vesa; Wolff, Henrik; Nordman, Henrik

2003-02-01

The chlorofluorocarbons (CFC) used in refrigeration systems decompose on heating and produce substances that are highly irritating to the airways (eg, chlorine, carbonyl fluoride, and hydrogen fluoride). This study examined persistent respiratory symptoms among several workers exposed to thermal decomposition products of CFC. Seven patients with respiratory symptoms caused by inadvertent exposure to thermal decomposition products of CFC in a restaurant kitchen or during refrigerator repair were studied with the use of spirometry, peak flow follow-up, and histamine challenge tests. Three patients also underwent bronchoscopy and bronchoalveolar lavage. In five of the cases, cough or dyspnea lasted longer than 1 month; for three of the five, the symptoms lasted more than 4 years. Three cases showed increased bronchial hyperreactivity, and two of the three had increased diurnal peak flow variation. Three patients fulfilled the criteria for acute irritant-induced asthma or reactive airway dysfunction syndrome. One case exhibited bronchiolitis while, for the other six, the clinical picture was consistent with bronchitis. The studied cases indicate that the thermal decomposition products of CFC used in refrigerators may cause irritant-induced airway diseases of long duration.

The products of the thermal decomposition of CH{sub 3}CHO

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

Vasiliou, AnGayle; National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, Colorado 80401; Piech, Krzysztof M.

2011-07-07

We have used a heated 2 cm x 1 mm SiC microtubular ({mu}tubular) reactor to decompose acetaldehyde: CH{sub 3}CHO +{Delta}{yields} products. Thermal decomposition is followed at pressures of 75-150 Torr and at temperatures up to 1675 K, conditions that correspond to residence times of roughly 50-100 {mu}s in the {mu}tubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: vacuum ultraviolet photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH{sub 3}CHO, we have studied three isotopologues, CH{sub 3}CDO, CD{sub 3}CHO, and CD{sub 3}CDO. We have identified the thermal decomposition productsmore » CH{sub 3} (PIMS), CO (IR, PIMS), H (PIMS), H{sub 2} (PIMS), CH{sub 2}CO (IR, PIMS), CH{sub 2}=CHOH (IR, PIMS), H{sub 2}O (IR, PIMS), and HC{identical_to}CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH{sub 3}CHO; namely, radical decomposition: CH{sub 3}CHO +{Delta}{yields} CH{sub 3}+[HCO]{yields} CH{sub 3}+ H + CO; elimination: CH{sub 3}CHO +{Delta}{yields} H{sub 2}+ CH{sub 2}=C=O; isomerization/elimination: CH{sub 3}CHO +{Delta}{yields}[CH{sub 2}=CH-OH]{yields} HC{identical_to}CH + H{sub 2}O. An interesting result is that both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH{sub 2}=C:, as an intermediate in the decomposition of vinyl alcohol: CH{sub 2}=CH-OH +{Delta}{yields}[CH{sub 2}=C:]+ H{sub 2}O {yields} HC{identical_to}CH + H{sub 2}O.« less

Surface-Mediated Solvent Decomposition in Li–Air Batteries: Impact of Peroxide and Superoxide Surface Terminations

DOE PAGES

Kumar, Nitin; Radin, Maxwell D.; Wood, Brandon C.; ...

2015-04-13

A viable Li/O 2 battery will require the development of stable electrolytes that do not continuously decompose during cell operation. In some recent experiments it is suggested that reactions occurring at the interface between the liquid electrolyte and the solid lithium peroxide (Li 2O 2) discharge phase are a major contributor to these instabilities. To clarify the mechanisms associated with these reactions, a variety of atomistic simulation techniques, classical Monte Carlo, van der Waals-augmented density functional theory, ab initio molecular dynamics, and various solvation models, are used to study the initial decomposition of the common electrolyte solvent, dimethoxyethane (DME), onmore » surfaces of Li 2O 2. Comparisons are made between the two predominant Li 2O 2 surface charge states by calculating decomposition pathways on peroxide-terminated (O 2 2–) and superoxide-terminated (O 2 1–) facets. For both terminations, DME decomposition proceeds exothermically via a two-step process comprised of hydrogen abstraction (H-abstraction) followed by nucleophilic attack. In the first step, abstracted H dissociates a surface O 2 dimer, and combines with a dissociated oxygen to form a hydroxide ion (OH –). In the remaining surface oxygen then attacks the DME, resulting in a DME fragment that is strongly bound to the Li 2O 2 surface. DME decomposition is predicted to be more exothermic on the peroxide facet; nevertheless, the rate of DME decomposition is faster on the superoxide termination. The impact of solvation (explicit vs implicit) and an applied electric field on the reaction energetics are investigated. Finally, our calculations suggest that surface-mediated electrolyte decomposition should out-pace liquid-phase processes such as solvent auto-oxidation by dissolved O 2.« less

Litter chemistry prevails over litter consumers in mediating effects of past steel industry activities on leaf litter decomposition.

PubMed

Lucisine, Pierre; Lecerf, Antoine; Danger, Michaël; Felten, Vincent; Aran, Delphine; Auclerc, Apolline; Gross, Elisabeth M; Huot, Hermine; Morel, Jean-Louis; Muller, Serge; Nahmani, Johanne; Maunoury-Danger, Florence

2015-12-15

Soil pollution has adverse effects on the performance and life history traits of microorganisms, plants, and animals, yet evidence indicates that even the most polluted sites can support structurally-complex and dynamic ecosystems. The present study aims at determining whether and how litter decomposition, one of the most important soil ecological processes leaf, is affected in a highly trace-metal polluted site. We postulated that past steel mill activities resulting in soil pollution and associated changes in soil characteristics would influence the rate of litter decomposition through two non-exclusive pathways: altered litter chemistry and responses of decomposers to lethal and sub-lethal toxic stress. We carried out a litter-bag experiment using Populus tremula L. leaf litter collected at, and allowed to decompose in, a trace metal polluted site and in three unpolluted sites used as controls. We designed a fully-factorial transplant experimental design to assess effects of litter origin and exposure site on the rate of litter decomposition. We further determined initial litter chemistry, fungal biomass, mesofauna abundance in litter bags, and the soil macrofauna community. Irrespective of the site of litter exposure, litter originating from the polluted site had a two-fold faster decomposition than litter from the unpolluted sites. Litter chemistry, notably the lignin content, seemed most important in explaining the degradation rate of the leaf litter. Abundance of meso and macro-detritivores was higher at the polluted site than at the unpolluted sites. However, litter decomposition proceeded at similar rates in polluted and unpolluted sites. Our results show that trace metal pollution and associated soil and litter changes do not necessarily weaken consumer control on litter decomposition through lethal and sub-lethal toxic stress. Copyright © 2015. Published by Elsevier B.V.

Decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H2O2 and UV/TiO2 oxidation processes.

PubMed

Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu

2017-02-01

3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.

Decoupling the direct and indirect effects of climate on plant litter decomposition: Accounting for stress-induced modifications in plant chemistry.

PubMed

Suseela, Vidya; Tharayil, Nishanth

2018-04-01

Decomposition of plant litter is a fundamental ecosystem process that can act as a feedback to climate change by simultaneously influencing both the productivity of ecosystems and the flux of carbon dioxide from the soil. The influence of climate on decomposition from a postsenescence perspective is relatively well known; in particular, climate is known to regulate the rate of litter decomposition via its direct influence on the reaction kinetics and microbial physiology on processes downstream of tissue senescence. Climate can alter plant metabolism during the formative stage of tissues and could shape the final chemical composition of plant litter that is available for decomposition, and thus indirectly influence decomposition; however, these indirect effects are relatively poorly understood. Climatic stress disrupts cellular homeostasis in plants and results in the reprogramming of primary and secondary metabolic pathways, which leads to changes in the quantity, composition, and organization of small molecules and recalcitrant heteropolymers, including lignins, tannins, suberins, and cuticle within the plant tissue matrix. Furthermore, by regulating metabolism during tissue senescence, climate influences the resorption of nutrients from senescing tissues. Thus, the final chemical composition of plant litter that forms the substrate of decomposition is a combined product of presenescence physiological processes through the production and resorption of metabolites. The changes in quantity, composition, and localization of the molecular construct of the litter could enhance or hinder tissue decomposition and soil nutrient cycling by altering the recalcitrance of the lignocellulose matrix, the composition of microbial communities, and the activity of microbial exo-enzymes via various complexation reactions. Also, the climate-induced changes in the molecular composition of litter could differentially influence litter decomposition and soil nutrient cycling. Compared with temperate ecosystems, the indirect effects of climate on litter decomposition in the tropics are not well understood, which underscores the need to conduct additional studies in tropical biomes. We also emphasize the need to focus on how climatic stress affects the root chemistry as roots contribute significantly to biogeochemical cycling, and on utilizing more robust analytical approaches to capture the molecular composition of tissue matrix that fuel microbial metabolism. © 2017 John Wiley & Sons Ltd.

Decomposition of the Total Effect in the Presence of Multiple Mediators and Interactions.

PubMed

Bellavia, Andrea; Valeri, Linda

2018-06-01

Mediation analysis allows decomposing a total effect into a direct effect of the exposure on the outcome and an indirect effect operating through a number of possible hypothesized pathways. Recent studies have provided formal definitions of direct and indirect effects when multiple mediators are of interest and have described parametric and semiparametric methods for their estimation. Investigating direct and indirect effects with multiple mediators, however, can be challenging in the presence of multiple exposure-mediator and mediator-mediator interactions. In this paper we derive a decomposition of the total effect that unifies mediation and interaction when multiple mediators are present. We illustrate the properties of the proposed framework in a secondary analysis of a pragmatic trial for the treatment of schizophrenia. The decomposition is employed to investigate the interplay of side effects and psychiatric symptoms in explaining the effect of antipsychotic medication on quality of life in schizophrenia patients. Our result offers a valuable tool to identify the proportions of total effect due to mediation and interaction when more than one mediator is present, providing the finest decomposition of the total effect that unifies multiple mediators and interactions.

Pressure-induced metallization of condensed phase β-HMX under shock loadings via molecular dynamics simulations in conjunction with multi-scale shock technique.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Zhao, Feng; Chen, Xiang-Rong; Ji, Guang-Fu

2014-07-01

The electronic structure and initial decomposition in high explosive HMX under conditions of shock loading are examined. The simulation is performed using quantum molecular dynamics in conjunction with multi-scale shock technique (MSST). A self-consistent charge density-functional tight-binding (SCC-DFTB) method is adapted. The results show that the N-N-C angle has a drastic change under shock wave compression along lattice vector b at shock velocity 11 km/s, which is the main reason that leads to an insulator-to-metal transition for the HMX system. The metallization pressure (about 130 GPa) of condensed-phase HMX is predicted firstly. We also detect the formation of several key products of condensed-phase HMX decomposition, such as NO2, NO, N2, N2O, H2O, CO, and CO2, and all of them have been observed in previous experimental studies. Moreover, the initial decomposition products include H2 due to the C-H bond breaking as a primary reaction pathway at extreme condition, which presents a new insight into the initial decomposition mechanism of HMX under shock loading at the atomistic level.

Effects of long-term continuous cropping on soil nematode community and soil condition associated with replant problem in strawberry habitat.

PubMed

Li, Xingyue; Lewis, Edwin E; Liu, Qizhi; Li, Heqin; Bai, Chunqi; Wang, Yuzhu

2016-08-10

Continuous cropping changes soil physiochemical parameters, enzymes and microorganism communities, causing "replant problem" in strawberry cultivation. We hypothesized that soil nematode community would reflect the changes in soil conditions caused by long-term continuous cropping, in ways that are consistent and predictable. To test this hypothesis, we studied the soil nematode communities and several soil parameters, including the concentration of soil phenolic acids, organic matter and nitrogen levels, in strawberry greenhouse under continuous-cropping for five different durations. Soil pH significantly decreased, and four phenolic acids, i.e., p-hydroxybenzoic acid, ferulic acid, cinnamic acid and p-coumaric acid, accumulated with time under continuous cropping. The four phenolic acids were highly toxic to Acrobeloides spp., the eudominant genus in non-continuous cropping, causing it to reduce to a resident genus after seven-years of continuous cropping. Decreased nematode diversity indicated loss of ecosystem stability and sustainability because of continuous-cropping practice. Moreover, the dominant decomposition pathway was altered from bacterial to fungal under continuous cropping. Our results suggest that along with the continuous-cropping time in strawberry habitat, the soil food web is disturbed, and the available plant nutrition as well as the general health of the soil deteriorates; these changes can be indicated by soil nematode community.

Effects of long-term continuous cropping on soil nematode community and soil condition associated with replant problem in strawberry habitat

NASA Astrophysics Data System (ADS)

Li, Xingyue; Lewis, Edwin E.; Liu, Qizhi; Li, Heqin; Bai, Chunqi; Wang, Yuzhu

2016-08-01

Continuous cropping changes soil physiochemical parameters, enzymes and microorganism communities, causing “replant problem” in strawberry cultivation. We hypothesized that soil nematode community would reflect the changes in soil conditions caused by long-term continuous cropping, in ways that are consistent and predictable. To test this hypothesis, we studied the soil nematode communities and several soil parameters, including the concentration of soil phenolic acids, organic matter and nitrogen levels, in strawberry greenhouse under continuous-cropping for five different durations. Soil pH significantly decreased, and four phenolic acids, i.e., p-hydroxybenzoic acid, ferulic acid, cinnamic acid and p-coumaric acid, accumulated with time under continuous cropping. The four phenolic acids were highly toxic to Acrobeloides spp., the eudominant genus in non-continuous cropping, causing it to reduce to a resident genus after seven-years of continuous cropping. Decreased nematode diversity indicated loss of ecosystem stability and sustainability because of continuous-cropping practice. Moreover, the dominant decomposition pathway was altered from bacterial to fungal under continuous cropping. Our results suggest that along with the continuous-cropping time in strawberry habitat, the soil food web is disturbed, and the available plant nutrition as well as the general health of the soil deteriorates; these changes can be indicated by soil nematode community.

Holocene carbon stocks and carbon accumulation rates altered in soils undergoing permafrost thaw

Treesearch

Caitlin E. Hicks Pries; Edward A.G. Schuur; K. Grace Crummer

2012-01-01

Permafrost soils are a significant global store of carbon (C) with the potential to become a large C source to the atmosphere. Climate change is causing permafrost to thaw, which can affect primary production and decomposition, therefore affecting ecosystem C balance. We modeled decadal and millennial soil C inputs, decomposition constants, and C accumulation rates by...

Artifact removal from EEG data with empirical mode decomposition

NASA Astrophysics Data System (ADS)

Grubov, Vadim V.; Runnova, Anastasiya E.; Efremova, Tatyana Yu.; Hramov, Alexander E.

2017-03-01

In the paper we propose the novel method for dealing with the physiological artifacts caused by intensive activity of facial and neck muscles and other movements in experimental human EEG recordings. The method is based on analysis of EEG signals with empirical mode decomposition (Hilbert-Huang transform). We introduce the mathematical algorithm of the method with following steps: empirical mode decomposition of EEG signal, choosing of empirical modes with artifacts, removing empirical modes with artifacts, reconstruction of the initial EEG signal. We test the method on filtration of experimental human EEG signals from movement artifacts and show high efficiency of the method.

Effective brain network analysis with resting-state EEG data: a comparison between heroin abstinent and non-addicted subjects

NASA Astrophysics Data System (ADS)

Hu, Bin; Dong, Qunxi; Hao, Yanrong; Zhao, Qinglin; Shen, Jian; Zheng, Fang

2017-08-01

Objective. Neuro-electrophysiological tools have been widely used in heroin addiction studies. Previous studies indicated that chronic heroin abuse would result in abnormal functional organization of the brain, while few heroin addiction studies have applied the effective connectivity tool to analyze the brain functional system (BFS) alterations induced by heroin abuse. The present study aims to identify the abnormality of resting-state heroin abstinent BFS using source decomposition and effective connectivity tools. Approach. The resting-state electroencephalograph (EEG) signals were acquired from 15 male heroin abstinent (HA) subjects and 14 male non-addicted (NA) controls. Multivariate autoregressive models combined independent component analysis (MVARICA) was applied for blind source decomposition. Generalized partial directed coherence (GPDC) was applied for effective brain connectivity analysis. Effective brain networks of both HA and NA groups were constructed. The two groups of effective cortical networks were compared by the bootstrap method. Abnormal causal interactions between decomposed source regions were estimated in the 1-45 Hz frequency domain. Main results. This work suggested: (a) there were clear effective network alterations in heroin abstinent subject groups; (b) the parietal region was a dominant hub of the abnormally weaker causal pathways, and the left occipital region was a dominant hub of the abnormally stronger causal pathways. Significance. These findings provide direct evidence that chronic heroin abuse induces brain functional abnormalities. The potential value of combining effective connectivity analysis and brain source decomposition methods in exploring brain alterations of heroin addicts is also implied.

Thermal Decomposition of Methyl Acetate (CH_3COOCH_3) in a Flash-Pyrolysis Micro-Reactor

NASA Astrophysics Data System (ADS)

Porterfield, Jessica P.; Bross, David H.; Ruscic, Branko; Thorpe, James H.; Nguyen, Thanh Lam; Baraban, Joshua H.; Stanton, John F.; Daily, John W.; Ellison, Barney

2017-06-01

The thermal decomposition of methyl acetate (CH_3COOCH_3) has been studied in a set of flash pyrolysis micro-reactors. Samples were diluted to (0.06 - 0.13%) in carrier gases (He, Ar) and subjected to temperatures of 300 - 1600 K at roughly 20 Torr. After residence times of approximately 25 - 150 μseconds, the unimolecular pyrolysis products were detected by vacuum ultraviolet photoionization mass spectrometry at 10.487 eV (118.2 nm). Complementary product identification was provided by matrix isolation infrared spectroscopy. Decomposition began at 1000 K with the observation of (CH_2=C=O, CH_3OH), products of a four centered rearrangement with a Δ_{rxn}H_{298} = 39.1 ± 0.2 kcal mol^{-1}. As the micro-reactor was heated to 1300 K, a mixture of (CH_2=C=O, CH_3OH, CH_3, CH_2=O, H, CO, CO_2) appeared. A new novel pathway is calculated in which both methyl groups leave behind CO_2 simultaneously, Δ_{rxn}H_{298} = 74.5 ± 0.4 kcal mol^{-1}. This pathway is in contrast to step-wise loss of methyl radical, which can go in two ways: Δ_{rxn}H_{298} (CH_3COOCH_3 → CH_3 + COOCH_3) = 95.4 ± 0.4 kcal mol^{-1}, Δ_{rxn}H_{298} (CH_3COOCH_3 → CH_3COO + CH_3) = 88.0 ± 0.3 kcal mol^{-1}.

Effective brain network analysis with resting-state EEG data: a comparison between heroin abstinent and non-addicted subjects.

PubMed

Hu, Bin; Dong, Qunxi; Hao, Yanrong; Zhao, Qinglin; Shen, Jian; Zheng, Fang

2017-08-01

Neuro-electrophysiological tools have been widely used in heroin addiction studies. Previous studies indicated that chronic heroin abuse would result in abnormal functional organization of the brain, while few heroin addiction studies have applied the effective connectivity tool to analyze the brain functional system (BFS) alterations induced by heroin abuse. The present study aims to identify the abnormality of resting-state heroin abstinent BFS using source decomposition and effective connectivity tools. The resting-state electroencephalograph (EEG) signals were acquired from 15 male heroin abstinent (HA) subjects and 14 male non-addicted (NA) controls. Multivariate autoregressive models combined independent component analysis (MVARICA) was applied for blind source decomposition. Generalized partial directed coherence (GPDC) was applied for effective brain connectivity analysis. Effective brain networks of both HA and NA groups were constructed. The two groups of effective cortical networks were compared by the bootstrap method. Abnormal causal interactions between decomposed source regions were estimated in the 1-45 Hz frequency domain. This work suggested: (a) there were clear effective network alterations in heroin abstinent subject groups; (b) the parietal region was a dominant hub of the abnormally weaker causal pathways, and the left occipital region was a dominant hub of the abnormally stronger causal pathways. These findings provide direct evidence that chronic heroin abuse induces brain functional abnormalities. The potential value of combining effective connectivity analysis and brain source decomposition methods in exploring brain alterations of heroin addicts is also implied.

Characterization of Thermo-Physical Properties of EVA/ATH: Application to Gasification Experiments and Pyrolysis Modeling.

PubMed

Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge

2015-11-20

The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material.

Characterization of Thermo-Physical Properties of EVA/ATH: Application to Gasification Experiments and Pyrolysis Modeling

PubMed Central

Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge

2015-01-01

The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material. PMID:28793682

Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

NASA Technical Reports Server (NTRS)

Fan, Wendy

2011-01-01

The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

Preparation and characterization of ligand types intermediate in the metal catalyzed conversion of coal to methane, methanol, and higher alkanes and alcohols. Second technical progress report, September 1, 1979-February 28, 1981

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

Gladysz, J. A.

1980-11-10

Mechanistic studies of anionic formyl complexes were made. The rate of decomposition of the formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CHO)/sup -/ anion as a function of counter-ion and trialkylborane present was examined. The deuterated formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CDO)/sup -/ was prepared and its decomposition was monitored by H/sup 2/ NMR. The data obtained indicate that the formyl decomposes by a disproportionative pathway not by initial CO loss, as commonly noted for formyl complexes.

Domain decomposition methods in computational fluid dynamics

NASA Technical Reports Server (NTRS)

Gropp, William D.; Keyes, David E.

1991-01-01

The divide-and-conquer paradigm of iterative domain decomposition, or substructuring, has become a practical tool in computational fluid dynamic applications because of its flexibility in accommodating adaptive refinement through locally uniform (or quasi-uniform) grids, its ability to exploit multiple discretizations of the operator equations, and the modular pathway it provides towards parallelism. These features are illustrated on the classic model problem of flow over a backstep using Newton's method as the nonlinear iteration. Multiple discretizations (second-order in the operator and first-order in the preconditioner) and locally uniform mesh refinement pay dividends separately, and they can be combined synergistically. Sample performance results are included from an Intel iPSC/860 hypercube implementation.

New evidence favoring multilevel decomposition and optimization

NASA Technical Reports Server (NTRS)

Padula, Sharon L.; Polignone, Debra A.

1990-01-01

The issue of the utility of multilevel decomposition and optimization remains controversial. To date, only the structural optimization community has actively developed and promoted multilevel optimization techniques. However, even this community acknowledges that multilevel optimization is ideally suited for a rather limited set of problems. It is warned that decomposition typically requires eliminating local variables by using global variables and that this in turn causes ill-conditioning of the multilevel optimization by adding equality constraints. The purpose is to suggest a new multilevel optimization technique. This technique uses behavior variables, in addition to design variables and constraints, to decompose the problem. The new technique removes the need for equality constraints, simplifies the decomposition of the design problem, simplifies the programming task, and improves the convergence speed of multilevel optimization compared to conventional optimization.

Catalytic pyrolysis-gc/ms of spirulina: evaluation of a highly proteinaceous biomass source for production of fuels and chemicals

USDA-ARS?s Scientific Manuscript database

Pyrolysis of microalgae offers a pathway towards the production of compounds derived from the thermal decomposition of triglycerides, proteins as well as lignocelluloses and their combinations thereof. When catalytically induced, this could lead to the production of fuels and chemicals including aro...

Finding a common path: predicting gene function using inferred evolutionary trees.

PubMed

Reynolds, Kimberly A

2014-07-14

Reporting in Cell, Li and colleagues (2014) describe an innovative method to functionally classify genes using evolutionary information. This approach demonstrates broad utility for eukaryotic gene annotation and suggests an intriguing new decomposition of pathways and complexes into evolutionarily conserved modules. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of gamma radiation on sugars and vitamin C: Radiolytic pathways.

PubMed

Ramírez-Cahero, Hiram F; Valdivia-López, Ma Angeles

2018-04-15

The radiolytic decomposition of glucose, fructose, sucrose, ascorbic acid (H 2 A) and dehydroascorbic acid (DHAA), induced by ionizing radiation, was investigated. Aqueous solutions of these compounds were gamma-irradiated at doses of 0.5, 0.7 and 1 kGy, with a dose rate of 0.04 kGy/min, in the presence of air, followed by HPLC, HPLC-MS, EPR, and UV-VIS spectroscopy analysis of the resulting mixtures. Carboxylic acids, 2-furaldehyde, 5-hydroxymethyl-2-furaldehyde, furfuryl alcohol, 2-furoic acid and 2(5H)-furanone were identified in solutions of sugars and vitamin C, by comparing with standards. EPR studies exhibited a higher amount of free radicals for fructose than the other sugars, and more for DHAA than H 2 A. Additionally, spectroscopic determinations showed a typical UV-VIS absorption for furans during the storage of irradiated solutions. Formation and decomposition routes for furanoids and aliphatic carboxylic acids, and mechanistic pathways for the radiolytic induced rupture of glucose, fructose, sucrose and vitamin C have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermoanalytical Investigation of Some Sulfone-Containing Drugs

PubMed Central

Salama, Nahla N.; El Ries, Mohammed A.; Toubar, Safaa; Abd El Hamid, Maha; Walash, Mohammed I.

2012-01-01

The thermal behavior of some sulfone-containing drugs, namely, dapsone (DDS), dimethylsulfone (MSM), and topiramate (TOP) in drug substances, and products were investigated using different thermal techniques. These include thermogravimetry (TGA), derivative thermogravimetry (DTG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The thermogravimetric data allowed the determination of the kinetic parameters: activation energy (E a), frequency factor (A), and reaction order (n). The thermal degradation of dapsone and topiramate was followed a first-order kinetic behavior. The calculated data evidenced a zero-order kinetic for dimethylsulfone. The relative thermal stabilities of the studied drugs have been evaluated and follow the order DDS > TOP > MSM. The purity was determined using DSC for the studied compounds, in drug substances and products. The results were in agreement with the recommended pharmacopoeia and manufacturer methods. DSC curves obtained from the tablets suggest compatibility between the drugs, excipients and/or coformulated drugs. The fragmentation pathway of dapsone with mass spectrometry was taken as example, to correlate the thermal decomposition with the resulted MS-EI. The decomposition modes were investigated, and the possible fragmentation pathways were suggested by mass spectrometry. PMID:22792516

Thermoanalytical investigation of some sulfone-containing drugs.

PubMed

Salama, Nahla N; El Ries, Mohammed A; Toubar, Safaa; Abd El Hamid, Maha; Walash, Mohammed I

2012-01-01

The thermal behavior of some sulfone-containing drugs, namely, dapsone (DDS), dimethylsulfone (MSM), and topiramate (TOP) in drug substances, and products were investigated using different thermal techniques. These include thermogravimetry (TGA), derivative thermogravimetry (DTG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The thermogravimetric data allowed the determination of the kinetic parameters: activation energy (E(a)), frequency factor (A), and reaction order (n). The thermal degradation of dapsone and topiramate was followed a first-order kinetic behavior. The calculated data evidenced a zero-order kinetic for dimethylsulfone. The relative thermal stabilities of the studied drugs have been evaluated and follow the order DDS > TOP > MSM. The purity was determined using DSC for the studied compounds, in drug substances and products. The results were in agreement with the recommended pharmacopoeia and manufacturer methods. DSC curves obtained from the tablets suggest compatibility between the drugs, excipients and/or coformulated drugs. The fragmentation pathway of dapsone with mass spectrometry was taken as example, to correlate the thermal decomposition with the resulted MS-EI. The decomposition modes were investigated, and the possible fragmentation pathways were suggested by mass spectrometry.

Moisture drives surface decomposition in thawing tundra

NASA Astrophysics Data System (ADS)

Hicks Pries, Caitlin E.; Schuur, E. A. G.; Vogel, Jason G.; Natali, Susan M.

2013-07-01

Permafrost thaw can affect decomposition rates by changing environmental conditions and litter quality. As permafrost thaws, soils warm and thermokarst (ground subsidence) features form, causing some areas to become wetter while other areas become drier. We used a common substrate to measure how permafrost thaw affects decomposition rates in the surface soil in a natural permafrost thaw gradient and a warming experiment in Healy, Alaska. Permafrost thaw also changes plant community composition. We decomposed 12 plant litters in a common garden to test how changing plant litter inputs would affect decomposition. We combined species' tissue-specific decomposition rates with species and tissue-level estimates of aboveground net primary productivity to calculate community-weighted decomposition constants at both the thaw gradient and warming experiment. Moisture, specifically growing season precipitation and water table depth, was the most significant driver of decomposition. At the gradient, an increase in growing season precipitation from 200 to 300 mm increased mass loss of the common substrate by 100%. At the warming experiment, a decrease in the depth to the water table from 30 to 15 cm increased mass loss by 100%. At the gradient, community-weighted decomposition was 21% faster in extensive than in minimal thaw, but was similar when moss production was included. Overall, the effect of climate change and permafrost thaw on surface soil decomposition are driven more by precipitation and soil environment than by changes to plant communities. Increasing soil moisture is thereby another mechanism by which permafrost thaw can become a positive feedback to climate change.

Influence of Polymer-Clay Interfacial Interactions on the Ignition Time of Polymer/Clay Nanocomposites

PubMed Central

Zope, Indraneel S.; Yu, Zhong-Zhen

2017-01-01

Metal ions present on smectite clay (montmorillonite) platelets have preferential reactivity towards peroxy/alkoxy groups during polyamide 6 (PA6) thermal decomposition. This changes the decomposition pathway and negatively affects the ignition response of PA6. To restrict these interfacial interactions, high-temperature-resistant polymers such as polyetherimide (PEI) and polyimide (PI) were used to coat clay layers. PEI was deposited on clay by solution-precipitation, whereas PI was deposited through a solution-imidization-precipitation technique before melt blending with PA6. The absence of polymer-clay interfacial interactions has resulted in a similar time-to-ignition of PA6/PEI-clay (133 s) and PA6/PI-clay (139 s) composites as neat PA6 (140 s). On the contrary, PA6 with conventional ammonium-based surfactant modified clay has showed a huge drop in time-to-ignition (81 s), as expected. The experimental evidences provided herein reveal the role of the catalytic activity of clay during the early stages of polymer decomposition. PMID:28800095

Flash Pyrolysis of t-Butyl Hydroperoxide and Di-t-butyl Peroxide: Evidence of Roaming in the Decomposition of Organic Hydroperoxides.

PubMed

Jones, Paul J; Riser, Blake; Zhang, Jingsong

2017-10-19

Thermal decomposition of t-butyl hydroperoxide and di-t-butyl peroxide was investigated using flash pyrolysis (in a short reaction time of <100 μs) and vacuum-ultraviolet (λ = 118.2 nm) single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) at temperatures up to 1120 K and quantum computational methods. Acetone and methyl radical were detected as the predominant products in the initial decomposition of di-t-butyl peroxide via O-O bond fission. In the initial dissociation of t-butyl hydroperoxide, acetone, methyl radical, isobutylene, and isobutylene oxide products were identified. The novel detection of the unimolecular formation of isobutylene oxide, as supported by the computational study, was found to proceed via a roaming hydroxyl radical facilitated by a hydrogen-bonded intermediate. This new pathway could provide a new class of reactions to consider in the modeling of the low temperature oxidation of alkanes.

Improved Steroids Detection and Evidence for Their Regiospecific Decompositions Using Anion Attachment Mass Spectrometry.

PubMed

Dumont, Quentin; Bárcenas, Mariana; Dossmann, Héloïse; Bailloux, Isabelle; Buisson, Corinne; Mechin, Nathalie; Molina, Adeline; Lasne, Françoise; Rannulu, Nalaka S; Cole, Richard B

2016-04-05

Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification.

Fluidized-bed reactor modeling for production of silicon by silane pyrolysis

NASA Technical Reports Server (NTRS)

Dudukovic, M. P.; Ramachandran, P. A.; Lai, S.

1986-01-01

An ideal backmixed reactor model (CSTR) and a fluidized bed bubbling reactor model (FBBR) were developed for silane pyrolysis. Silane decomposition is assumed to occur via two pathways: homogeneous decomposition and heterogeneous chemical vapor deposition (CVD). Both models account for homogeneous and heterogeneous silane decomposition, homogeneous nucleation, coagulation and growth by diffusion of fines, scavenging of fines by large particles, elutriation of fines and CVD growth of large seed particles. At present the models do not account for attrition. The preliminary comparison of the model predictions with experimental results shows reasonable agreement. The CSTR model with no adjustable parameter yields a lower bound on fines formed and upper estimate on production rates. The FBBR model overpredicts the formation of fines but could be matched to experimental data by adjusting the unkown jet emulsion exchange efficients. The models clearly indicate that in order to suppress the formation of fines (smoke) good gas-solid contacting in the grid region must be achieved and the formation of the bubbles suppressed.

Decomposition mechanisms and kinetics of novel energetic molecules BNFF-1 and ANFF-1: quantum-chemical modeling.

PubMed

Tsyshevsky, Roman V; Kuklja, Maija M

2013-07-18

Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO₂ homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

Influence of Polymer-Clay Interfacial Interactions on the Ignition Time of Polymer/Clay Nanocomposites.

PubMed

Zope, Indraneel S; Dasari, Aravind; Yu, Zhong-Zhen

2017-08-11

Metal ions present on smectite clay (montmorillonite) platelets have preferential reactivity towards peroxy/alkoxy groups during polyamide 6 (PA6) thermal decomposition. This changes the decomposition pathway and negatively affects the ignition response of PA6. To restrict these interfacial interactions, high-temperature-resistant polymers such as polyetherimide (PEI) and polyimide (PI) were used to coat clay layers. PEI was deposited on clay by solution-precipitation, whereas PI was deposited through a solution-imidization-precipitation technique before melt blending with PA6. The absence of polymer-clay interfacial interactions has resulted in a similar time-to-ignition of PA6/PEI-clay (133 s) and PA6/PI-clay (139 s) composites as neat PA6 (140 s). On the contrary, PA6 with conventional ammonium-based surfactant modified clay has showed a huge drop in time-to-ignition (81 s), as expected. The experimental evidences provided herein reveal the role of the catalytic activity of clay during the early stages of polymer decomposition.

Intramolecular distribution of stable nitrogen and oxygen isotopes of nitrous oxide emitted during coal combustion.

PubMed

Ogawa, Mitsuteru; Yoshida, Naohiro

2005-11-01

The intramolecular distribution of stable isotopes in nitrous oxide that is emitted during coal combustion was analyzed using an isotopic ratio mass spectrometer equipped with a modified ion collector system (IRMS). The coal was combusted in a test furnace fitted with a single burner and the flue gases were collected at the furnace exit following removal of SO(x), NO(x), and H2O in order to avoid the formation of artifact nitrous oxide. The nitrous oxide in the flue gases proved to be enriched in 15N relative to the fuel coal. In air-staged combustion experiments, the staged air ratio was controlled over a range of 0 (unstaged combustion), 20%, and 30%. As the staged air ratio increased, the delta15N and delta18O of the nitrous oxide in the flue gases became depleted. The central nitrogen of the nitrous oxide molecule, N(alpha), was enriched in 15N relative to that occupying the end position of the molecule, N(beta), but this preference, expressed as delta15N(alpha)-delta15N(beta), decreased with the increase in the staged air ratio. Thermal decomposition and hydrogen reduction experiments carried out using a tube reactor allowed qualitative estimates of the kinetic isotope effects that occurred during the decomposition of the nitrous oxide and quantitative estimates of the extent to which the nitrous oxide had decomposed. The site preference of nitrous oxide increased with the extent of the decomposition reactions. Assuming that no site preference exists in nitrous oxide before decomposition, the behavior of nitrous oxide in the test combustion furnace was analyzed using the Rayleigh equation based on a single distillation model. As a result, the extent of decomposition of nitrous oxide was estimated as 0.24-0.26 during the decomposition reaction governed by the thermal decomposition and as 0.35-0.38 during the decomposition reaction governed by the hydrogen reduction in staged combustion. The intramolecular distribution of nitrous oxide can be a valuable parameter to estimate the extent of decomposition reaction and to understand the reaction pathway of nitrous oxide at the high temperature.

Decomposition of metabolic network into functional modules based on the global connectivity structure of reaction graph.

PubMed

Ma, Hong-Wu; Zhao, Xue-Ming; Yuan, Ying-Jin; Zeng, An-Ping

2004-08-12

Metabolic networks are organized in a modular, hierarchical manner. Methods for a rational decomposition of the metabolic network into relatively independent functional subsets are essential to better understand the modularity and organization principle of a large-scale, genome-wide network. Network decomposition is also necessary for functional analysis of metabolism by pathway analysis methods that are often hampered by the problem of combinatorial explosion due to the complexity of metabolic network. Decomposition methods proposed in literature are mainly based on the connection degree of metabolites. To obtain a more reasonable decomposition, the global connectivity structure of metabolic networks should be taken into account. In this work, we use a reaction graph representation of a metabolic network for the identification of its global connectivity structure and for decomposition. A bow-tie connectivity structure similar to that previously discovered for metabolite graph is found also to exist in the reaction graph. Based on this bow-tie structure, a new decomposition method is proposed, which uses a distance definition derived from the path length between two reactions. An hierarchical classification tree is first constructed from the distance matrix among the reactions in the giant strong component of the bow-tie structure. These reactions are then grouped into different subsets based on the hierarchical tree. Reactions in the IN and OUT subsets of the bow-tie structure are subsequently placed in the corresponding subsets according to a 'majority rule'. Compared with the decomposition methods proposed in literature, ours is based on combined properties of the global network structure and local reaction connectivity rather than, primarily, on the connection degree of metabolites. The method is applied to decompose the metabolic network of Escherichia coli. Eleven subsets are obtained. More detailed investigations of the subsets show that reactions in the same subset are really functionally related. The rational decomposition of metabolic networks, and subsequent studies of the subsets, make it more amenable to understand the inherent organization and functionality of metabolic networks at the modular level. http://genome.gbf.de/bioinformatics/

Decomposition characteristics of three different kinds of aquatic macrophytes and their potential application as carbon resource in constructed wetland.

PubMed

Wu, Suqing; He, Shengbing; Zhou, Weili; Gu, Jianya; Huang, Jungchen; Gao, Lei; Zhang, Xu

2017-12-01

Decomposition of aquatic macrophytes usually generates significant influence on aquatic environment. Study on the aquatic macrophytes decomposition may help reusing the aquatic macrophytes litters, as well as controlling the water pollution caused by the decomposition process. This study verified that the decomposition processes of three different kinds of aquatic macrophytes (water hyacinth, hydrilla and cattail) could exert significant influences on water quality of the receiving water, including the change extent of pH, dissolved oxygen (DO), the contents of carbon, nitrogen and phosphorus, etc. The influence of decomposition on water quality and the concentrations of the released chemical materials both followed the order of water hyacinth > hydrilla > cattail. Greater influence was obtained with higher dosage of plant litter addition. The influence also varied with sediment addition. Moreover, nitrogen released from the decomposition of water hyacinth and hydrilla were mainly NH 3 -N and organic nitrogen while those from cattail litter included organic nitrogen and NO 3 - -N. After the decomposition, the average carbon to nitrogen ratio (C/N) in the receiving water was about 2.6 (water hyacinth), 5.3 (hydrilla) and 20.3 (cattail). Therefore, cattail litter might be a potential plant carbon source for denitrification in ecological system of a constructed wetland. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chronic impacts of TiO2 nanoparticles on Populus nigra L. leaf decomposition in freshwater ecosystem.

PubMed

Du, Jingjing; Zhang, Yuyan; Guo, Wei; Li, Ningyun; Gao, Chaoshuai; Cui, Minghui; Lin, Zhongdian; Wei, Mingbao; Zhang, Hongzhong

2018-05-15

Titanium dioxide (TiO 2 ) nanoparticles have been applied in diverse commercial products, which could lead to toxic effects on aquatic microbes and would inhibit some important ecosystem processes. The study aimed to investigate the chronic impacts of TiO 2 nanoparticles with different concentrations (5, 50, and 500 mg L -1 ) on Populus nigra L. leaf decomposition in the freshwater ecosystem. After 50 d of decomposing, a significant decrease in decomposition rates was observed with higher concentrations of TiO 2 nanoparticles. During the period of litter decomposition, exposure of TiO 2 nanoparticles led to decreases in extracellular enzyme activities, which was caused by the reduction of microbial especially fungal biomass. In addition, the diversity and composition of the fungal community associated with litter decomposition were strongly affected by the concentrations of TiO 2 nanoparticles. The diversity and composition of the fungal community associated with litter decomposition was strongly affected. The abundance of Tricladium chaetocladium decreased with the increasing concentrations of TiO 2 nanoparticles, indicating the little contribution of the species to the litter decomposition. In conclusion, this study provided the evidence for the chronic exposure effects of TiO 2 nanoparticles on the litter decomposition and further the functions of freshwater ecosystems. Copyright © 2018 Elsevier B.V. All rights reserved.

Decomposition of birch leaves in heavily polluted industrial barrens: relative importance of leaf quality and site of exposure.

PubMed

Kozlov, Mikhail V; Zvereva, Elena L

2015-07-01

The decrease in litter decomposition rate in polluted habitats is well documented, but the factors that explain the observed variation in the magnitude of this pollution effect on litter decomposition remain poorly understood. We explored effects of environmental conditions and leaf quality on decomposition rate of mountain birch (Betula pubescens ssp. czerepanovii) leaves in a heavily polluted industrial barren near the nickel-copper smelter at Monchegorsk. Litter bags filled with leaves collected from two heavily polluted barren sites and from two control forest sites were buried at 2.5-cm depth and exposed for 2 and 4 years at each of these four sites. The relative mass loss of native leaves in the industrial barren during 2 years of exposure was reduced to 49% of the loss observed in the unpolluted forest. We found a similar reduction in mass loss when leaves from control sites were exposed to polluted sites and when leaves from polluted sites were exposed to control sites. We conclude that the reduction in leaf litter decomposition in an industrial barren is caused by pollution-induced changes in both environmental conditions and leaf quality. This reduction is much smaller than expected, given the four-fold decrease in soil microbial activity and nearly complete extinction of saprophagous invertebrates in the polluted soil. We suggest that a longer snowless period and higher spring and summer temperatures at the barren sites have partially counterbalanced the adverse effects caused by the toxicity of metal pollutants.

Rate of warming affects temperature sensitivity of anaerobic peat decomposition and greenhouse gas production.

PubMed

Sihi, Debjani; Inglett, Patrick W; Gerber, Stefan; Inglett, Kanika S

2018-01-01

Temperature sensitivity of anaerobic carbon mineralization in wetlands remains poorly represented in most climate models and is especially unconstrained for warmer subtropical and tropical systems which account for a large proportion of global methane emissions. Several studies of experimental warming have documented thermal acclimation of soil respiration involving adjustments in microbial physiology or carbon use efficiency (CUE), with an initial decline in CUE with warming followed by a partial recovery in CUE at a later stage. The variable CUE implies that the rate of warming may impact microbial acclimation and the rate of carbon-dioxide (CO 2 ) and methane (CH 4 ) production. Here, we assessed the effects of warming rate on the decomposition of subtropical peats, by applying either a large single-step (10°C within a day) or a slow ramping (0.1°C/day for 100 days) temperature increase. The extent of thermal acclimation was tested by monitoring CO 2 and CH 4 production, CUE, and microbial biomass. Total gaseous C loss, CUE, and MBC were greater in the slow (ramp) warming treatment. However, greater values of CH 4 -C:CO 2 -C ratios lead to a greater global warming potential in the fast (step) warming treatment. The effect of gradual warming on decomposition was more pronounced in recalcitrant and nutrient-limited soils. Stable carbon isotopes of CH 4 and CO 2 further indicated the possibility of different carbon processing pathways under the contrasting warming rates. Different responses in fast vs. slow warming treatment combined with different endpoints may indicate alternate pathways with long-term consequences. Incorporations of experimental results into organic matter decomposition models suggest that parameter uncertainties in CUE and CH 4 -C:CO 2 -C ratios have a larger impact on long-term soil organic carbon and global warming potential than uncertainty in model structure, and shows that particular rates of warming are central to understand the response of wetland soils to global climate change. © 2017 John Wiley & Sons Ltd.

Analysis of Self-Associating Proteins by Singular Value Decomposition of Solution Scattering Data

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

Williamson, Tim E.; Craig, Bruce A.; Kondrashkina, Elena

2008-07-08

We describe a method by which a single experiment can reveal both association model (pathway and constants) and low-resolution structures of a self-associating system. Small-angle scattering data are collected from solutions at a range of concentrations. These scattering data curves are mass-weighted linear combinations of the scattering from each oligomer. Singular value decomposition of the data yields a set of basis vectors from which the scattering curve for each oligomer is reconstructed using coefficients that depend on the association model. A search identifies the association pathway and constants that provide the best agreement between reconstructed and observed data. Using simulatedmore » data with realistic noise, our method finds the correct pathway and association constants. Depending on the simulation parameters, reconstructed curves for each oligomer differ from the ideal by 0.050.99% in median absolute relative deviation. The reconstructed scattering curves are fundamental to further analysis, including interatomic distance distribution calculation and low-resolution ab initio shape reconstruction of each oligomer in solution. This method can be applied to x-ray or neutron scattering data from small angles to moderate (or higher) resolution. Data can be taken under physiological conditions, or particular conditions (e.g., temperature) can be varied to extract fundamental association parameters ({Delta}H{sub ass}, S{sub ass}).« less

Morphological decomposition of 2-D binary shapes into convex polygons: a heuristic algorithm.

PubMed

Xu, J

2001-01-01

In many morphological shape decomposition algorithms, either a shape can only be decomposed into shape components of extremely simple forms or a time consuming search process is employed to determine a decomposition. In this paper, we present a morphological shape decomposition algorithm that decomposes a two-dimensional (2-D) binary shape into a collection of convex polygonal components. A single convex polygonal approximation for a given image is first identified. This first component is determined incrementally by selecting a sequence of basic shape primitives. These shape primitives are chosen based on shape information extracted from the given shape at different scale levels. Additional shape components are identified recursively from the difference image between the given image and the first component. Simple operations are used to repair certain concavities caused by the set difference operation. The resulting hierarchical structure provides descriptions for the given shape at different detail levels. The experiments show that the decomposition results produced by the algorithm seem to be in good agreement with the natural structures of the given shapes. The computational cost of the algorithm is significantly lower than that of an earlier search-based convex decomposition algorithm. Compared to nonconvex decomposition algorithms, our algorithm allows accurate approximations for the given shapes at low coding costs.

Stability of cyanocobalamin in sugar-coated tablets.

PubMed

Ohmori, Shinji; Kataoka, Masumi; Koyama, Hiroyoshi

2007-06-07

The purpose of this study was to clarify the stability of cyanocobalamin (VB(12)-CN) in sugar-coated tablets containing fursultiamine hydrochloride (TTFD-HCl), riboflavin (VB(2)), and pyridoxine hydrochloride (VB(6)), and to identify the factors affecting the stability of VB(12)-CN in these sugar-coated tablets. The stability of VB(12)-CN was investigated using high-performance liquid chromatography while decomposition was evaluated kinetically. The decomposition of VB(12)-CN in sugar-coated tablets with high equilibrium relative humidity (more than 60%) under closed conditions showed complex kinetics and followed an Avrami-Erofe'ev equation, which expresses a random nucleation (two-dimensional growth of nuclei) model. We showed that equilibrium relative humidity, the incorporation of VB(2) and VB(6), and sugar coating, are the main factors influencing decomposition and that these factors cause the complex decomposition kinetics.

Girls' Spatial Skills and Arithmetic Strategies in First Grade as Predictors of Fifth-Grade Analytical Math Reasoning

ERIC Educational Resources Information Center

Casey, Beth M.; Lombardi, Caitlin McPherran; Pollock, Amanda; Fineman, Bonnie; Pezaris, Elizabeth

2017-01-01

This study investigated longitudinal pathways leading from early spatial skills in first-grade girls to their fifth-grade analytical math reasoning abilities (N = 138). First-grade assessments included spatial skills, verbal skills, addition/subtraction skills, and frequency of choice of a decomposition or retrieval strategy on the…

Supercritical Catalytic Cracking of Hydrocarbon Feeds Insight

DTIC Science & Technology

2016-04-21

University teamed with Spectral Energies, LLC to develop appropriate spatiotemporal imaging capabilities in single body zeolites to describe beneficial...We demonstrated the ability to follow in a spatiotemporal fashion, the decomposition of the structure-directing agent used to template the zeolite ...appropriate spatiotemporal imaging capabilities in single body zeolites to describe beneficial and parasitic catalytic cracking pathways. Beneficial

Thermal Decomposition Of Hydroxylamine Nitrate

NASA Astrophysics Data System (ADS)

Oxley, Jimmie C.; Brower, Kay R.

1988-05-01

used hydroxylamine nitrate decomposes within a few minutes in the temperature range 130-140°C. Added ammonium ion is converted to N2, while hydrazinium ion is converted to HN3. Nitrous acid is an intermediate and its formation is rate-determining. A hygride transfer process is postulated. The reaction pathways have been elucidated by use of N tracers.

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

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

Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore » C-NO{sub 2} to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.« less

Mortality inequality in populations with equal life expectancy: Arriaga's decomposition method in SAS, Stata, and Excel.

PubMed

Auger, Nathalie; Feuillet, Pascaline; Martel, Sylvie; Lo, Ernest; Barry, Amadou D; Harper, Sam

2014-08-01

Life expectancy is used to measure population health, but large differences in mortality can be masked even when there is no life expectancy gap. We demonstrate how Arriaga's decomposition method can be used to assess inequality in mortality between populations with near equal life expectancy. We calculated life expectancy at birth for Quebec and the rest of Canada from 2005 to 2009 using life tables and partitioned the gap between both populations into age and cause-specific components using Arriaga's method. The life expectancy gap between Quebec and Canada was negligible (<0.1 years). Decomposition of the gap showed that higher lung cancer mortality in Quebec was offset by cardiovascular mortality in the rest of Canada, resulting in identical life expectancy in both groups. Lung cancer in Quebec had a greater impact at early ages, whereas cardiovascular mortality in Canada had a greater impact at older ages. Despite the absence of a gap, we demonstrate using decomposition analyses how lung cancer at early ages lowered life expectancy in Quebec, whereas cardiovascular causes at older ages lowered life expectancy in Canada. We provide SAS/Stata code and an Excel spreadsheeet to facilitate application of Arriaga's method to other settings. Copyright © 2014 Elsevier Inc. All rights reserved.

A density functional theory study on the adsorption and decomposition of methanol on B12N12 fullerene-like nanocage

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-03-01

The adsorption and dissociative reaction of methanol on B12N12 fullerene-like nanocage is investigated by using density functional calculations. Equilibrium geometries, adsorption energies, and electronic properties of CH3OH adsorption on the surface of the B12N12 were identified. The calculated adsorption energies range from -1.3 to -34.9 kcal/mol. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3OH. The mechanism of methanol decomposition via CO and OH bond scissions is also studied. The results indicate that OH bond scission is the most favorable pathway on the B12N12 surface.

Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

NASA Astrophysics Data System (ADS)

Veals, Jeffrey D.; Thompson, Donald L.

2014-04-01

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.

PubMed

Cobos, C J; Sölter, L; Tellbach, E; Troe, J

2014-06-07

The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.

Flux Analysis of Free Amino Sugars and Amino Acids in Soils by Isotope Tracing with a Novel Liquid Chromatography/High Resolution Mass Spectrometry Platform.

PubMed

Hu, Yuntao; Zheng, Qing; Wanek, Wolfgang

2017-09-05

Soil fluxomics analysis can provide pivotal information for understanding soil biochemical pathways and their regulation, but direct measurement methods are rare. Here, we describe an approach to measure soil extracellular metabolite (amino sugar and amino acid) concentrations and fluxes based on a 15 N isotope pool dilution technique via liquid chromatography and high-resolution mass spectrometry. We produced commercially unavailable 15 N and 13 C labeled amino sugars and amino acids by hydrolyzing peptidoglycan isolated from isotopically labeled bacterial biomass and used them as tracers ( 15 N) and internal standards ( 13 C). High-resolution (Orbitrap Exactive) MS with a resolution of 50 000 allowed us to separate different stable isotope labeled analogues across a large range of metabolites. The utilization of 13 C internal standards greatly improved the accuracy and reliability of absolute quantification. We successfully applied this method to two types of soils and quantified the extracellular gross fluxes of 2 amino sugars, 18 amino acids, and 4 amino acid enantiomers. Compared to the influx and efflux rates of most amino acids, similar ones were found for glucosamine, indicating that this amino sugar is released through peptidoglycan and chitin decomposition and serves as an important nitrogen source for soil microorganisms. d-Alanine and d-glutamic acid derived from peptidoglycan decomposition exhibited similar turnover rates as their l-enantiomers. This novel approach offers new strategies to advance our understanding of the production and transformation pathways of soil organic N metabolites, including the unknown contributions of peptidoglycan and chitin decomposition to soil organic N cycling.

Decomposition of energetic molecules by interfacing with a catalytic oxide: opportunities and challenges

NASA Astrophysics Data System (ADS)

Wang, Fenggong; Tsyshevsky, Roman; Zverev, Anton; Mitrofanov, Anatoly; Kuklja, Maija

Organic-inorganic interfaces provide both intrigues and opportunities for designing systems that possess properties and functionalities inaccessible by each individual component. In particular, mixing with a photocatalyst may significantly affect the adsorption, decomposition, and photoresponse of organic molecules. Here, we choose the formulation of TiO2 and trinitrotoluene (TNT), a highly catalytic oxide and a prominent explosive, as a prototypical example to explore the interaction at the interface on the photosensitivity of energetic materials. We show that, whether or not a catalytic oxide additive can help molecular decompositions under light illumination depends largely on the band alignment between the oxide surface and the energetic molecule. Furthermore, an oxygen vacancy can lead to the electron density transfer from the surface to the energetic molecules, causing an enhancement of the bonding between molecules and surface and a reduction of the molecular decomposition activation barriers.

Stress-induced activation of decomposition of organic explosives: a simple way to understand.

PubMed

Zhang, Chaoyang

2013-01-01

We provide a very simply way to understand the stress-induced activation of decomposition of organic explosives by taking the simplest explosive molecule nitromethane (NM) as a prototype and constraining one or two NM molecules in a shell to represent the condensed phrase of NM against the stress caused by tension and compression, sliding and rotational shear, and imperfection. The results show that the stress loaded on NM molecule can always reduce the barriers of its decomposition. We think the origin of this stress-induced activation is due to the increased repulsive intra- and/or inter- molecular interaction potentials in explosives resulted from the stress, whose release is positive to accelerate the decomposition. Besides, by these models, we can understand that the explosives in gaseous state are easier to analyze than those in condensed state and the voids in condensed explosives make them more sensitive to external stimuli relative to the perfect crystals.

Adaptive variational mode decomposition method for signal processing based on mode characteristic

NASA Astrophysics Data System (ADS)

Lian, Jijian; Liu, Zhuo; Wang, Haijun; Dong, Xiaofeng

2018-07-01

Variational mode decomposition is a completely non-recursive decomposition model, where all the modes are extracted concurrently. However, the model requires a preset mode number, which limits the adaptability of the method since a large deviation in the number of mode set will cause the discard or mixing of the mode. Hence, a method called Adaptive Variational Mode Decomposition (AVMD) was proposed to automatically determine the mode number based on the characteristic of intrinsic mode function. The method was used to analyze the simulation signals and the measured signals in the hydropower plant. Comparisons have also been conducted to evaluate the performance by using VMD, EMD and EWT. It is indicated that the proposed method has strong adaptability and is robust to noise. It can determine the mode number appropriately without modulation even when the signal frequencies are relatively close.

Study of the solid-phase thermal decomposition of NTO using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS)

NASA Technical Reports Server (NTRS)

Minier, L.; Behrens, R.; Burkey, T. J.

1997-01-01

The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log(sub 10) p(torr) = 12.5137 + 6,296.553(1/t(k)) and the Delta-H(sub subl) = 28.71 +/- 0.07 kcal/mol (120.01 +/- 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-C-13, NTO-1,2- (15)N2 and NTO-(2)H2. Identification of the products show the major gaseous products to be N2, CO2, NO, HNCO, H2O and some N2O, CO, HCN and NH3. The N2 is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO2 is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C(2.1)H(.26)N(2.9)O and FTIR analysis suggests that the residue is polyurea- and polycarbamate- like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H2O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

Thermodynamic Changes in the Coal Matrix - Gas - Moisture System Under Pressure Release and Phase Transformations of Gas Hydrates

NASA Astrophysics Data System (ADS)

Dyrdin, V. V.; Smirnov, V. G.; Kim, T. L.; Manakov, A. Yu.; Fofanov, A. A.; Kartopolova, I. S.

2017-06-01

The physical processes occurring in the coal - natural gas system under the gas pressure release were studied experimentally. The possibility of gas hydrates presence in the inner space of natural coal was shown, which decomposition leads to an increase in the amount of gas passing into the free state. The decomposition of gas hydrates can be caused either by the seam temperature increase or the pressure decrease to lower than the gas hydrates equilibrium curve. The contribution of methane released during gas hydrates decomposition should be taken into account in the design of safe mining technologies for coal seams prone to gas dynamic phenomena.

Can visible light impact litter decomposition under pollution of ZnO nanoparticles?

PubMed

Du, Jingjing; Zhang, Yuyan; Liu, Lina; Qv, Mingxiang; Lv, Yanna; Yin, Yifei; Zhou, Yinfei; Cui, Minghui; Zhu, Yanfeng; Zhang, Hongzhong

2017-11-01

ZnO nanoparticles is one of the most used materials in a wide range including antibacterial coating, electronic device, and personal care products. With the development of nanotechnology, ecotoxicology of ZnO nanoparticles has been received increasing attention. To assess the phototoxicity of ZnO nanoparticles in aquatic ecosystem, microcosm experiments were conducted on Populus nigra L. leaf litter decomposition under combined effect of ZnO nanoparticles and visible light radiation. Litter decomposition rate, pH value, extracellular enzyme activity, as well as the relative contributions of fungal community to litter decomposition were studied. Results showed that long-term exposure to ZnO nanoparticles and visible light led to a significant decrease in litter decomposition rate (0.26 m -1 vs 0.45 m -1 ), and visible light would increase the inhibitory effect (0.24 m -1 ), which caused significant decrease in pH value of litter cultures, fungal sporulation rate, as well as most extracellular enzyme activities. The phototoxicity of ZnO nanoparticles also showed impacts on fungal community composition, especially on the genus of Varicosporium, whose abundance was significantly and positively related to decomposition rate. In conclusion, our study provides the evidence for negatively effects of ZnO NPs photocatalysis on ecological process of litter decomposition and highlights the contribution of visible light radiation to nanoparticles toxicity in freshwater ecosystems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Micronized copper wood preservatives: an efficiency and potential health risk assessment for copper-based nanoparticles.

PubMed

Civardi, Chiara; Schwarze, Francis W M R; Wick, Peter

2015-05-01

Copper (Cu) is an essential biocide for wood protection, but fails to protect wood against Cu-tolerant wood-destroying fungi. Recently Cu particles (size range: 1 nm-25 μm) were introduced to the wood preservation market. The new generation of preservatives with Cu-based nanoparticles (Cu-based NPs) is reputedly more efficient against wood-destroying fungi than conventional formulations. Therefore, it has the potential to become one of the largest end uses for wood products worldwide. However, during decomposition of treated wood Cu-based NPs and/or their derivate may accumulate in the mycelium of Cu-tolerant fungi and end up in their spores that are dispersed into the environment. Inhaled Cu-loaded spores can cause harm and could become a potential risk for human health. We collected evidence and discuss the implications of the release of Cu-based NPs by wood-destroying fungi and highlight the exposure pathways and subsequent magnitude of health impact. Copyright © 2015 Elsevier Ltd. All rights reserved.

Decomposition and N cycling changes in redwood forests caused by sudden oak death

Treesearch

Richard C. Cobb; David M. Rizzo

2012-01-01

Phytophthora ramorum is an emergent pathogen in redwood forests which causes the disease sudden oak death. Although the disease does not kill coast redwood (Sequoia sempervirens), extensive and rapid mortality of tanoak (Notholithocarpus densiflorus) has removed this...

Effects of long-term continuous cropping on soil nematode community and soil condition associated with replant problem in strawberry habitat

PubMed Central

Li, Xingyue; Lewis, Edwin E.; Liu, Qizhi; Li, Heqin; Bai, Chunqi; Wang, Yuzhu

2016-01-01

Continuous cropping changes soil physiochemical parameters, enzymes and microorganism communities, causing “replant problem” in strawberry cultivation. We hypothesized that soil nematode community would reflect the changes in soil conditions caused by long-term continuous cropping, in ways that are consistent and predictable. To test this hypothesis, we studied the soil nematode communities and several soil parameters, including the concentration of soil phenolic acids, organic matter and nitrogen levels, in strawberry greenhouse under continuous-cropping for five different durations. Soil pH significantly decreased, and four phenolic acids, i.e., p-hydroxybenzoic acid, ferulic acid, cinnamic acid and p-coumaric acid, accumulated with time under continuous cropping. The four phenolic acids were highly toxic to Acrobeloides spp., the eudominant genus in non-continuous cropping, causing it to reduce to a resident genus after seven-years of continuous cropping. Decreased nematode diversity indicated loss of ecosystem stability and sustainability because of continuous-cropping practice. Moreover, the dominant decomposition pathway was altered from bacterial to fungal under continuous cropping. Our results suggest that along with the continuous-cropping time in strawberry habitat, the soil food web is disturbed, and the available plant nutrition as well as the general health of the soil deteriorates; these changes can be indicated by soil nematode community. PMID:27506379

Characteristic of retained austenite decomposition during tempering and its effect on impact toughness in SA508 Gr.3 steel

NASA Astrophysics Data System (ADS)

Yan, Guanghua; Han, Lizhan; Li, Chuanwei; Luo, Xiaomeng; Gu, Jianfeng

2017-01-01

Retained austenite(RA) usually presents in the quenched Nuclear Pressure-Vessel SA508 Gr.3 steel. In the present work, the characteristic of RA decomposition and its effect on the impact toughness were investigated by microstructure observation, dilatometric experiments and Charpy impact tests. The results show that the RA transformed into martensite and bainite during tempering at 230 °C and 400 °C respectively, while mixture of long rod carbides and ferrite formed at 650 °C. The long rod carbides formed from RA decomposition decrease the critical cleavage stress for initiation of micro-cracks, and deteriorate the impact toughness of the steel. Pre-tempering at a low temperature such as 230 °C or 400 °C leading to the decomposition of RA into martensite or baintie can eliminate the deterioration of the toughness caused by direct decomposition into long rod carbides. The absorbed energy indicate that pre-tempering at 400 °C can drive dramatically improvement in the toughness of the steel.

Effects of Solute Concentrations on Kinetic Pathways in Ni-Al-Cr Alloys

NASA Technical Reports Server (NTRS)

Booth-Morrison, Christopher; Weninger, Jessica; Sudbrack, Chantal K.; Mao, Zugang; Seidman, David N.; Noebe, Ronald D.

2008-01-01

The kinetic pathways resulting from the formation of coherent gamma'-precipitates from the gamma-matrix are studied for two Ni-Al-Cr alloys with similar gamma'-precipitate volume fractions at 873 K. The details of the phase decompositions of Ni-7.5Al-8.5Cr at.% and Ni-5.2Al-14.2Cr at.% for aging times from 1/6 to 1024 h are investigated by atom-probe tomography, and are found to differ significantly from a mean-field description of coarsening. The morphologies of the gamma'-precipitates of the alloys are similar, though the degrees of gamma'-precipitate coagulation and coalescence differ. Quantification within the framework of classical nucleation theory reveals that differences in the chemical driving forces for phase decomposition result in differences in the nucleation behavior of the two alloys. The temporal evolution of the gamma'-precipitate average radii and the gamma-matrix supersaturations follow the predictions of classical coarsening models. The compositional trajectories of the gamma-matrix phases of the alloys are found to follow approximately the equilibrium tie-lines, while the trajectories of the gamma'-precipitates do not, resulting in significant differences in the partitioning ratios of the solute elements.

An analysis of gene expression data involving examination of signaling pathways activation reveals new insights into the mechanism of action of minoxidil topical foam in men with androgenetic alopecia

PubMed Central

Wu, Jeff; Pappas, Apostolos; Mirmirani, Paradi; McCormick, Thomas S.; Cooper, Kevin D.; Schastnaya, Jane; Ozerov, Ivan V.; Aliper, Alexander; Zhavoronkov, Alex

2017-01-01

ABSTRACT Androgenetic alopecia is the most common form of hair loss. Minoxidil has been approved for the treatment of hair loss, however its mechanism of action is still not fully clarified. In this study, we aimed to elucidate the effects of 5% minoxidil topical foam on gene expression and activation of signaling pathways in vertex and frontal scalp of men with androgenetic alopecia. We identified regional variations in gene expression and perturbed signaling pathways using in silico Pathway Activation Network Decomposition Analysis (iPANDA) before and after treatment with minoxidil. Vertex and frontal scalp of patients showed a generally similar response to minoxidil. Both scalp regions showed upregulation of genes that encode keratin associated proteins and downregulation of ILK, Akt, and MAPK signaling pathways after minoxidil treatment. Our results provide new insights into the mechanism of action of minoxidil topical foam in men with androgenetic alopecia. PMID:28594262

An analysis of gene expression data involving examination of signaling pathways activation reveals new insights into the mechanism of action of minoxidil topical foam in men with androgenetic alopecia.

PubMed

Stamatas, Georgios N; Wu, Jeff; Pappas, Apostolos; Mirmirani, Paradi; McCormick, Thomas S; Cooper, Kevin D; Consolo, Mary; Schastnaya, Jane; Ozerov, Ivan V; Aliper, Alexander; Zhavoronkov, Alex

2017-01-01

Androgenetic alopecia is the most common form of hair loss. Minoxidil has been approved for the treatment of hair loss, however its mechanism of action is still not fully clarified. In this study, we aimed to elucidate the effects of 5% minoxidil topical foam on gene expression and activation of signaling pathways in vertex and frontal scalp of men with androgenetic alopecia. We identified regional variations in gene expression and perturbed signaling pathways using in silico Pathway Activation Network Decomposition Analysis (iPANDA) before and after treatment with minoxidil. Vertex and frontal scalp of patients showed a generally similar response to minoxidil. Both scalp regions showed upregulation of genes that encode keratin associated proteins and downregulation of ILK, Akt, and MAPK signaling pathways after minoxidil treatment. Our results provide new insights into the mechanism of action of minoxidil topical foam in men with androgenetic alopecia.

Bioaugmentation of Syntrophic Acetate-Oxidizing Culture in Biogas Reactors Exposed to Increasing Levels of Ammonia

PubMed Central

Westerholm, Maria; Levén, Lotta

2012-01-01

The importance of syntrophic acetate oxidation for process stability in methanogenic systems operating at high ammonia concentrations has previously been emphasized. In this study we investigated bioaugmentation of syntrophic acetate-oxidizing (SAO) cultures as a possible method for decreasing the adaptation period of biogas reactors operating at gradually increased ammonia concentrations (1.5 to 11 g NH4+-N/liter). Whole stillage and cattle manure were codigested semicontinuously for about 460 days in four mesophilic anaerobic laboratory-scale reactors, and a fixed volume of SAO culture was added daily to two of the reactors. Reactor performance was evaluated in terms of biogas productivity, methane content, pH, alkalinity, and volatile fatty acid (VFA) content. The decomposition pathway of acetate was analyzed by isotopic tracer experiments, and population dynamics were monitored by quantitative PCR analyses. A shift in dominance from aceticlastic methanogenesis to SAO occurred simultaneously in all reactors, indicating no influence by bioaugmentation on the prevailing pathway. Higher abundances of Clostridium ultunense and Tepidanaerobacter acetatoxydans were associated with bioaugmentation, but no influence on Syntrophaceticus schinkii or the methanogenic population was distinguished. Overloading or accumulation of VFA did not cause notable dynamic effects on the population. Instead, the ammonia concentration had a substantial impact on the abundance level of the microorganisms surveyed. The addition of SAO culture did not affect process performance or stability against ammonia inhibition, and all four reactors deteriorated at high ammonia concentrations. Consequently, these findings further demonstrate the strong influence of ammonia on the methane-producing consortia and on the representative methanization pathway in mesophilic biogas reactors. PMID:22923397

Effect of water level drawdown on decomposition in boreal peatlands

NASA Astrophysics Data System (ADS)

Straková, Petra; Penttilä, Timo; Laiho, Raija

2010-05-01

Plant litter production and decomposition are key processes in element cycling in most ecosystems. In peatlands, there has been a long-term imbalance between litter production and decay caused by high water levels (WL) and consequent anoxia. This has resulted in peatlands being a significant sink of carbon (C) from the atmosphere. However, peatlands are experiencing both "natural" (global climate change) and anthropogenic (ditching) changes that threaten their ability to retain this ecosystem identity and function. Many of these alterations can be traced back to WL drawdown, which can cause increased aeration, higher acidity, falling temperatures, and a greater probability of drought. Such changes are also associated with an increasing decomposition rate, and therefore a greater amount of C released back to the atmosphere. Yet studies about how the overall C balance of peatlands will be affected have come up with conflicting conclusions, demonstrating that the C store could increase, decrease, or remain static. A factor that has been largely overlooked is the change in litter type composition following persistent WL drawdown. It is the aim of our study, then, to help to resolve this issue. We studied the effects of short-term (ca. 4 years) and long-term (ca. 40 years) persistent WL drawdown on the decomposition of numerous types of above-ground and below-ground plant litters at three boreal peatland sites: bog, oligotrophic fen and mesotrophic fen. We thus believe that enough permutations have been created to obtain a good assessment of how each factor, site nutrient level, WL regime, and litter type composition, influences decomposition. We used the litter bag method to measure the decomposition rates: placed measured amounts of plant litter, or cellulose strips as a control, into closed mesh bags, and installed the bags in the natural environment for decomposition for each litter type for varying amounts of time. Following litter bag recovery, the litter was cleaned of excess debris and analyzed for changes in mass, enzyme activity, mesofauna presence, and microbial community composition, among other things. The experiment has a run-time of ten years, the results from the first two years are presented in the poster.

Decomposition of energetic chemicals contaminated with iron or stainless steel.

PubMed

Chervin, Sima; Bodman, Glenn T; Barnhart, Richard W

2006-03-17

Contamination of chemicals or reaction mixtures with iron or stainless steel is likely to take place during chemical processing. If energetic and thermally unstable chemicals are involved in a manufacturing process, contamination with iron or stainless steel can impact the decomposition characteristics of these chemicals and, subsequently, the safety of the processes, and should be investigated. The goal of this project was to undertake a systematic approach to study the impact of iron or stainless steel contamination on the decomposition characteristics of different chemical classes. Differential scanning calorimetry (DSC) was used to study the decomposition reaction by testing each chemical pure, and in mixtures with iron and stainless steel. The following classes of energetic chemicals were investigated: nitrobenzenes, tetrazoles, hydrazines, hydroxylamines and oximes, sulfonic acid derivatives and monomers. The following non-energetic groups were investigated for contributing effects: halogens, hydroxyls, amines, amides, nitriles, sulfonic acid esters, carbonyl halides and salts of hydrochloric acid. Based on the results obtained, conclusions were drawn regarding the sensitivity of the decomposition reaction to contamination with iron and stainless steel for the chemical classes listed above. It was demonstrated that the most sensitive classes are hydrazines and hydroxylamines/oximes. Contamination of these chemicals with iron or stainless steel not only destabilizes them, leading to decomposition at significantly lower temperatures, but also sometimes causes increased severity of the decomposition. The sensitivity of nitrobenzenes to contamination with iron or stainless steel depended upon the presence of other contributing groups: the presence of such groups as acid chlorides or chlorine/fluorine significantly increased the effect of contamination on decomposition characteristics of nitrobenzenes. The decomposition of sulfonic acid derivatives and tetrazoles was not impacted by presence of iron or stainless steel.

Hydrolytic stability of biomolecules at high temperatures and its implication for life at 250 °C

NASA Astrophysics Data System (ADS)

White, Robert H.

1984-08-01

The upper temperature at which a living system can exist is limited by the hydrolytic breakdown rate of its chemical constituents. The peptide bonds of proteins, the phosphodiester and N-glycosyl bonds in RNA and DNA, and the pyrophosphate and N-glycosyl bonds in nucleotides such as ATP and NAD are among the more important bonds that will undergo hydrolysis. The decomposition of biomolecules via non-hydrolytic pathways such as decarboxylations and dehydrations may also be critical factors in determining this upper temperature limit. Baross and Deming1 recently reported `black smoker' bacteria, which they isolated from deep-sea hydrothermal vents, growing at 250 °C. Here I have attempted to establish the rates for the hydrolysis and/or decomposition of critical biomolecules to determine their ability to exist at this temperature. My results clearly indicate that if these organisms exist, and if their metabolic reactions occur in an aqueous environment, they could not survive at this temperature if they were composed of biomolecules such as proteins and nucleic acids, due to the very rapid rate of decomposition of such molecules.

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

PubMed

Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

2015-02-01

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

Production of furfural from palm oil empty fruit bunches: kinetic model comparation

NASA Astrophysics Data System (ADS)

Panjaitan, J. R. H.; Monica, S.; Gozan, M.

2017-05-01

Furfural is a chemical compound that can be applied to pharmaceuticals, cosmetics, resins and cleaning compound which can be produced by acid hydrolysis of biomass. Indonesia’s demand for furfural in 2010 reached 790 tons that still imported mostly 72% from China. In this study, reaction kinetic models of furfural production from oil palm empty fruit bunches with submitting acid catalyst at the beginning of the experiment will be determine. Kinetic data will be obtained from hydrolysis of empty oil palm bunches using sulfuric acid catalyst 3% at temperature 170°C, 180°C and 190°C for 20 minutes. From this study, the kinetic model to describe the production of furfural is the kinetic model where generally hydrolysis reaction with an acid catalyst in hemicellulose and furfural will produce the same decomposition product which is formic acid with different reaction pathways. The activation energy obtained for the formation of furfural, the formation of decomposition products from furfural and the formation of decomposition products from hemicellulose is 8.240 kJ/mol, 19.912 kJ/mol and -39.267 kJ / mol.

Solventless synthesis, morphology, structure and magnetic properties of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Das, Bratati; Kusz, Joachim; Reddy, V. Raghavendra; Zubko, Maciej; Bhattacharjee, Ashis

2017-12-01

In this study we report the solventless synthesis of iron oxide through thermal decomposition of acetyl ferrocene as well as its mixtures with maliec anhydride and characterization of the synthesized product by various comprehensive physical techniques. Morphology, size and structure of the reaction products were investigated by scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction technique, respectively. Physical characterization techniques like FT-IR spectroscopy, dc magnetization study as well as 57Fe Mössbauer spectroscopy were employed to characterize the magnetic property of the product. The results observed from these studies unequivocally established that the synthesized materials are hematite. Thermal decomposition has been studied with the help of thermogravimetry. Reaction pathway for synthesis of hematite has been proposed. It is noted that maliec anhydride in the solid reaction environment as well as the gaseous reaction atmosphere strongly affect the reaction yield as well as the particle size. In general, a method of preparing hematite nanoparticles through solventless thermal decomposition technique using organometallic compounds and the possible use of reaction promoter have been discussed in detail.

Modular decomposition of metabolic reaction networks based on flux analysis and pathway projection.

PubMed

Yoon, Jeongah; Si, Yaguang; Nolan, Ryan; Lee, Kyongbum

2007-09-15

The rational decomposition of biochemical networks into sub-structures has emerged as a useful approach to study the design of these complex systems. A biochemical network is characterized by an inhomogeneous connectivity distribution, which gives rise to several organizational features, including modularity. To what extent the connectivity-based modules reflect the functional organization of the network remains to be further explored. In this work, we examine the influence of physiological perturbations on the modular organization of cellular metabolism. Modules were characterized for two model systems, liver and adipocyte primary metabolism, by applying an algorithm for top-down partition of directed graphs with non-uniform edge weights. The weights were set by the engagement of the corresponding reactions as expressed by the flux distribution. For the base case of the fasted rat liver, three modules were found, carrying out the following biochemical transformations: ketone body production, glucose synthesis and transamination. This basic organization was further modified when different flux distributions were applied that describe the liver's metabolic response to whole body inflammation. For the fully mature adipocyte, only a single module was observed, integrating all of the major pathways needed for lipid storage. Weaker levels of integration between the pathways were found for the early stages of adipocyte differentiation. Our results underscore the inhomogeneous distribution of both connectivity and connection strengths, and suggest that global activity data such as the flux distribution can be used to study the organizational flexibility of cellular metabolism. Supplementary data are available at Bioinformatics online.

Thermal Decomposition Behaviors and Burning Characteristics of AN/Nitramine-Based Composite Propellant

NASA Astrophysics Data System (ADS)

Naya, Tomoki; Kohga, Makoto

2015-04-01

Ammonium nitrate (AN) has attracted much attention due to its clean burning nature as an oxidizer. However, an AN-based composite propellant has the disadvantages of low burning rate and poor ignitability. In this study, we added nitramine of cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX) as a high-energy material to AN propellants to overcome these disadvantages. The thermal decomposition and burning rate characteristics of the prepared propellants were examined as the ratio of AN and nitramine was varied. In the thermal decomposition process, AN/RDX propellants showed unique mass loss peaks in the lower temperature range that were not observed for AN or RDX propellants alone. AN and RDX decomposed continuously as an almost single oxidizer in the AN/RDX propellant. In contrast, AN/HMX propellants exhibited thermal decomposition characteristics similar to those of AN and HMX, which decomposed almost separately in the thermal decomposition of the AN/HMX propellant. The ignitability was improved and the burning rate increased by the addition of nitramine for both AN/RDX and AN/HMX propellants. The increased burning rates of AN/RDX propellants were greater than those of AN/HMX. The difference in the thermal decomposition and burning characteristics was caused by the interaction between AN and RDX.

Carbon availability triggers the decomposition of plant litter and assimilation of nitrogen by an ectomycorrhizal fungus

PubMed Central

Rineau, F; Shah, F; Smits, M M; Persson, P; Johansson, T; Carleer, R; Troein, C; Tunlid, A

2013-01-01

The majority of nitrogen in forest soils is found in organic matter–protein complexes. Ectomycorrhizal fungi (EMF) are thought to have a key role in decomposing and mobilizing nitrogen from such complexes. However, little is known about the mechanisms governing these processes, how they are regulated by the carbon in the host plant and the availability of more easily available forms of nitrogen sources. Here we used spectroscopic analyses and transcriptome profiling to examine how the presence or absence of glucose and/or ammonium regulates decomposition of litter material and nitrogen mobilization by the ectomycorrhizal fungus Paxillus involutus. We found that the assimilation of nitrogen and the decomposition of the litter material are triggered by the addition of glucose. Glucose addition also resulted in upregulation of the expression of genes encoding enzymes involved in oxidative degradation of polysaccharides and polyphenols, peptidases, nitrogen transporters and enzymes in pathways of the nitrogen and carbon metabolism. In contrast, the addition of ammonium to organic matter had relatively minor effects on the expression of transcripts and the decomposition of litter material, occurring only when glucose was present. On the basis of spectroscopic analyses, three major types of chemical modifications of the litter material were observed, each correlated with the expression of specific sets of genes encoding extracellular enzymes. Our data suggest that the expression of the decomposition and nitrogen assimilation processes of EMF can be tightly regulated by the host carbon supply and that the availability of inorganic nitrogen as such has limited effects on saprotrophic activities. PMID:23788332

Oxidation of lignin and cellulose, humification and coalification

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

Volborth, A.

1976-06-09

Oxygen plays an important role in the first stages of the decomposition of organic substances derived from plant material. The decomposition and reformation of such organic matter as cellulose and lignin leads, through-humification and a sequence of metamorphic processes, to the formation of coal. Initially, oxidation reactions cause the formation of dark-colored humic acids, later under more anaerobic conditions, pressure and higher temperatures, polymerization occurs as the sediment becomes buried. Under these conditions phenolic compounds are more stable, also during the processes of decomposition phenolic substances are more resistant to microorganisms, and thus seem to accumulate. The humification process maymore » be considered as the first step in coalification. It starts by rapid decomposition of the cellulose and by enzymatic degradation of the lignin of the rotting plant substance to form C/sub 6/-C/sub 3/ or C/sub 6/-C/sub 1/ compounds. These lose methoxyl groups and carboxyl groups and can form hydroquinones which may polymerize and combine, forming humic acids. Degradation may proceed also to aliphatic compounds. Most of the reactions seem to lead to benzoquinones which dimerize and polymerize further, causing an increase in aromatization with age, and under more anaerobic conditions later during coalification. When conditions become anaerobic, melanoidin and glucosamin compounds form and nitrogen fixation occurs. This explains the presence of about 1 to 3.5 percent nitrogen in humic acid concentrates, lignin, lignite, subbituminous and bituminous coal. The fixation of nitrogen also results in further reduction of carbon in humic substance during the later stages of humification. Further coalification of buried humified strata of decomposed organic material causes reduction as the methoxyl and oxygen group content decreases, and CO and CO/sub 2/ gases and H/sub 2/O evolve and gradual dehydration occurs.« less

Reactivation of model cholinesterases by oximes and intermediate phosphyloximes: A computational study

PubMed Central

Vyas, Shubham; Hadad, Christopher M.

2008-01-01

Phosphyloximes (POX) are generated upon the reactivation of organophosphorus (OP) inhibited cholinesterases (ChEs) by pyridinium oximes. These POXs are known to be potent inhibitors of the ChEs following reactivation. However, they can also decompose to give an OP derivative and a cyano derivative of the oxime when a base abstracts the benzylic proton. Using density functional theory, thermodynamic properties were calculated for the reactivation and decomposition pathways of three different oximes (2-PAM, 3-PAM and 4-PAM) with six different OPs (cyclosarin, paraoxon, sarin, tabun, VR and VX). For reactivation purposes, 2-PAM is predicted to be more efficient than 3- and 4-PAM. Based on atomic charges and relative energies, 2-POXs were found to be more inclined towards the decomposition process. PMID:18582852

Multiple Mechanisms for the Thermal Decomposition of Metallaisoxazolin-5-ones from Computational Investigations.

PubMed

Zhou, Chen-Chen; Hawthorne, M Frederick; Houk, K N; Jiménez-Osés, Gonzalo

2017-08-18

The thermal decompositions of metallaisoxazolin-5-ones containing Ir, Rh, or Co are investigated using density functional theory. The experimentally observed decarboxylations of these molecules are found to proceed through retro-(3+2)-cycloaddition reactions, generating the experimentally reported η 2 side-bonded nitrile complexes. These intermediates can isomerize in situ to yield a η 1 nitrile complex. A competitive alternative pathway is also found where the decarboxylation happens concertedly with an aryl migration process, producing a η 1 isonitrile complex. Despite their comparable stability, these η 1 bonded species were not detected experimentally. The experimentally detected η 2 side bound species are likely involved in the subsequent C-H activation reactions with hydrocarbon solvents reported for some of these metallaisoxazolin-5-ones.

Evaluating litter decomposition and soil organic matter dynamics in earth system models: contrasting analysis of long-term litter decomposition and steady-state soil carbon

NASA Astrophysics Data System (ADS)

Bonan, G. B.; Wieder, W. R.

2012-12-01

Decomposition is a large term in the global carbon budget, but models of the earth system that simulate carbon cycle-climate feedbacks are largely untested with respect to litter decomposition. Here, we demonstrate a protocol to document model performance with respect to both long-term (10 year) litter decomposition and steady-state soil carbon stocks. First, we test the soil organic matter parameterization of the Community Land Model version 4 (CLM4), the terrestrial component of the Community Earth System Model, with data from the Long-term Intersite Decomposition Experiment Team (LIDET). The LIDET dataset is a 10-year study of litter decomposition at multiple sites across North America and Central America. We show results for 10-year litter decomposition simulations compared with LIDET for 9 litter types and 20 sites in tundra, grassland, and boreal, conifer, deciduous, and tropical forest biomes. We show additional simulations with DAYCENT, a version of the CENTURY model, to ask how well an established ecosystem model matches the observations. The results reveal large discrepancy between the laboratory microcosm studies used to parameterize the CLM4 litter decomposition and the LIDET field study. Simulated carbon loss is more rapid than the observations across all sites, despite using the LIDET-provided climatic decomposition index to constrain temperature and moisture effects on decomposition. Nitrogen immobilization is similarly biased high. Closer agreement with the observations requires much lower decomposition rates, obtained with the assumption that nitrogen severely limits decomposition. DAYCENT better replicates the observations, for both carbon mass remaining and nitrogen, without requirement for nitrogen limitation of decomposition. Second, we compare global observationally-based datasets of soil carbon with simulated steady-state soil carbon stocks for both models. The models simulations were forced with observationally-based estimates of annual litterfall and model-derived climatic decomposition index. While comparison with the LIDET 10-year litterbag study reveals sharp contrasts between CLM4 and DAYCENT, simulations of steady-state soil carbon show less difference between models. Both CLM4 and DAYCENT significantly underestimate soil carbon. Sensitivity analyses highlight causes of the low soil carbon bias. The terrestrial biogeochemistry of earth system models must be critically tested with observations, and the consequences of particular model choices must be documented. Long-term litter decomposition experiments such as LIDET provide a real-world process-oriented benchmark to evaluate models and can critically inform model development. Analysis of steady-state soil carbon estimates reveal additional, but here different, inferences about model performance.

Iterative variational mode decomposition based automated detection of glaucoma using fundus images.

PubMed

Maheshwari, Shishir; Pachori, Ram Bilas; Kanhangad, Vivek; Bhandary, Sulatha V; Acharya, U Rajendra

2017-09-01

Glaucoma is one of the leading causes of permanent vision loss. It is an ocular disorder caused by increased fluid pressure within the eye. The clinical methods available for the diagnosis of glaucoma require skilled supervision. They are manual, time consuming, and out of reach of common people. Hence, there is a need for an automated glaucoma diagnosis system for mass screening. In this paper, we present a novel method for an automated diagnosis of glaucoma using digital fundus images. Variational mode decomposition (VMD) method is used in an iterative manner for image decomposition. Various features namely, Kapoor entropy, Renyi entropy, Yager entropy, and fractal dimensions are extracted from VMD components. ReliefF algorithm is used to select the discriminatory features and these features are then fed to the least squares support vector machine (LS-SVM) for classification. Our proposed method achieved classification accuracies of 95.19% and 94.79% using three-fold and ten-fold cross-validation strategies, respectively. This system can aid the ophthalmologists in confirming their manual reading of classes (glaucoma or normal) using fundus images. Copyright © 2017 Elsevier Ltd. All rights reserved.

An Appraisal of Decomposition Cases Received at the Johannesburg Forensic Pathology Service Medico-legal Mortuary During 2010-2011.

PubMed

Keyes, Craig A; Hill, Lawrence; Gordon, Guinevere M

2016-03-01

Decomposed bodies pose many questions for researchers regarding environmental effects, cause of death, and patterns. This study aimed to observe the factors associated with decomposed bodies autopsied at the Johannesburg Forensic Pathology Service Medico-legal Mortuary. A total of 4876 autopsies were conducted from 2010 to 2011, of which 109 were decomposed. Black individuals made up the largest proportion (67%) followed by White (26%). Males comprised 86.2%, while 12.8% were female. The mean age was 42.78 years. Most cases were in the early stages of decomposition (49.5%), with 32.1% bloated, 11.9% in active decay, 2.8% in advanced decay, and 3.7% were skeletal. Insect activity was identified in 25.7% of decomposition cases. Cause of death was determined in 48.6% of cases. Of all the cases, 64% were found indoors and 23% outdoors, while 23% had insufficient information regarding the location. Of considerable interest was the number of cases from hospitals and clinics. © 2015 American Academy of Forensic Sciences.

Putrefactive rigor: apparent rigor mortis due to gas distension.

PubMed

Gill, James R; Landi, Kristen

2011-09-01

Artifacts due to decomposition may cause confusion for the initial death investigator, leading to an incorrect suspicion of foul play. Putrefaction is a microorganism-driven process that results in foul odor, skin discoloration, purge, and bloating. Various decompositional gases including methane, hydrogen sulfide, carbon dioxide, and hydrogen will cause the body to bloat. We describe 3 instances of putrefactive gas distension (bloating) that produced the appearance of inappropriate rigor, so-called putrefactive rigor. These gases may distend the body to an extent that the extremities extend and lose contact with their underlying support surface. The medicolegal investigator must recognize that this is not true rigor mortis and the body was not necessarily moved after death for this gravity-defying position to occur.

Thermal Decomposition Behaviors and Burning Characteristics of Composite Propellants Prepared Using Combined Ammonium Perchlorate/Ammonium Nitrate Particles

NASA Astrophysics Data System (ADS)

Kohga, Makoto; Handa, Saori

2018-01-01

The thermal decomposition behaviors and burning characteristics of propellants prepared with combined ammonium perchlorate (AP)/ammonium nitrate (AN) particles greatly depended on the AN content (χ) of the AP/AN sample. The thermal decomposition behaviors of the propellants prepared with the combined samples almost matched those of the propellants prepared by physically mixing AP and AN particles, while their burning characteristics differed. The use of combined AP/AN particles decreased the heterogeneity of the combustion waves of the AP/AN propellants because of the difference in the combustion wave structure. In contrast, the addition of Fe2O3 caused unsteady combustion of the propellants prepared using samples with χ values lower than 8.1%.

Rapid characterization of lithium ion battery electrolytes and thermal aging products by low-temperature plasma ambient ionization high-resolution mass spectrometry.

PubMed

Vortmann, Britta; Nowak, Sascha; Engelhard, Carsten

2013-03-19

Lithium ion batteries (LIBs) are key components for portable electronic devices that are used around the world. However, thermal decomposition products in the battery reduce its lifetime, and decomposition processes are still not understood. In this study, a rapid method for in situ analysis and reaction monitoring in LIB electrolytes is presented based on high-resolution mass spectrometry (HR-MS) with low-temperature plasma probe (LTP) ambient desorption/ionization for the first time. This proof-of-principle study demonstrates the capabilities of ambient mass spectrometry in battery research. LTP-HR-MS is ideally suited for qualitative analysis in the ambient environment because it allows direct sample analysis independent of the sample size, geometry, and structure. Further, it is environmental friendly because it eliminates the need of organic solvents that are typically used in separation techniques coupled to mass spectrometry. Accurate mass measurements were used to identify the time-/condition-dependent formation of electrolyte decomposition compounds. A LIB model electrolyte containing ethylene carbonate and dimethyl carbonate was analyzed before and after controlled thermal stress and over the course of several weeks. Major decomposition products identified include difluorophosphoric acid, monofluorophosphoric acid methyl ester, monofluorophosphoric acid dimethyl ester, and hexafluorophosphate. Solvents (i.e., dimethyl carbonate) were partly consumed via an esterification pathway. LTP-HR-MS is considered to be an attractive method for fundamental LIB studies.

Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

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

Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.

2012-04-19

Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 releasemore » properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.« less

Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product.

PubMed

Leszczyński, Piotr J; Budzianowski, Armand; Dobrzycki, Lukasz; Cyrański, Michał K; Derzsi, Mariana; Grochala, Wojciech

2012-01-14

High purity samples of a [Ag(pyrazine)(2)]S(2)O(8) complex were obtained using modified synthetic pathways. Di(pyrazine)silver(II) peroxydisulfate is sensitive to moisture forming [Ag(pyrazine)(2)](S(2)O(8))(H(2)O) hydrate which degrades over time yielding HSO(4)(-) derivatives and releasing oxygen. One polymorphic form of pyrazinium hydrogensulfate, β-(pyrazineH(+))(HSO(4)(-)), is found among the products of chemical decomposition together with unique [Ag(i)(pyrazine)](5)(H(2)O)(2)(HSO(4))(2)[H(SO(4))(2)]. Chemical degradation of [Ag(pyrazine)(2)]S(2)O(8) in the presence of trace amounts of moisture can explain the very low yield of wet synthesis (11-15%). Attempts have failed to obtain a mixed valence Ag(II)/Ag(I) pyrazine complex via partial chemical reduction of the [Ag(pyrazine)(2)]S(2)O(8) precursor with a variety of inorganic and organic reducing agents, or via controlled thermal decomposition. Thermal degradation of [Ag(pyrazine)(2)]S(2)O(8) containing occluded water proceeds at T > 90 °C via evolution of O(2); simultaneous release of pyrazine and SO(3) is observed during the next stages of thermal decomposition (120-285 °C), while Ag(2)SO(4) and Ag are obtained upon heating to 400-450 °C.

Net ecosystem productivity and carbon dynamics of the traditionally managed Imperata grasslands of North East India.

PubMed

Pathak, Karabi; Malhi, Yadvinder; Sileshi, G W; Das, Ashesh Kumar; Nath, Arun Jyoti

2018-09-01

There have been few comprehensive descriptions of how fire management and harvesting affect the carbon dynamics of grasslands. Grasslands dominated by the invasive weed Imperata cylindrica are considered as environmental threats causing low land productivity throughout the moist tropical regions in Asia. Imperata grasslands in North East India are unique in that they are traditionally managed and culturally important in the rural landscapes. Given the importance of fire in the management of Imperata grassland, we aimed to assess (i) the seasonal pattern of biomass production, (ii) the eventual pathways for the produced biomass, partitioned between in situ decomposition, harvesting and combustion, and (iii) the effect of customary fire management on the ecosystem carbon cycle. Comparatively high biomass production was recorded during pre-monsoon (154 g m -2  month -1 ) and monsoon (214 g m -2  month -1 ) compared to the post-monsoon (91 g m -2  month -1 ) season, and this is attributed to nutrient return into the soil immediately after fire in February. Post fire effects might have killed roots and rhizomes leading to high belowground litter production 30-35 g m -2 during March to August. High autotrophic respiration was recorded during March-July, which was related to high belowground biomass production (35-70 g m -2 ) during that time. Burning removed all the surface litter in March and this appeared to hinder surface decomposition and result in low heterotrophic respiration. Annual total biomass carbon production was estimated at 886 g C m -2 . Annual harvest of biomass (estimated at 577 g C m -2 ) was the major pathway for carbon fluxes from the system. Net ecosystem production (NEP) of Imperata grassland was estimated at 91 g C m -2  yr -1 indicating that these grasslands are a net sink of CO 2 , although this is greatly influenced by weather and fire management. Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.

Flux Analysis of Free Amino Sugars and Amino Acids in Soils by Isotope Tracing with a Novel Liquid Chromatography/High Resolution Mass Spectrometry Platform

PubMed Central

2017-01-01

Soil fluxomics analysis can provide pivotal information for understanding soil biochemical pathways and their regulation, but direct measurement methods are rare. Here, we describe an approach to measure soil extracellular metabolite (amino sugar and amino acid) concentrations and fluxes based on a 15N isotope pool dilution technique via liquid chromatography and high-resolution mass spectrometry. We produced commercially unavailable 15N and 13C labeled amino sugars and amino acids by hydrolyzing peptidoglycan isolated from isotopically labeled bacterial biomass and used them as tracers (15N) and internal standards (13C). High-resolution (Orbitrap Exactive) MS with a resolution of 50 000 allowed us to separate different stable isotope labeled analogues across a large range of metabolites. The utilization of 13C internal standards greatly improved the accuracy and reliability of absolute quantification. We successfully applied this method to two types of soils and quantified the extracellular gross fluxes of 2 amino sugars, 18 amino acids, and 4 amino acid enantiomers. Compared to the influx and efflux rates of most amino acids, similar ones were found for glucosamine, indicating that this amino sugar is released through peptidoglycan and chitin decomposition and serves as an important nitrogen source for soil microorganisms. d-Alanine and d-glutamic acid derived from peptidoglycan decomposition exhibited similar turnover rates as their l-enantiomers. This novel approach offers new strategies to advance our understanding of the production and transformation pathways of soil organic N metabolites, including the unknown contributions of peptidoglycan and chitin decomposition to soil organic N cycling. PMID:28776982

The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

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

Buckingham, Grant T.; Ormond, Thomas K.; National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401

2015-01-28

The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C{sub 6}H{sub 5}CH{sub 2}, as well as a set of isotopically labeled radicals: C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C{sub 5}H{submore » 4}=C=CH{sub 2}, H atom, C{sub 5}H{sub 4}—C ≡ CH, C{sub 5}H{sub 5}, HCCCH{sub 2}, and HC ≡ CH. Pyrolysis of the C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2} benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C{sub 6}H{sub 5}CH{sub 2}⇋C{sub 7}H{sub 7}. These labeling studies suggest that there must be other thermal decomposition routes for the C{sub 6}H{sub 5}CH{sub 2} radical that differ from the fulvenallene pathway.« less

Can we infer post mortem interval on the basis of decomposition rate? A case from a Portuguese cemetery.

PubMed

Ferreira, M Teresa; Cunha, Eugénia

2013-03-10

Post mortem interval estimation is crucial in forensic sciences for both positive identification and reconstruction of perimortem events. However, reliable dating of skeletonized remains poses a scientific challenge since human remains decomposition involves a set of complex and highly variable processes. Many of the difficulties in determining post mortem interval and/or the permanence of a body in a specific environment relates with the lack of systematic observations and research in human body decomposition modalities in different environments. In March 2006, in order to solve a problem of misidentification, a team of the South Branch of Portuguese National Institute of Legal Medicine carried out the exhumation of 25 identified individuals buried for almost five years in the same cemetery plot. Even though all individuals shared similar post mortem intervals, they presented different stages of decomposition. In order to analyze the post mortem factors associated with the different stages of decomposition displayed by the 25 exhumed individuals, the stages of decomposition were scored. Information regarding age at death and sex of the individuals were gathered and recorded as well as data in the cause of death and grave and coffin characteristics. Although the observed distinct decay stages may be explained by the burial conditions, namely by the micro taphonomic environments, individual endogenous factors also play an important role on differential decomposition as witnessed by the present case. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Catalytically induced electrokinetics for motors and micropumps.

PubMed

Paxton, Walter F; Baker, Paul T; Kline, Timothy R; Wang, Yang; Mallouk, Thomas E; Sen, Ayusman

2006-11-22

We have explored the role of electrokinetics in the spontaneous motion of platinum-gold nanorods suspended in hydrogen peroxide (H2O2) solutions that may arise from the bimetallic electrochemical decomposition of H2O2. The electrochemical decomposition pathway was confirmed by measuring the steady-state short-circuit current between platinum and gold interdigitated microelectrodes (IMEs) in the presence of H2O2. The resulting ion flux from platinum to gold implies an electric field in the surrounding solution that can be estimated from Ohm's Law. This catalytically generated electric field could in principle bring about electrokinetic effects that scale with the Helmholtz-Smoluchowski equation. Accordingly, we observed a linear relationship between bimetallic rod speed and the resistivity of the bulk solution. Previous observations relating a decrease in speed to an increase in ethanol concentration can be explained in terms of a decrease in current density caused by the presence of ethanol. Furthermore, we found that the catalytically generated electric field in the solution near a Pt/Au IME in the presence of H2O2 is capable of inducing electroosmotic fluid flow that can be switched on and off externally. We demonstrate that the velocity of the fluid flow in the plane of the IME is a function of the electric field, whether catalytically generated or applied from an external current source. Our findings indicate that the motion of PtAu nanorods in H2O2 is primarily due to a catalytically induced electrokinetic phenomenon and that other mechanisms, such as those related to interfacial tension gradients, play at best a minor role.

Electromagnetic Characterization of Carbon Nanotube Films Subject to an Oxidative Treatment at Elevated Temperature (Preprint)

DTIC Science & Technology

2010-07-01

response to the tip causes a redistribution of charge on the tip in order to maintain the equipotential surface of the sphere, and also results in a shift...can be obtained. In some instances these treatments lead to uncapping of nanotubes. Geng et al. [25] have shown that the surfaces of SWNT bundles...20] discovered a new and catalyst-free method for the growth of CNTs: surface decomposition of silicon carbide (SiC). This thermal decomposition

Decomposition of educational differences in life expectancy by age and causes of death among South Korean adults.

PubMed

Jung-Choi, Kyunghee; Khang, Young-Ho; Cho, Hong-Jun; Yun, Sung-Cheol

2014-06-05

Decomposition of socioeconomic inequalities in life expectancy by ages and causes allow us to better understand the nature of socioeconomic mortality inequalities and to suggest priority areas for policy and intervention. This study aimed to quantify age- and cause-specific contributions to socioeconomic differences in life expectancy at age 25 by educational level among South Korean adult men and women. We used National Death Registration records in 2005 (129,940 men and 106,188 women) and national census data in 2005 (15, 215, 523 men and 16,077,137 women aged 25 and over). Educational attainment as the indicator of socioeconomic position was categorized into elementary school graduation or less, middle or high school graduation, and college graduation or higher. Differences in life expectancy at age 25 by educational level were estimated by age- and cause-specific mortality differences using Arriaga's decomposition method. Differences in life expectancy at age 25 between college or higher education and elementary or less education were 16.23 years in men and 7.69 years in women. Young adult groups aged 35-49 in men and aged 25-39 in women contributed substantially to the differences between college or higher education and elementary or less education in life expectancy. Suicide and liver disease were the most important causes of death contributing to the differences in life expectancy in young adult groups. For older age groups, cerebrovascular disease and lung cancer were important to explain educational differential in life expectancy at 25-29 between college or higher education and middle or higher education. The contribution of the causes of death to socioeconomic inequality in life expectancy at age 25 in South Korea varied by age groups and differed by educational comparisons. The age specific contributions for different causes of death to life expectancy inequalities by educational attainment should be taken into account in establishing effective policy strategies to reduce socioeconomic inequalities in life expectancy.

Factors and processes causing accelerated decomposition in human cadavers - An overview.

PubMed

Zhou, Chong; Byard, Roger W

2011-01-01

Artefactually enhanced putrefactive and autolytic changes may be misinterpreted as indicating a prolonged postmortem interval and throw doubt on the veracity of witness statements. Review of files from Forensic Science SA and the literature revealed a number of external and internal factors that may be responsible for accelerating these processes. Exogenous factors included exposure to elevated environmental temperatures, both outdoors and indoors, exacerbated by increased humidity or fires. Situations indoor involved exposure to central heating, hot water, saunas and electric blankets. Deaths within motor vehicles were also characterized by enhanced decomposition. Failure to quickly or adequately refrigerate bodies may also lead to early decomposition. Endogenous factors included fever, infections, illicit and prescription drugs, obesity and insulin-dependent diabetes mellitus. When these factors or conditions are identified at autopsy less significance should, therefore, be attached to changes of decomposition as markers of time since death. Copyright © 2010 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

Direct and indirect controls on organic matter decomposition in four coastal wetland communities along a landscape salinity gradient

USGS Publications Warehouse

Stagg, Camille L.; Baustian, Melissa M.; Perry, Carey L.; Carruthers, Tim J.B.; Hall, Courtney T.

2018-01-01

Coastal wetlands store more carbon than most ecosystems globally. As sea level rises, changes in flooding and salinity will potentially impact ecological functions, such as organic matter decomposition, that influence carbon storage. However, little is known about the mechanisms that control organic matter loss in coastal wetlands at the landscape scale. As sea level rises, how will the shift from fresh to salt-tolerant plant communities impact organic matter decomposition? Do long-term, plant-mediated, effects of sea-level rise differ from direct effects of elevated salinity and flooding?We identified internal and external factors that regulated indirect and direct pathways of sea-level rise impacts, respectively, along a landscape-scale salinity gradient that incorporated changes in wetland type (fresh, oligohaline, mesohaline and polyhaline marshes). We found that indirect and direct impacts of sea-level rise had opposing effects on organic matter decomposition.Salinity had an indirect effect on litter decomposition that was mediated through litter quality. Despite significant variation in environmental conditions along the landscape gradient, the best predictors of above- and below-ground litter decomposition were internal drivers, initial litter nitrogen content and initial litter lignin content respectively. Litter decay constants were greatest in the oligohaline marsh and declined with increasing salinity, and the fraction of litter remaining (asymptote) was greatest in the mesohaline marsh. In contrast, direct effects of salinity and flooding were positive. External drivers, salinity and flooding, stimulated cellulytic activity, which was highest in the polyhaline marsh.Synthesis. Our results indicate that as sea level rises, initial direct effects of salinity will stimulate decay of labile carbon, but over time as plant communities shift from fresh to polyhaline marsh, litter decay will decline, yielding greater potential for long-term carbon storage. These findings highlight the importance of quantifying carbon loss at multiple temporal scales, not only in coastal wetlands but also in other ecosystems where plant-mediated responses to climate change will have significant impacts on carbon cycling.

Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

NASA Astrophysics Data System (ADS)

Abbas, N.; Madix, R. J.

The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

The response of soil carbon storage and microbially mediated carbon turnover to simulated climatic disturbance in a northern peatland forest. Revisiting the concept of soil organic matter recalcitrance

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

Kostka, Joel

The goal of this project was to investigate changes in the structure of dissolved and solid phase organic matter, the production of CO 2 and CH 4, and the composition of decomposer microbial communities in response to the climatic forcing of environmental processes that determine the balance between carbon gas production versus storage and sequestration in peatlands. Cutting-edge analytical chemistry and next generation sequencing of microbial genes were been applied to habitats at the Marcell Experimental Forest (MEF), where the US DOE’s Oak Ridge National Laboratory and the USDA Forest Service are constructing a large-scale ecosystem study entitled, “Spruce andmore » Peatland Responses Under Climatic and Environmental Change”(SPRUCE). Our study represented a comprehensive characterization of the sources, transformation, and decomposition of organic matter in the S1 bog at MEF. Multiple lines of evidence point to distinct, vertical zones of organic matter transformation: 1) the acrotelm consisting of living mosses, root material, and newly formed litter (0-30 cm), 2) the mesotelm, a mid-depth transition zone (30-75 cm) characterized by labile organic C compounds and intense decomposition, and 3) the underlying catotelm (below 75cm) characterized by refractory organic compounds as well as relatively low decomposition rates. These zones are in part defined by physical changes in hydraulic conductivity and water table depth. O-alkyl-C, which represents the carbohydrate fraction in the peat, was shown to be an excellent proxy for soil decomposition rates. The carbon cycle in deep peat was shown to be fueled by modern carbon sources further indicating that hydrology and surface vegetation play a role in belowground carbon cycling. We provide the first metagenomic study of an ombrotrophic peat bog, with novel insights into microbial specialization and functions in this unique terrestrial ecosystem. Vertical structuring of microbial communities closely paralleled the chemical evolution of peat, with large shifts in microbial populations occurring in the biogeochemical hotspot, the mesotelm, where the highest rates of decomposition were detected. Stable isotope geochemistry and potential rates of methane production paralleled vertical changes in methanogen community composition to indicate a predominance of acetoclastic methanogenesis mediated by the Methanosarcinales in the mesotelm, while hydrogen-utilizing methanogens dominated in the deeper catotelm. Evidence pointed to the availability of phosphorus as well as nitrogen limiting the microbially-mediated turnover of organic carbon at MEF. Prior to initiation of the experimental treatments, our study provided key baseline data for the SPRUCE site on the vertical stratification of peat decomposition, key enzymatic pathways, and microbial taxa containing these pathways. The sensitivity of soil carbon turnover to climate change is strongly linked to recalcitrant carbon stocks and the temperature sensitivity of decomposition is thought to increase with increasing molecular complexity of carbon substrates. This project delivered results on how climate change perturbations impact the microbially-mediated turnover of recalcitrant organic matter in peatland forest soils, both under controlled conditions in the laboratory and at the ecosystem-scale in the field. This project revisited the concept of “recalcitrance” in the regulation of soil carbon turnover using a combination of natural abundance radiocarbon and optical spectroscopic measurements on bulk DOM, and high resolution molecular characterization of DOM. The project elucidated how organic matter reactivity and decomposition will respond to climate change in a both a qualitative (organic matter lability) and quantitiative (increased rates) manner. An Aromaticity Index was developed to represent a more direct and accurate parameter for modeling of DOM reactivity in peatlands. The abundance and community composition of soil microorganisms that mediate C cycling were interrogated with depth in the peat, with season, and in manipulated climate enclosures at unprecedented resolution. Therefore this project delivered strategic new insights on the functioning of peatland ecosystems that collectively store approximately one-third of the world's soil carbon. Furthermore, results from the detailed characterization of DOM lability and microbial community structure/ function will be employed to further develop biogeochemical models to include microbial respiration pathways as well as to track carbon flow with a term that incorporates relative reactivity based on aromaticity index. As it stands now, detailed soil organic matter structure and microbial parameters are not included in Earth system models.« less

Reassessment of the NH4 NO3 thermal decomposition technique for calibration of the N2 O isotopic composition.

PubMed

Mohn, Joachim; Gutjahr, Wilhelm; Toyoda, Sakae; Harris, Eliza; Ibraim, Erkan; Geilmann, Heike; Schleppi, Patrick; Kuhn, Thomas; Lehmann, Moritz F; Decock, Charlotte; Werner, Roland A; Yoshida, Naohiro; Brand, Willi A

2016-09-08

In the last few years, the study of N 2 O site-specific nitrogen isotope composition has been established as a powerful technique to disentangle N 2 O emission pathways. This trend has been accelerated by significant analytical progress in the field of isotope-ratio mass-spectrometry (IRMS) and more recently quantum cascade laser absorption spectroscopy (QCLAS). Methods The ammonium nitrate (NH 4 NO 3 ) decomposition technique provides a strategy to scale the 15 N site-specific (SP ≡ δ 15 N α - δ 15 N β ) and bulk (δ 15 N bulk  = (δ 15 N α  + δ 15 N β )/2) isotopic composition of N 2 O against the international standard for the 15 N/ 14 N isotope ratio (AIR-N 2 ). Within the current project 15 N fractionation effects during thermal decomposition of NH 4 NO 3 on the N 2 O site preference were studied using static and dynamic decomposition techniques. The validity of the NH 4 NO 3 decomposition technique to link NH 4 + and NO 3 - moiety-specific δ 15 N analysis by IRMS to the site-specific nitrogen isotopic composition of N 2 O was confirmed. However, the accuracy of this approach for the calibration of δ 15 N α and δ 15 N β values was found to be limited by non-quantitative NH 4 NO 3 decomposition in combination with substantially different isotope enrichment factors for the conversion of the NO 3 - or NH 4 + nitrogen atom into the α or β position of the N 2 O molecule. The study reveals that the completeness and reproducibility of the NH 4 NO 3 decomposition reaction currently confine the anchoring of N 2 O site-specific isotopic composition to the international isotope ratio scale AIR-N 2 . The authors suggest establishing a set of N 2 O isotope reference materials with appropriate site-specific isotopic composition, as community standards, to improve inter-laboratory compatibility. This article is protected by copyright. All rights reserved.

The influence of minerals on decomposition of the n-alkyl-α-amino acid norvaline under hydrothermal conditions

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.

2013-03-01

Laboratory experiments were conducted to observe the effect of iron oxide and sulfide minerals on decomposition reactions of norvaline, a representative of a group of alkyl-α-amino acids observed in meteorites and prebiotic synthesis experiments. The primary products observed during heating of aqueous solutions of norvaline at temperatures of 156-186 °C in the presence of minerals included CO2, NH3, butyric acid, and valeric acid. The products indicated that norvaline predominantly decomposed by a combination of pathways that included both decarboxylation followed rapidly by oxidative deamination (norvaline → butanamide + CO2 → butyric acid + NH3) and deamination directly to valeric acid (norvaline → valeric acid + NH3). An experiment performed with alanine under similar conditions showed it decomposed by analogous reactions that produced acetic and propionic acids along with CO2 and NH3. For both amino acids, the presence of minerals accelerated decomposition rates as well as altered the final products of reaction, when compared with decomposition in the absence of mineral substrates. In addition, decomposition of norvaline was found to proceed much faster in the presence of the mineral assemblage hematite-magnetite-pyrite (HMP) than with the assemblage pyrite-pyrrhotite-magnetite (PPM), a trend that has been observed for several other organic compounds. The influence of minerals on decomposition reactions of these amino acids appears to be attributable to a combination of surface catalysis and production of dissolved sulfur compounds. Overall, the results indicate that minerals may exert a substantial influence on amino acid stability in many geologic environments, and emphasize the need to consider the impact of minerals when evaluating the lifetimes and decomposition rates of amino acids in terrestrial and planetary systems. Estimated half-lives for alkyl-α-amino acids based on the experimental results indicate that moderately hot hydrothermal environments (<˜100 °C) would have been the most favorable for accumulation of these amino acids in the early solar system, and that the predominance of alkyl-α-amino acids in some meteorites may only be compatible with temperature remaining below about 60 °C following their formation.

Elucidating the thermal, chemical, and mechanical mechanisms of ultraviolet ablation in poly(methyl methacrylate) via molecular dynamics simulations.

PubMed

Conforti, Patrick F; Prasad, Manish; Garrison, Barbara J

2008-08-01

[Figure: see text]. Laser ablation harnesses photon energy to remove material from a surface. Although applications such as laser-assisted in situ keratomileusis (LASIK) surgery, lithography, and nanoscale device fabrication take advantage of this process, a better understanding the underlying mechanism of ablation in polymeric materials remains much sought after. Molecular simulation is a particularly attractive technique to study the basic aspects of ablation because it allows control over specific process parameters and enables observation of microscopic mechanistic details. This Account describes a hybrid molecular dynamics-Monte Carlo technique to simulate laser ablation in poly(methyl methacrylate) (PMMA). It also discusses the impact of thermal and chemical excitation on the ensuing ejection processes. We used molecular dynamics simulation to study the molecular interactions in a coarse-grained PMMA substrate following photon absorption. To ascertain the role of chemistry in initiating ablation, we embedded a Monte Carlo protocol within the simulation framework. These calculations permit chemical reactions to occur probabilistically during the molecular dynamics calculation using predetermined reaction pathways and Arrhenius rates. With this hybrid scheme, we can examine thermal and chemical pathways of decomposition separately. In the simulations, we observed distinct mechanisms of ablation for each type of photoexcitation pathway. Ablation via thermal processes is governed by a critical number of bond breaks following the deposition of energy. For the case in which an absorbed photon directly causes a bond scission, ablation occurs following the rapid chemical decomposition of material. A detailed analysis of the processes shows that a critical energy for ablation can describe this complex series of events. The simulations show a decrease in the critical energy with a greater amount of photochemistry. Additionally, the simulations demonstrate the effects of the energy deposition rate on the ejection mechanism. When the energy is deposited rapidly, not allowing for mechanical relaxation of the sample, the formation of a pressure wave and subsequent tensile wave dominates the ejection process. This study provides insight into the influence of thermal, chemical, and mechanical processes in PMMA and facilitates greater understanding of the complex nature of polymer ablation. These simulations complement experiments that have used chemical design to harness the photochemical properties of materials to enhance laser ablation. We successfully fit the results of the simulations to established analytical models of both photothermal and photochemical ablation and demonstrate their relevance. Although the simulations are for PMMA, the mechanistic concepts are applicable to a large range of systems and provide a conceptual foundation for interpretation of experimental data.

Interspecific variations in mangrove leaf litter decomposition are related to labile nitrogenous compounds

NASA Astrophysics Data System (ADS)

Nordhaus, Inga; Salewski, Tabea; Jennerjahn, Tim C.

2017-06-01

Mangrove leaves form a large pool of carbon, nitrogen and energy that is a major driver of element cycles and detrital food webs inside mangrove forests as well as in adjacent coastal waters. However, there are large gaps in knowledge on the transformation pathways and ultimate fate of leaf nitrogen. Therefore, the main objective of this study was to determine the amount and composition of nitrogenous organic matter and possible species-specific differences during the decomposition of mangrove leaf litter. For that purpose a three month decomposition experiment with litterbags was conducted using leaves of Aegiceras corniculatum, Avicennia alba, Ceriops decandra, Rhizophora apiculata, and Sonneratia caseolaris in the mangrove forest of the Segara Anakan Lagoon, Java, Indonesia. Detrital leaves were analyzed for bulk carbon and total nitrogen (N), stable carbon and nitrogen isotope composition (δ13C, δ15N), total hydrolyzable amino acids (THAA) and total hydrolyzable hexosamines (THHA). Decomposition rates (k d-1) were highest and tM50 values (when 50% of the original mass had been degraded) lowest in S. caseolaris (k = 0.0382 d-1; tM50 = 18 days), followed by A. alba, C. decandra, A. corniculatum, and R. apiculata (k = 0.0098 d-1; tM50 = 71 days). The biochemical composition of detrital leaves differed significantly among species and over time. S. caseolaris and A. alba had higher concentrations of N, THAA and THHA and a lower C/N ratio than the other three species. For most of the species concentrations of N, THAA and THHA increased during decomposition. The hexosamine galactosamine, indicative of bacterial cell walls, was first found in leaves after 5-7 days of decomposition and increased afterwards. Our findings suggest an increasing, but species-specific varying, portion of labile nitrogenous OM and total N in decomposing leaves over time that is partly related to the activity of leaf-colonizing bacteria. Despite a higher relative nitrogen content in the remaining litter of the fast decomposing S. caseolaris and A. alba as compared to the other three species, the total loss of nitrogen was even higher because of the much higher mass loss after three months of decomposition. It is inferred that the amount of labile nitrogenous organic matter plays a major role in determining the rate of decomposition of leaf litter in mangroves.

Decomposition of naphthalene by dc gliding arc gas discharge.

PubMed

Yu, Liang; Li, Xiaodong; Tu, Xin; Wang, Yu; Lu, Shengyong; Yan, Jianhua

2010-01-14

Gliding arc discharge has been proved to be effective in treatment of gas and liquid contaminants. In this study, physical characteristics of dc gliding arc discharge and its application to naphthalene destruction are investigated with different external resistances and carrier gases. The decomposition rate increases with increasing of oxygen concentration and decreases with external resistance. This value can be achieved up to 92.3% at the external resistance of 50 kOmega in the oxygen discharge, while the highest destruction energy efficiency reaches 3.6 g (kW h)(-1) with the external resistance of 93 kOmega. Possible reaction pathways and degradation mechanisms in the plasma with different gases are proposed by qualitative analysis of postdestructed products. In the air and oxygen gliding arc discharges, the naphthalene degradation is mainly governed by reactions with oxygen-derived radicals.

Reaction paths of alane dissociation on the Si(0 0 1) surface

NASA Astrophysics Data System (ADS)

Smith, Richard; Bowler, David R.

2018-03-01

Building on our earlier study, we examine the kinetic barriers to decomposition of alane, AlH3, on the Si(0 0 1) surface, using the nudged elastic band approach within density functional theory. We find that the initial decomposition to AlH with two H atoms on the surface proceeds without a significant barrier. There are several pathways available to lose the final hydrogen, though these present barriers of up to 1 eV. Incorporation is more challenging, with the initial structures less stable in several cases than the starting structures, just as was found for phosphorus. We identify a stable route for Al incorporation following selective surface hydrogen desorption (e.g. by scanning tunneling microscope tip). The overall process parallels PH3, and indicates that atomically precise acceptor doping should be possible.

Azole energetic materials: Initial mechanisms for the energy release from electronical excited nitropyrazoles

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2014-01-21

Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustratemore » that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S{sub 2} nitropyraozles can nonradiatively relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{sub 1}/S{sub 0}){sub CI} conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S{sub 1} state or S{sub 0} state. In model systems, NO is generated in the S{sub 1} state, while in the energetic material DNP, NO is produced on the ground state surface, as the S{sub 1} decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.« less

Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2)--untangling the reaction mechanisms involved in the decomposition of model energetic materials.

PubMed

Maksyutenko, Pavlo; Muzangwa, Lloyd G; Jones, Brant M; Kaiser, Ralf I

2015-03-21

Solid nitromethane (CH3NO2) along with its isotopically labelled counterpart D3-nitromethane (CD3NO2) ices were exposed to Lyman α photons to investigate the mechanism involved in the decomposition of energetic materials in the condensed phase. The chemical processes in the ices were monitored online and in situ via infrared spectroscopy complimented by temperature programmed desorption studies utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with pulsed photoionization (ReTOF-PI) at 10.49 eV. The infrared data revealed the formation of cis-methylnitrite (CH3ONO), formaldehyde (H2CO), water (H2O), carbon monoxide (CO), and carbon dioxide (CO2). Upon sublimation of the irradiated samples, three classes of higher molecular weight products, which are uniquely formed in the condensed phase, were identified via ReTOF-PI: (i) nitroso compounds [nitrosomethane (CH3NO), nitrosoethane (C2H5NO), nitrosopropane (C3H7NO)], (ii) nitrite compounds [methylnitrite (CH3ONO), ethylnitrite (C2H5ONO), propylnitrite (C3H7ONO)], and (iii) higher molecular weight molecules [CH3NONOCH3, CH3NONO2CH3, CH3OCH2NO2, ONCH2CH2NO2]. The mechanistical information obtained in the present study suggest that the decomposition of nitromethane in the condensed phase is more complex compared to the gas phase under collision-free conditions opening up not only hitherto unobserved decomposition pathways of nitromethane (hydrogen atom loss, oxygen atom loss, retro carbene insertion), but also the blocking of several initial decomposition steps due to the 'matrix cage effect'.

Factors influencing organic carbon preservation in marine sediments

NASA Technical Reports Server (NTRS)

Canfield, D. E.

1994-01-01

The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

Decomposition of potent greenhouse gas sulfur hexafluoride (SF6) by Kirschsteinite-dominant stainless steel slag.

PubMed

Zhang, Jia; Zhou, Ji Zhi; Xu, Zhi Ping; Li, Yajun; Cao, Tiehua; Zhao, Jun; Ruan, Xiuxiu; Liu, Qiang; Qian, Guangren

2014-01-01

In this investigation, kirschsteinite-dominant stainless steel slag (SSS) has been found to decompose sulfur hexafluoride (SF6) with the activity higher than pure metal oxides, such as Fe2O3 and CaO. SSS is mainly made up of CaO·FeO·SiO2(CFS)/MgO·FeO·MnO(RO) phase conglomeration. The SF6 decomposition reaction with SSS at 500-700 °C generated solid MF2/MF3 and gaseous SiF4, SO2/SO3 as well as HF. When 10 wt % of SSS was replaced by Fe2O3 or CaO, the SF6 decomposition amount decreased from 21.0 to 15.2 or 15.0 mg/g at 600 °C. The advantage of SSS over Fe2O3 or CaO in the SF6 decomposition is related to its own special microstructure and composition. The dispersion of each oxide component in SSS reduces the sintering of freshly formed MF2/MF3, which is severe in the case of pure metal oxides and inhibits the continuous reaction of inner components. Moreover, SiO2 in SSS reacts with SF6 and evolves as gaseous SiF4, which leaves SSS with voids and consequently exposes inner oxides for further reactions. In addition, we have found that oxygen significantly inhibited the SF6 decomposition with SSS while H2O did not, which could be explained in terms of reaction pathways. This research thus demonstrates that waste material SSS could be potentially an effective removal reagent of greenhouse gas SF6.

Mitigation of Manhole Events Caused by Secondary Cable Failure

NASA Astrophysics Data System (ADS)

Zhang, Lili

"Manhole event" refers to a range of phenomena, such as smokers, fires and explosions which occur on underground electrical infrastructure, primarily in major cities. The most common cause of manhole events is decomposition of secondary cable initiated by an electric fault. The work presented in this thesis addresses various aspects related to the evolution and mitigation of the manhole events caused by secondary cable insulation failure. Manhole events develop as a result of thermal decomposition of organic materials present in the cable duct and manholes. Polymer characterization techniques are applied to intensively study the materials properties as related to manhole events, mainly the thermal decomposition behaviors of the polymers present in the cable duct. Though evolved gas analysis, the combustible gases have been quantitatively identified. Based on analysis and knowledge of field conditions, manhole events is divided into at least two classes, those in which exothermic chemical reactions dominate and those in which electrical energy dominates. The more common form of manhole event is driven by air flow down the duct. Numerical modeling of smolder propagation in the cable duct demonstrated that limiting air flow is effective in reducing the generation rate of combustible gas, in other words, limiting manhole events to relatively minor "smokers". Besides manhole events, another by-product of secondary cable insulation breakdown is stray voltage. The danger to personnel due to stray voltage is mostly caused by the 'step potential'. The amplitude of step potential as a result of various types of insulation defects is calculated using Finite Element Analysis (FEA) program.

Hydrogen Peroxide - Material Compatibility Studied by Microcalorimetry

NASA Technical Reports Server (NTRS)

Homung, Steven D.; Davis, Dennis D.; Baker, David; Popp, Christopher G.

2003-01-01

Environmental and toxicity concerns with current hypergolic propellants have led to a renewed interest in propellant grade hydrogen peroxide (HP) for propellant applications. Storability and stability has always been an issue with HP. Contamination or contact of HP with metallic surfaces may cause decomposition, which can result in the evolution of heat and gas leading to increased pressure or thermal hazards. The NASA Johnson Space Center White Sands Test Facility has developed a technique to monitor the decompositions of hydrogen peroxide at temperatures ranging from 25 to 60 C. Using isothermal microcalorimetry we have measured decomposition rates at the picomole/s/g level showing the catalytic effects of materials of construction. In this paper we will present the results of testing with Class 1 and 2 materials in 90 percent hydrogen peroxide.

Glucose and Fructose to Platform Chemicals: Understanding the Thermodynamic Landscapes of Acid-Catalysed Reactions Using High-Level ab Initio Methods

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

Assary, Rajeev S.; Kim, Taijin; Low, John

Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of themore » fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2–OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2–OH position, which includes a C–C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.« less

Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods.

PubMed

Assary, Rajeev S; Kim, Taejin; Low, John J; Greeley, Jeff; Curtiss, Larry A

2012-12-28

Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2-OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2-OH position, which includes a C-C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.

Forming trifluoromethylmetallates: competition between decarboxylation and C-F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]-.

PubMed

Rijs, Nicole J; O'Hair, Richard A J

2012-03-28

A combination of gas-phase 3D quadrupole ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the mechanism of thermal decomposition of fluorinated coinage metal carboxylates. The precursor anions, [CF(3)CO(2)MO(2)CCF(3)](-) (M = Cu, Ag and Au), were introduced into the gas-phase via electrospray ionization. Multistage mass spectrometry (MS(n)) experiments were conducted utilizing collision-induced dissociation, yielding a series of trifluoromethylated organometallic species and fluorides via the loss of CO(2), CF(2) or "CF(2)CO(2)". Carboxylate ligand loss was insignificant or absent in all cases. DFT calculations were carried out on a range of potentially competing fragmentation pathways for [CF(3)CO(2)MO(2)CCF(3)](-), [CF(3)CO(2)MCF(3)](-) and [CF(3)CO(2)MF](-). These shed light on possible products and mechanisms for loss of "CF(2)CO(2)", namely, concerted or step-wise loss of CO(2) and CF(2) and a CF(2)CO(2) lactone pathway. The lactone pathway was found to be higher in energy in all cases. In addition, the possibility of forming [CF(3)MCF(3)](-) and [CF(3)MF](-), via decarboxylation is discussed. For the first time the novel fluoride complexes [FMF](-), M = Cu, Ag and Au have been experimentally observed. Finally, the decomposition reactions of [CF(3)CO(2)ML](-) (where L = CF(3) and CF(3)CO(2)) and [CH(3)CO(2)ML](-) (where L = CH(3) and CH(3)CO(2)) are compared.

Diagnostic System for Decomposition Studies of Energetic Materials

DTIC Science & Technology

2017-10-03

transition states and reaction pathways are sought. The overall objective for these combined experimental studies and quantum mechanics investigations...peak-to-peak 1 min: 50,000:1 ( 8.6×10-6 AU noise) peak-to-peak Interferometer UltraScan linear air bearing scanner with True -Alignment Aperture... True 24 bit dynamic range for all scan velocities, dual channel data acquisition Validation Internal validation unit, 6 positions, certified

Influences of growth parameters on the reaction pathway during GaN synthesis

NASA Astrophysics Data System (ADS)

Zhang, Zhi; Liu, Zhongyi; Fang, Haisheng

2018-01-01

Gallium nitride (GaN) film growth is a complicated physical and chemical process including fluid flow, heat transfer, species transport and chemical reaction. Study of the reaction mechanism, i.e., the reaction pathway, is important for optimizing the growth process in the actual manufacture. In the paper, the growth pathway of GaN in a closed-coupled showerhead metal-organic chemical vapor deposition (CCS-MOCVD) reactor is investigated in detail using computational fluid dynamics (CFD). Influences of the process parameters, such as the chamber pressure, the inlet temperature, the susceptor temperature and the pre-exponential factor, on the reaction pathway are examined. The results show that increases of the chamber pressure or the inlet temperature, as well as reductions of the susceptor temperature or the pre-exponential factor lead to the adduct route dominating the growth. The deposition rate contributed by the decomposition route, however, can be enhanced dramatically by increasing the inlet temperature, the susceptor temperature and the pre-exponential factor.

Pyrolysis characteristics and pathways of protein, lipid and carbohydrate isolated from microalgae Nannochloropsis sp.

PubMed

Wang, Xin; Sheng, Lili; Yang, Xiaoyi

2017-04-01

Microalgal components were isolated gradually to get lipid-rich, protein-rich and carbohydrate-rich components. The aim of this work was to study pyrolysis mechanism of microalgae by real isolated real algae components. Thermogrametric analysis (DTG) curve of microalgae was fitted by single pyrolysis curves of protein, lipid and carbohydrate except special zones, which likely affected by cell disruption and hydrolysis mass loss. Experimental microalgae liquefaction without water index N was 0.6776, 0.3861 and 0.2856 for isolated lipid, protein and carbohydrate. Pyrolysis pathways of lipid are decarboxylation, decarbonylation, fragmentation of glycerin moieties and steroid to form hydrocarbons, carboxylic acids and esters. Pyrolysis pathways of protein are decarboxylation, deamination, hydrocarbon residue fragmentation, dimerization and fragmentation of peptide bonds to form amide/amines/nitriles, esters, hydrocarbons and N-heterocyclic compounds, especially diketopiperazines (DKPs). Pyrolysis pathways of carbohydrate are dehydrated reactions and further fragmentation to form ketones and aldehyde, decomposition of lignin to form phenols, and fragmentation of lipopolysaccharides. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.

PubMed

Gunawan, Richard; Zhang, Dongke

2009-06-15

The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.

Exploring metabolic pathway disruption in the subchronic phencyclidine model of schizophrenia with the Generalized Singular Value Decomposition

PubMed Central

2011-01-01

Background The quantification of experimentally-induced alterations in biological pathways remains a major challenge in systems biology. One example of this is the quantitative characterization of alterations in defined, established metabolic pathways from complex metabolomic data. At present, the disruption of a given metabolic pathway is inferred from metabolomic data by observing an alteration in the level of one or more individual metabolites present within that pathway. Not only is this approach open to subjectivity, as metabolites participate in multiple pathways, but it also ignores useful information available through the pairwise correlations between metabolites. This extra information may be incorporated using a higher-level approach that looks for alterations between a pair of correlation networks. In this way experimentally-induced alterations in metabolic pathways can be quantitatively defined by characterizing group differences in metabolite clustering. Taking this approach increases the objectivity of interpreting alterations in metabolic pathways from metabolomic data. Results We present and justify a new technique for comparing pairs of networks--in our case these networks are based on the same set of nodes and there are two distinct types of weighted edges. The algorithm is based on the Generalized Singular Value Decomposition (GSVD), which may be regarded as an extension of Principle Components Analysis to the case of two data sets. We show how the GSVD can be interpreted as a technique for reordering the two networks in order to reveal clusters that are exclusive to only one. Here we apply this algorithm to a new set of metabolomic data from the prefrontal cortex (PFC) of a translational model relevant to schizophrenia, rats treated subchronically with the N-methyl-D-Aspartic acid (NMDA) receptor antagonist phencyclidine (PCP). This provides us with a means to quantify which predefined metabolic pathways (Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolite pathway database) were altered in the PFC of PCP-treated rats. Several significant changes were discovered, notably: 1) neuroactive ligands active at glutamate and GABA receptors are disrupted in the PFC of PCP-treated animals, 2) glutamate dysfunction in these animals was not limited to compromised glutamatergic neurotransmission but also involves the disruption of metabolic pathways linked to glutamate; and 3) a specific series of purine reactions Xanthine ← Hypoxyanthine ↔ Inosine ← IMP → adenylosuccinate is also disrupted in the PFC of PCP-treated animals. Conclusions Network reordering via the GSVD provides a means to discover statistically validated differences in clustering between a pair of networks. In practice this analytical approach, when applied to metabolomic data, allows us to quantify the alterations in metabolic pathways between two experimental groups. With this new computational technique we identified metabolic pathway alterations that are consistent with known results. Furthermore, we discovered disruption in a novel series of purine reactions that may contribute to the PFC dysfunction and cognitive deficits seen in schizophrenia. PMID:21575198

Simulated acid rain alters litter decomposition and enhances the allelopathic potential of the invasive plant Wedelia trilobata (Creeping Daisy)

USDA-ARS?s Scientific Manuscript database

Invasive species and acid rain cause global environmental problems. Limited information exists, however, concerning the effects of acid rain on the invasiveness of these plants. For example, creeping daisy, an invasive exotic allelopathic weed, has caused great damage in southern China where acid ra...

S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering

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

Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de; Ellerbrock, Roman, E-mail: roman.ellerbrock@uni-bielefeld.de

2016-05-28

A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. Inmore » contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail.« less

Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO 3, U 2O 7, and UO 4

DOE PAGES

Guo, Xiaofeng; Wu, Di; Xu, Hongwu; ...

2016-09-01

The thermal decomposition of studtite (UO 2)O 2(H 2O) 2·2H 2O results in a series of intermediate X-ray amorphous materials with general composition UO 3+x (x = 0, 0.5, 1). As an extension of a structural study on U 2O 7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solutionmore » calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO 3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO 3+x materials that pose the risk of significant O 2 gas. Quantitative knowledge of the energy landscape of amorphous UO 3+x was provided for stability analysis and assessment of conditions for decomposition.« less

Fast flux module detection using matroid theory.

PubMed

Reimers, Arne C; Bruggeman, Frank J; Olivier, Brett G; Stougie, Leen

2015-05-01

Flux balance analysis (FBA) is one of the most often applied methods on genome-scale metabolic networks. Although FBA uniquely determines the optimal yield, the pathway that achieves this is usually not unique. The analysis of the optimal-yield flux space has been an open challenge. Flux variability analysis is only capturing some properties of the flux space, while elementary mode analysis is intractable due to the enormous number of elementary modes. However, it has been found by Kelk et al. (2012) that the space of optimal-yield fluxes decomposes into flux modules. These decompositions allow a much easier but still comprehensive analysis of the optimal-yield flux space. Using the mathematical definition of module introduced by Müller and Bockmayr (2013b), we discovered useful connections to matroid theory, through which efficient algorithms enable us to compute the decomposition into modules in a few seconds for genome-scale networks. Using that every module can be represented by one reaction that represents its function, in this article, we also present a method that uses this decomposition to visualize the interplay of modules. We expect the new method to replace flux variability analysis in the pipelines for metabolic networks.

Influence of Cooking (Microwaving and Broiling) on Cylindrospermopsin Concentration in Muscle of Nile Tilapia (Oreochromis niloticus) and Characterization of Decomposition Products

PubMed Central

Prieto, Ana I.; Guzmán-Guillén, Remedios; Valderrama-Fernández, Rocío; Jos, Ángeles; Cameán, Ana M.

2017-01-01

Cylindrospermopsin (CYN) has become increasingly important as a freshwater algal toxin, showing cytotoxic effects. This toxin is able to bioaccumulate in freshwater food webs, representing a serious human health problem. Normally, fish is cooked before consumption, and CYN concentration can be altered. For the first time, the effects of microwaving and broiling for 1 and 2 min on CYN concentration and its decomposition products in fish muscle (Oreochromis niloticus) contaminated in the laboratory were investigated, using UPLC-MS/MS and Orbitrap. The results show that cooking the fish reduced unconjugated CYN levels by 11, 10 and 15% after microwaving for 1 and 2 min, and broiling for 2 min, respectively, compared to control fish. Different CYN decomposition products with m/z 416.1234 (7-epi-CYN) and m/z 336.16663 (diasteroisomers C-3A, C-3C, C-3D, C-3E, C-3F) are generated in fish samples submitted to cooking. Based on the relative abundance of the decomposition products, the possible degradation pathways taking place by microwaving may be through the formation of 7-epi-CYN and m/z 336.16663 compounds, whereas in the case of broiling the last route is the only one observed in this study. The influence of cooking and the toxicity characterization of the degradation products generated in CYN-contaminated fish are of importance for more realistic risk evaluation related to their consumption. PMID:28587145

Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Chen, Lin; Yin, Linlin; Zhang, Jie

2017-01-03

The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H 2 S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H 2 S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H 2 S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H 2 S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H 2 S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H 2 S contributions from microwave and conventional pyrolysis, the significant increase of H 2 S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H 2 S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H 2 S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.

Influence of Cooking (Microwaving and Broiling) on Cylindrospermopsin Concentration in Muscle of Nile Tilapia (Oreochromis niloticus) and Characterization of Decomposition Products.

PubMed

Prieto, Ana I; Guzmán-Guillén, Remedios; Valderrama-Fernández, Rocío; Jos, Ángeles; Cameán, Ana M

2017-05-26

Cylindrospermopsin (CYN) has become increasingly important as a freshwater algal toxin, showing cytotoxic effects. This toxin is able to bioaccumulate in freshwater food webs, representing a serious human health problem. Normally, fish is cooked before consumption, and CYN concentration can be altered. For the first time, the effects of microwaving and broiling for 1 and 2 min on CYN concentration and its decomposition products in fish muscle ( Oreochromis niloticus ) contaminated in the laboratory were investigated, using UPLC-MS/MS and Orbitrap. The results show that cooking the fish reduced unconjugated CYN levels by 11, 10 and 15% after microwaving for 1 and 2 min, and broiling for 2 min, respectively, compared to control fish. Different CYN decomposition products with m / z 416.1234 (7-epi-CYN) and m / z 336.16663 (diasteroisomers C-3A, C-3C, C-3D, C-3E, C-3F) are generated in fish samples submitted to cooking. Based on the relative abundance of the decomposition products, the possible degradation pathways taking place by microwaving may be through the formation of 7-epi-CYN and m / z 336.16663 compounds, whereas in the case of broiling the last route is the only one observed in this study. The influence of cooking and the toxicity characterization of the degradation products generated in CYN-contaminated fish are of importance for more realistic risk evaluation related to their consumption.

Study of a Novel Method for the Thermolysis of Solutes in Aqueous Solution Using a Low Temperature Bubble Column Evaporator.

PubMed

Shahid, Muhammad; Xue, Xinkai; Fan, Chao; Ninham, Barry W; Pashley, Richard M

2015-06-25

An enhanced thermal decomposition of chemical compounds in aqueous solution has been achieved at reduced solution temperatures. The technique exploits hitherto unrecognized properties of a bubble column evaporator (BCE). It offers better heat transfer efficiency than conventional heat transfer equipment. This is obtained via a continuous flow of hot, dry air bubbles of optimal (1-3 mm) size. Optimal bubble size is maintained by using the bubble coalescence inhibition property of some salts. This novel method is illustrated by a study of thermal decomposition of ammonium bicarbonate (NH4HCO3) and potassium persulfate (K2S2O8) in aqueous solutions. The decomposition occurs at significantly lower temperatures than those needed in bulk solution. The process appears to work via the continuous production of hot (e.g., 150 °C) dry air bubbles, which do not heat the solution significantly but produce a transient hot surface layer around each rising bubble. This causes the thermal decomposition of the solute. The decomposition occurs due to the effective collision of the solute with the surface of the hot bubbles. The new process could, for example, be applied to the regeneration of the ammonium bicarbonate draw solution used in forward osmosis.

Polysulfides as biologically active ingredients of garlic.

PubMed

Münchberg, Ute; Anwar, Awais; Mecklenburg, Susanne; Jacob, Claus

2007-05-21

Garlic has long been considered as a natural remedy against a range of human illnesses, including various bacterial, viral and fungal infections. This kind of antibiotic activity of garlic has mostly been associated with the thiosulfinate allicin. Even so, recent studies have pointed towards a significant biological activity of trisulfides and tetrasulfides found in various Allium species, including a wide range of antibiotic properties and the ability of polysulfides to cause the death of certain cancer cells. The chemistry underlying the biological activity of these polysulfides is currently emerging. It seems to include a combination of several distinct transformations, such as oxidation reactions, superoxide radical and peroxide generation, decomposition with release of highly electrophilic S(x) species, inhibition of metalloenzymes, disturbance of metal homeostasis and membrane integrity and interference with different cellular signalling pathways. Further research in this area is required to provide a better understanding of polysulfide reactions within a biochemical context. This knowledge may ultimately form the basis for the development of 'green' antibiotics, fungicides and possibly anticancer agents with dramatically reduced side effects in humans.

Uncoupling of the Pathway of Methanogenesis in Northern Wetlands: Connection to Vegetation, and Implications for Variability and Predictability.

NASA Astrophysics Data System (ADS)

Hines, M. E.; Duddleston, K. N.; Chanton, J. P.

2006-12-01

Typical methanogenic decomposition pathways include near terminal carbon intermediates that turn over rapidly with small pool sizes. However, incubation and field experiments demonstrated that these organic intermediates accumulate in northern wetlands due to the lack of consumption by methanogenic bacteria. Acetate is the major organic end product of decomposition rather than CH4, and methanogenesis can be insignificant. The ratio of CO2:acetate:CH4 varied with vegetation type, and habitats dominated by non-vascular plants (Sphagnum) produced more acetate-C than CO2 or CH4. This ratio correlated well with stable C isotope alpha values used to delineate the path of CH4 formation. We suggest that methanogenesis in general is inhibited in oligotrophic wetlands, but that the conversion of acetate to CH4 is more sensitive, which increases the importance of the conversion of H2/CO2 to CH4. The relative importance of CH4 as an end product increased greatly in sites containing even small populations of Carex compared to sites inhabited only by Sphagnum, suggesting that subtle vegetation changes expected to occur during warming could lead to changes in the path of methanogenesis, increasing production. In addition, depth profiles revealed an active surficial (0-7 cm) C cycle that is sensitive to hydrology that may also greatly affect variability of CH4 formation. Acetate production represented a terminal process and was a sink for a large portion of metabolized C whose ultimate fate was aerobic oxidation to CO2. C destined for CH4 is thus bypassed to CO2 and does not contribute to atmospheric CH4. However, the connection and sensitivity of the pathway of methanogenesis to even small vegetation changes suggests that pathways can be mapped, they vary greatly over small distances, and they can change drastically with relatively small temperature increases.

Application of spectral decomposition of ²²²Rn activity concentration signal series measured in Niedźwiedzia Cave to identification of mechanisms responsible for different time-period variations.

PubMed

Przylibski, Tadeusz Andrzej; Wyłomańska, Agnieszka; Zimroz, Radosław; Fijałkowska-Lichwa, Lidia

2015-10-01

The authors present an application of spectral decomposition of (222)Rn activity concentration signal series as a mathematical tool used for distinguishing processes determining temporal changes of radon concentration in cave air. The authors demonstrate that decomposition of monitored signal such as (222)Rn activity concentration in cave air facilitates characterizing the processes affecting changes in the measured concentration of this gas. Thanks to this, one can better correlate and characterize the influence of various processes on radon behaviour in cave air. Distinguishing and characterising these processes enables the understanding of radon behaviour in cave environment and it may also enable and facilitate using radon as a precursor of geodynamic phenomena in the lithosphere. Thanks to the conducted analyses, the authors confirmed the unquestionable influence of convective air exchange between the cave and the atmosphere on seasonal and short-term (diurnal) changes in (222)Rn activity concentration in cave air. Thanks to the applied methodology of signal analysis and decomposition, the authors also identified a third process affecting (222)Rn activity concentration changes in cave air. This is a deterministic process causing changes in radon concentration, with a distribution different from the Gaussian one. The authors consider these changes to be the effect of turbulent air movements caused by the movement of visitors in caves. This movement is heterogeneous in terms of the number of visitors per group and the number of groups visiting a cave per day and per year. Such a process perfectly elucidates the observed character of the registered changes in (222)Rn activity concentration in one of the decomposed components of the analysed signal. The obtained results encourage further research into precise relationships between the registered (222)Rn activity concentration changes and factors causing them, as well as into using radon as a precursor of geodynamic phenomena in the lithosphere. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of macrophyte decomposition on growth rate and community structure of okefenokee swamp bacterioplankton.

PubMed

Murray, R E; Hodson, R E

1986-02-01

Dissolved substances released during decomposition of the white water lily (Nymphaea odorata) can alter the growth rate of Okefenokee Swamp bacterioplankton. In microcosm experiments dissolved compounds released from senescent Nymphaea leaves caused a transient reduction in the abundance and activity of water column bacterioplankton, followed by a period of intense bacterial growth. Rates of [H]thymidine incorporation and turnover of dissolved d-glucose were depressed by over 85%, 3 h after the addition of Nymphaea leachates to microcosms containing Okefenokee Swamp water. Bacterial activity subsequently recovered; after 20 h [H]thymidine incorporation in leachate-treated microcosms was 10-fold greater than that in control microcosms. The recovery of activity was due to a shift in the composition of the bacterial population toward resistance to the inhibitory compounds present in Nymphaea leachates. Inhibitory compounds released during the decomposition of aquatic macrophytes thus act as selective agents which alter the community structure of the bacterial population with respect to leachate resistance. Soluble compounds derived from macrophyte decomposition influence the rate of bacterial secondary production and the availability of microbial biomass to microconsumers.

Decomposition of S-nitrosocysteine via S- to N-transnitrosation

PubMed Central

Peterson, Lisa A.; Wagener, Tanja; Sies, Helmut; Stahl, Wilhelm

2008-01-01

S-Nitrosothiols are thought to be important intermediates in nitric oxide signaling pathways. These compounds are unstable, in part, through their ability to donate NO. One model S-nitrosothiol, S-nitrosocysteine is particularly unstable. Recently, it was proposed that this compound decomposed via intra- and intermolecular transfer of the NO group from the sulfur to the nitrogen to form N-nitrosocysteine. This primary nitrosamine is expected to rapidly rearrange to ultimately form a reactive diazonium ion intermediate. To test this hypothesis, we demonstrated that thiirane-2-carboxylic acid is formed during the decomposition of S-nitrosocysteine at neutral pH. Acrylic acid was another product of this reaction. These results indicate that a small but significant amount of S-nitrosocysteine decomposes via S- to N-transnitrosation. The formation of a reactive intermediate in this process indicates the potential for this reaction to contribute to the toxicological properties of nitric oxide. PMID:17439249

Oribatid mites and nutrient cycling. [Nutrient release by decomposition of leaf litter

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

Crossley, D.A. Jr.

1976-08-01

Communities of oribatid mites (Cryptostigmata) in leaf litter and forest soils consist of an impressive number of individuals. Total populations of the order of 10/sup 5/ oribatids per square meter are commonly reported from forest floors. Because of their numbers, oribatids have been believed to be important contributors to the breakdown of organic detritus. Results are reported from studies of mineral or nutrient element cycling in forest floor ecosystems using radioisotopes as tracers. The phenomenon of cycling allows for the study of feedback loops among ecosystem processes, whereas energy flow is unidirectional. Evaluation of feedback loops can be a meansmore » of quantifying indirect effects of consumers. The availability of radioactive isotopes or radioactive analogs of mineral elements allows for the direct measurement of transfer rates. In decomposition studies applications of radioactive tracers have helped to identify pathways of transfer from microflora to oribatids.« less

Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

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

Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

2015-10-03

Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasificationmore » severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.« less

Methanethiol chemistry on TiO 2-supported Ni clusters

NASA Astrophysics Data System (ADS)

Ozturk, O.; Park, J. B.; Black, T. J.; Rodriguez, J. A.; Hrbek, J.; Chen, D. A.

2008-10-01

The thermal decomposition of methanethiol on Ni clusters grown on TiO 2(1 1 0) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). On all of the Ni surfaces investigated, methane and hydrogen were observed as gaseous products in the TPD experiments, and the only sulfur-containing species that desorbed from the surface was methanethiol itself at low temperatures. The two pathways for methanethiol reaction were hydrodesulfurization to produce methane and nonselective decomposition, which leaves atomic carbon and sulfur on the surface. From high resolution XPS studies, methyl thiolate was identified as the surface intermediate for reaction on TiO 2 and on all of the Ni surfaces investigated, similar to what is observed on single-crystal Ni surfaces. However, the binding sites for methyl thiolate on the 1 ML (monolayer) Ni clusters were different from those on the Ni clusters at coverages of 2.5 ML and higher, based on the S(2p) binding energies for methyl thiolate. No distinct changes in activity or selectivity were observed for the smaller Ni clusters grown at low coverage compared to the more film-like Ni surfaces other than what could be accounted for by changes in total surface area. Interactions between the Ni clusters and the TiO 2 support had two main effects on chemical activity. First, carbon was oxidized by oxygen from the TiO 2 lattice to produce CO at temperatures above 800 K. Second, annealing induced encapsulation of the Ni clusters by reduced TiO x and chemisorbed oxygen. At 800 K, the Ni clusters were totally encapsulated, resulting in a complete loss of methanethiol activity; partial encapsulation at 700 K caused a smaller decrease in activity accompanied by increased oxidation of carbon by lattice oxygen.

Changes in peat chemistry associated with permafrost thaw increase greenhouse gas production

PubMed Central

Hodgkins, Suzanne B.; Tfaily, Malak M.; McCalley, Carmody K.; Logan, Tyler A.; Crill, Patrick M.; Saleska, Scott R.; Rich, Virginia I.; Chanton, Jeffrey P.

2014-01-01

Carbon release due to permafrost thaw represents a potentially major positive climate change feedback. The magnitude of carbon loss and the proportion lost as methane (CH4) vs. carbon dioxide (CO2) depend on factors including temperature, mobilization of previously frozen carbon, hydrology, and changes in organic matter chemistry associated with environmental responses to thaw. While the first three of these effects are relatively well understood, the effect of organic matter chemistry remains largely unstudied. To address this gap, we examined the biogeochemistry of peat and dissolved organic matter (DOM) along a ∼40-y permafrost thaw progression from recently- to fully thawed sites in Stordalen Mire (68.35°N, 19.05°E), a thawing peat plateau in northern Sweden. Thaw-induced subsidence and the resulting inundation along this progression led to succession in vegetation types accompanied by an evolution in organic matter chemistry. Peat C/N ratios decreased whereas humification rates increased, and DOM shifted toward lower molecular weight compounds with lower aromaticity, lower organic oxygen content, and more abundant microbially produced compounds. Corresponding changes in decomposition along this gradient included increasing CH4 and CO2 production potentials, higher relative CH4/CO2 ratios, and a shift in CH4 production pathway from CO2 reduction to acetate cleavage. These results imply that subsidence and thermokarst-associated increases in organic matter lability cause shifts in biogeochemical processes toward faster decomposition with an increasing proportion of carbon released as CH4. This impact of permafrost thaw on organic matter chemistry could intensify the predicted climate feedbacks of increasing temperatures, permafrost carbon mobilization, and hydrologic changes. PMID:24711402

Towards a physical understanding of stratospheric cooling under global warming through a process-based decomposition method

NASA Astrophysics Data System (ADS)

Yang, Yang; Ren, R.-C.; Cai, Ming

2016-12-01

The stratosphere has been cooling under global warming, the causes of which are not yet well understood. This study applied a process-based decomposition method (CFRAM; Coupled Surface-Atmosphere Climate Feedback Response Analysis Method) to the simulation results of a Coupled Model Intercomparison Project, phase 5 (CMIP5) model (CCSM4; Community Climate System Model, version 4), to demonstrate the responsible radiative and non-radiative processes involved in the stratospheric cooling. By focusing on the long-term stratospheric temperature changes between the "historical run" and the 8.5 W m-2 Representative Concentration Pathway (RCP8.5) scenario, this study demonstrates that the changes of radiative radiation due to CO2, ozone and water vapor are the main divers of stratospheric cooling in both winter and summer. They contribute to the cooling changes by reducing the net radiative energy (mainly downward radiation) received by the stratospheric layer. In terms of the global average, their contributions are around -5, -1.5, and -1 K, respectively. However, the observed stratospheric cooling is much weaker than the cooling by radiative processes. It is because changes in atmospheric dynamic processes act to strongly mitigate the radiative cooling by yielding a roughly 4 K warming on the global average base. In particular, the much stronger/weaker dynamic warming in the northern/southern winter extratropics is associated with an increase of the planetary-wave activity in the northern winter, but a slight decrease in the southern winter hemisphere, under global warming. More importantly, although radiative processes dominate the stratospheric cooling, the spatial patterns are largely determined by the non-radiative effects of dynamic processes.

Untangling climatic and autogenic signals in peat records

NASA Astrophysics Data System (ADS)

Morris, Paul J.; Baird, Andrew J.; Young, Dylan M.; Swindles, Graeme T.

2016-04-01

Raised bogs contain potentially valuable information about Holocene climate change. However, autogenic processes may disconnect peatland hydrological behaviour from climate, and overwrite and degrade climatic signals in peat records. How can genuine climate signals be separated from autogenic changes? What level of detail of climatic information should we expect to be able to recover from peat-based reconstructions? We used an updated version of the DigiBog model to simulate peatland development and response to reconstructed Holocene rainfall and temperature reconstructions. The model represents key processes that are influential in peatland development and climate signal preservation, and includes a network of feedbacks between peat accumulation, decomposition, hydraulic structure and hydrological processes. It also incorporates the effects of temperature upon evapotranspiration, plant (litter) productivity and peat decomposition. Negative feedbacks in the model cause simulated water-table depths and peat humification records to exhibit homeostatic recovery from prescribed changes in rainfall, chiefly through changes in drainage. However, the simulated bogs show less resilience to changes in temperature, which cause lasting alterations to peatland structure and function and may therefore be more readily detectable in peat records. The network of feedbacks represented in DigiBog also provide both high- and low-pass filters for climatic information, meaning that the fidelity with which climate signals are preserved in simulated peatlands is determined by both the magnitude and the rate of climate change. Large-magnitude climatic events of an intermediate frequency (i.e., multi-decadal to centennial) are best preserved in the simulated bogs. We found that simulated humification records are further degraded by a phenomenon known as secondary decomposition. Decomposition signals are consistently offset from the climatic events that generate them, and decomposition records of dry-wet-dry climate sequences appear to be particularly vulnerable to overwriting. Our findings have direct implications not only for the interpretation of peat-based records of past climates, but also for understanding the likely vulnerability of peatland ecosystems and carbon stocks to future climate change.

Designing and Thermal Analysis of Safe Lithium Ion Cathode Materials for High Energy Applications

NASA Astrophysics Data System (ADS)

Hu, Enyuan

Safety is one of the most critical issues facing lithium-ion battery application in vehicles. Addressing this issue requires the integration of several aspects, especially the material chemistry and the battery thermal management. First, thermal stability investigation was carried out on an attractive high energy density material LiNi0.5Mn1.5O4. New findings on the thermal-stability and thermal-decomposition-pathways related to the oxygen-release are discovered for the high-voltage spinel Li xNi0.5Mn1.5O4 (LNMO) with ordered (o-) and disordered (d-) structures at fully delithiated (charged) state using a combination of in situ time-resolved x-ray diffraction (TR-XRD) coupled with mass spectroscopy (MS) and x-ray absorption spectroscopy (XAS). Both fully charged o--LixNi0.5Mn1.5O 4 and d-LixNi0.5Mn1.5O 4 start oxygen-releasing structural changes at temperatures below 300 °C, which is in sharp contrast to the good thermal stability of the 4V-spinel LixMn2O4 with no oxygen being released up to 375 °C. This is mainly caused by the presence of Ni4+ in LNMO, which undergoes dramatic reduction during the thermal decomposition. In addition, charged o-LNMO shows better thermal stability than the d-LNMO counterpart, due to the Ni/Mn ordering and smaller amount of the rock-salt impurity phase in o-LNMO. Newly identified two thermal-decomposition-pathways from the initial LixNi0.5Mn1.5O 4 spinel to the final NiMn2O4-type spinel structure with and without the intermediate phases (NiMnO3 and alpha-Mn 2O3) are found to play key roles in thermal stability and oxygen release of LNMO during thermal decomposition. In addressing the safety issue associated with LNMO, Fe is selected to partially substitute Ni and Mn simultaneously utilizing the electrochemical activity and structure-stabilizing high spin Fe3+. The synthesized LiNi1/3Mn4/3Fe1/3O4 showed superior thermal stability and satisfactory electrochemical performance. At charged state, it is able to withstand the temperature as high as 500°C without observable oxygen release. It shows comparable cyclability performance to the LNMO material with better rate capability. The undiminished high voltage capacity is due to the electrochemical activity of Fe in the system. Fe also plays the key role of stabilizing the system at Fe3O4 type spinel phase against further phase transformation to the rock salt phase, accounting for the superior thermal stability of LiNi1/3Mn 4/3Fe1/3O4. Thermal analysis of the lithium-ion battery indicates the key role of electric current in contributing to a thermal runaway. FLUENT simulation on a 10-cell battery shows that under fast discharging conditions, the temperature level can easily reach the threshold of malfunction and the battery temperature features a large distribution of 18°C. Simple air cooling is not effective enough in addressing the problem. Designed air cooling or liquid cooling is required for the normal operation of lithium-ion batteries in vehicles.

Species and tissue type regulate long-term decomposition of brackish marsh plants grown under elevated CO2 conditions

NASA Astrophysics Data System (ADS)

Jones, Joshua A.; Cherry, Julia A.; McKee, Karen L.

2016-02-01

Organic matter accumulation, the net effect of plant production and decomposition, contributes to vertical soil accretion in coastal wetlands, thereby playing a key role in whether they keep pace with sea-level rise. Any factor that affects decomposition may affect wetland accretion, including atmospheric CO2 concentrations. Higher CO2 can influence decomposition rates by altering plant tissue chemistry or by causing shifts in plant species composition or biomass partitioning. A combined greenhouse-field experiment examined how elevated CO2 affected plant tissue chemistry and subsequent decomposition of above- and belowground tissues of two common brackish marsh species, Schoenoplectus americanus (C3) and Spartina patens (C4). Both species were grown in monoculture and in mixture under ambient (350-385 μL L-1) or elevated (ambient + 300 μL L-1) atmospheric CO2 conditions, with all other growth conditions held constant, for one growing season. Above- and belowground tissues produced under these treatments were decomposed under ambient field conditions in a brackish marsh in the Mississippi River Delta, USA. Elevated CO2 significantly reduced nitrogen content of S. americanus, but not sufficiently to affect subsequent decomposition. Instead, long-term decomposition (percent mass remaining after 280 d) was controlled by species composition and tissue type. Shoots of S. patens had more mass remaining (41 ± 2%) than those of S. americanus (12 ± 2%). Belowground material decomposed more slowly than that placed aboveground (62 ± 1% vs. 23 ± 3% mass remaining), but rates belowground did not differ between species. Increases in atmospheric CO2 concentration will likely have a greater effect on overall decomposition in this brackish marsh community through shifts in species dominance or biomass allocation than through effects on tissue chemistry. Consequent changes in organic matter accumulation may alter marsh capacity to accommodate sea-level rise through vertical accretion.

Species and tissue type regulate long-term decomposition of brackish marsh plants grown under elevated CO2 conditions

USGS Publications Warehouse

Jones, Joshua A; Cherry, Julia A; Mckee, Karen L.

2016-01-01

Organic matter accumulation, the net effect of plant production and decomposition, contributes to vertical soil accretion in coastal wetlands, thereby playing a key role in whether they keep pace with sea-level rise. Any factor that affects decomposition may affect wetland accretion, including atmospheric CO2 concentrations. Higher CO2 can influence decomposition rates by altering plant tissue chemistry or by causing shifts in plant species composition or biomass partitioning. A combined greenhouse-field experiment examined how elevated CO2 affected plant tissue chemistry and subsequent decomposition of above- and belowground tissues of two common brackish marsh species, Schoenoplectus americanus (C3) and Spartina patens (C4). Both species were grown in monoculture and in mixture under ambient (350-385 μL L-1) or elevated (ambient + 300 μL L-1) atmospheric CO2 conditions, with all other growth conditions held constant, for one growing season. Above- and belowground tissues produced under these treatments were decomposed under ambient field conditions in a brackish marsh in the Mississippi River Delta, USA. Elevated CO2 significantly reduced nitrogen content of S. americanus, but not sufficiently to affect subsequent decomposition. Instead, long-term decomposition (percent mass remaining after 280 d) was controlled by species composition and tissue type. Shoots of S. patens had more mass remaining (41 ± 2%) than those of S. americanus (12 ± 2 %). Belowground material decomposed more slowly than that placed aboveground (62 ± 1% vs. 23 ± 3% mass remaining), but rates belowground did not differ between species. Increases in atmospheric CO2concentration will likely have a greater effect on overall decomposition in this brackish marsh community through shifts in species dominance or biomass allocation than through effects on tissue chemistry. Consequent changes in organic matter accumulation may alter marsh capacity to accommodate sea-level rise through vertical accretion.

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

NASA Astrophysics Data System (ADS)

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

2016-07-01

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

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

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg

2016-07-05

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures upmore » to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

DOE PAGES

Rotavera, Brandon; Zádor, Judit; Welz, Oliver; ...

2014-09-19

The product formation from R + O 2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO 2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O 2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positivemore » dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O 2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.« less

Substrate biochemistry control on the pathways for the formation of soil organic matter

NASA Astrophysics Data System (ADS)

Almeida, L. F.; Hurtarte, L. C.; Souza, I. F.; Barros, E. M.; Vergutz, L.; Silva, I. R.

2017-12-01

Linking plant litter biochemistry, its decomposition and soil organic matter (SOM) formation is not straightforward. To address this issue, we evaluated the decomposition of four biochemical fractions operationally defined as i) hot-water extractable (HWE), ii) total solvent (acetone) extractable (TSE), iii) acid-base (HNO3-KOH) unhydrolyzable cellulosic fraction (CF), and iv) acid(H2SO4) unhydrolyzable (AUR) and the transfer of C from these fractions to SOM. Each biochemical fraction was Soxhlet-extracted from isotopically labeled (13C) leaves, twigs, bark and roots of eucalypt plants (120 days old). The molecular composition of each fraction was inferred from thermochemolysis with tertamethylammonium (TMAH), followed by gas chromatography coupled o mass spectrometry (GC-MS). For the incubation, we collected soil samples from the topsoil (0-20 cm) of a sandy-clay loam, kaolinitic Typic Hapludox (Haplic Ferralsol). Four plant organs and four biochemical fractions were arranged into a (4 4) + 1 factorial scheme, including one control treatment (soil only). The samples were incubated at 80% of their water-holding capacity and kept under controlled temperature (25 ºC). The decomposition of the biochemical fractions was monitored by determining the CO2 concentration into the headspace of the vials. Finished the incubation, soil samples were submitted to density followed by particle-size fractionation. HWE and CF was decomposed at faster rates than TSE and AUR throughout the incubation. The soil fraction <53 µm retained a significantly higher proportion of the initial input of HWE (32%) and AUR (31%) than TSE (19%) or CF (15%). Light fraction organic matter (LFOM) with density <1.8 g cm-3, retained a significant proportion of AUR (37%) and TSE (32%) while CF was mostly lost as CO2 (79%). Selective preservation of organic materials (e.g., long-chain lipids) within AUR and TSE fractions appears to be a significant pathway for SOM formation. A microbial-driven pathway cannot be ruled out for any biochemical fraction, but seems more relevant for HWE and CF. In short-term, substrate biochemistry exerts a strong influence on the conversion of eucalypt litter fractions into either CO2 or SOM. Such results warrant the relevance of field-based study to link plant litter biochemistry and SOM formation in long-term.

Synthesis and thermal stability studies of a series of metastable Dion-Jacobson double-layered neodymium-niobate perovskites

NASA Astrophysics Data System (ADS)

Josepha, Elisha A.; Farooq, Sara; Mitchell, Cinnamon M.; Wiley, John B.

2014-08-01

The Dion-Jacobson double-layered perovskite, RbNdNb2O7, is used as a precursor to synthesize the series ANdNb2O7 (A=H, Li, Na, K, NH4, Ag), and (MCl)NdNb2O7 (M=Mn, Fe, Cu) through ion-exchange reactions ≤400 °C. Thermal stability studies indicated that most of these compounds are metastable. A combination of X-ray powder diffraction and differential thermal analysis were used to determine various low temperature decomposition pathways; these pathways were very dependent on the interlayer species. Overall the ANdNb2O7 series was found to be less stable than the corresponding lanthanides, ALaNb2O7.

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

PubMed Central

2014-01-01

Conspectus One of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions. A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to be extremely active in numerous transformations (at least 20) as well as compatible with a broad range of reaction conditions, rendering it a versatile catalytic tool. It should be stated that the η5-phenyl indenyl ligand shows enhanced catalytic activity over related half-sandwich ruthenium complexes. The analogous half-sandwich (cyclopentadienyl and indenyl) ruthenium complexes show lower activity in transfer hydrogenation and allylic alcohol isomerization reactions. In addition, this catalyst allows access to new phenylindenyl ruthenium complexes, which can be achieved in a very straightforward manner and have been successfully used in catalysis. This Account provides an overview of how mechanistic insights into decomposition and stability of a well-known family of ruthenium metathesis precatalysts has resulted in a series of novel and versatile ruthenium complexes with unexpected reactivity. PMID:25264626

[The changing sex differences in life expectancy in Spain (1980-2012): decomposition by age and cause].

PubMed

García González, Juan Manuel; Grande, Rafael

To calculate and analyse the contributions of changes in mortality by age groups and selected causes of death to sex differences in life expectancy at birth in Spain from 1980 to 2012. Cross-sectional study with three time points (1980, 1995, and 2012). We used data from Human Cause-of-Death Database and Human Mortality Database. We use a decomposition method of the differences in life expectancy and gender differences in life expectancy from changes in mortality by 5-year age groups and causes of death between women and men. From 1980 to 1995, the lower mortality of women from 25 years old, and the differences in mortality by HIV/AIDS, lung cancer, and chronic obstructive pulmonary diseases contributed to the gap increase. From 1995 to 2012, greatest improvement in mortality of males under 74 years of age, and in improving male mortality from HIV/AIDS, acute myocardial infarction and traffic accidents contributed to the narrowing. The difference in life expectancy at birth between men and women has decreased since 1995 due to a greater improvement in mortality from causes of death associated with risky behaviours and habits of the working age male population. Copyright © 2017 SESPAS. Publicado por Elsevier España, S.L.U. All rights reserved.

Gender inequality in New Zealand life expectancy: decomposition by age and cause.

PubMed

Sandiford, Peter

2009-12-11

AIM To quantify gender inequality in life expectancy at birth (LEB) in New Zealand and the contribution to it made by different age groups and causes of death. To examine the response of the health sector.METHOD Determination of the trend in sex differences in LEB. Multiple decrement decomposition of LEB differences into components ages and causes. Review of the gender equity policies and priorities of New Zealand's main health sector stakeholders.RESULTS A difference between the sexes in LEB of 4.7 years for Māori and 4.0 years for non-Māori, reverses the historically lower gender disparity among the Māori. Over half of the sex difference in LEB is accounted for by heart disease and all types of cancer and almost a quarter by accidents and suicide but male survival disadvantage is evident in many other causes of death. The health sector is beginning to acknowledge the survival disadvantage of men as inequitable, and reducing disparity as a legitimate goal for health policy.CONCLUSION Although gender inequality in LEB is declining among the non-Māori it remains high among the Māori. Smoking habits may explain some of the difference in LEB but policies must also address the causes of sex differences in accidental death and suicide.

Role of Reactive Mn Complexes in a Litter Decomposition Model System

NASA Astrophysics Data System (ADS)

Nico, P. S.; Keiluweit, M.; Bougoure, J.; Kleber, M.; Summering, J. A.; Maynard, J. J.; Johnson, M.; Pett-Ridge, J.

2012-12-01

The search for controls on litter decomposition rates and pathways has yet to return definitive characteristics that are both statistically robust and can be understood as part of a mechanistic or numerical model. Herein we focus on Mn, an element present in all litter that is likely an active chemical agent of decomposition. Berg and co-workers (2010) found a strong correlation between Mn concentration in litter and the magnitude of litter degradation in boreal forests, suggesting that litter decomposition proceeds more efficiently in the presence of Mn. Although there is much circumstantial evidence for the potential role of Mn in lignin decomposition, few reports exist on mechanistic details of this process. For the current work, we are guided by the hypothesis that the dependence of decomposition on Mn is due to Mn (III)-oxalate complexes act as a 'pretreatment' for structurally intact ligno-carbohydrate complexes (LCC) in fresh plant cell walls (e.g. in litter, root and wood). Manganese (III)-ligand complexes such as Mn (III)-oxalate are known to be potent oxidizers of many different organic and inorganic compounds. In the litter system, the unique property of these complexes may be that they are much smaller than exo-enzymes and therefore more easily able to penetrate LCC complexes in plant cell walls. By acting as 'diffusible oxidizers' and reacting with the organic matrix of the cell wall, these compounds can increase the porosity of fresh litter thereby facilitating access of more specific lignin- and cellulose decomposing enzymes. This possibility was investigated by reacting cell walls of single Zinnia elegans tracheary elements with Mn (III)-oxalate complexes in a continuous flow reactor. The uniformity of these individual plant cells allowed us to examine Mn (III)-induced changes in cell wall chemistry and ultrastructure on the micro-scale using fluorescence and electron microscopy as well as IR and X-ray spectromicroscopy. This presentation will discuss the chemical changes induced by reaction of Mn (III)-complexes with the Zinnia cells, the impact of such reactions on cell integrity, and potential implications for soil C cycling.

Thermal shock resistance ceramic insulator

DOEpatents

Morgan, Chester S.; Johnson, William R.

1980-01-01

Thermal shock resistant cermet insulators containing 0.1-20 volume % metal present as a dispersed phase. The insulators are prepared by a process comprising the steps of (a) providing a first solid phase mixture of a ceramic powder and a metal precursor; (b) heating the first solid phase mixture above the minimum decomposition temperature of the metal precursor for no longer than 30 minutes and to a temperature sufficiently above the decomposition temperature to cause the selective decomposition of the metal precursor to the metal to provide a second solid phase mixture comprising particles of ceramic having discrete metal particles adhering to their surfaces, said metal particles having a mean diameter no more than 1/2 the mean diameter of the ceramic particles, and (c) densifying the second solid phase mixture to provide a cermet insulator having 0.1-20 volume % metal present as a dispersed phase.

New solution decomposition and minimization schemes for Poisson-Boltzmann equation in calculation of biomolecular electrostatics

NASA Astrophysics Data System (ADS)

Xie, Dexuan

2014-10-01

The Poisson-Boltzmann equation (PBE) is one widely-used implicit solvent continuum model in the calculation of electrostatic potential energy for biomolecules in ionic solvent, but its numerical solution remains a challenge due to its strong singularity and nonlinearity caused by its singular distribution source terms and exponential nonlinear terms. To effectively deal with such a challenge, in this paper, new solution decomposition and minimization schemes are proposed, together with a new PBE analysis on solution existence and uniqueness. Moreover, a PBE finite element program package is developed in Python based on the FEniCS program library and GAMer, a molecular surface and volumetric mesh generation program package. Numerical tests on proteins and a nonlinear Born ball model with an analytical solution validate the new solution decomposition and minimization schemes, and demonstrate the effectiveness and efficiency of the new PBE finite element program package.

Soft tissue decomposition of submerged, dismembered pig limbs enclosed in plastic bags.

PubMed

Pakosh, Caitlin M; Rogers, Tracy L

2009-11-01

This study examines underwater soft tissue decomposition of dismembered pig limbs deposited in polyethylene plastic bags. The research evaluates the level of influence that disposal method has on underwater decomposition processes and details observations specific to this scenario. To our knowledge, no other study has yet investigated decomposing, dismembered, and enclosed remains in water environments. The total sample size consisted of 120 dismembered pig limbs, divided into a subsample of 30 pig limbs per recovery period (34 and 71 days) for each treatment. The two treatments simulated non-enclosed and plastic enclosed disposal methods in a water context. The remains were completely submerged in Lake Ontario for 34 and 71 days. In both recovery periods, the non-enclosed samples lost soft tissue to a significantly greater extent than their plastic enclosed counterparts. Disposal of remains in plastic bags therefore results in preservation, most likely caused by bacterial inhibition and reduced oxygen levels.

Untangling climate signals from autogenic changes in long-term peatland development

NASA Astrophysics Data System (ADS)

Morris, Paul J.; Baird, Andy J.; Young, Dylan M.; Swindles, Graeme T.

2015-12-01

Peatlands represent important archives of Holocene paleoclimatic information. However, autogenic processes may disconnect peatland hydrological behavior from climate and overwrite climatic signals in peat records. We use a simulation model of peatland development driven by a range of Holocene climate reconstructions to investigate climate signal preservation in peat records. Simulated water-table depths and peat decomposition profiles exhibit homeostatic recovery from prescribed changes in rainfall, whereas changes in temperature cause lasting alterations to peatland structure and function. Autogenic ecohydrological feedbacks provide both high- and low-pass filters for climatic information, particularly rainfall. Large-magnitude climatic changes of an intermediate temporal scale (i.e., multidecadal to centennial) are most readily preserved in our simulated peat records. Simulated decomposition signals are offset from the climatic changes that generate them due to a phenomenon known as secondary decomposition. Our study provides the mechanistic foundations for a framework to separate climatic and autogenic signals in peat records.

Theoretical Studies of Some HEDM Species: Cyclic O4, Cyclic O3 and Cubane

NASA Technical Reports Server (NTRS)

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

1996-01-01

Calculations have been carried out for the HEDM species (cyclic O4, cyclic O3, and cubane) using CASSCF/derivative and CASSCF/ICCI methods. Cyclic O4 is of interest both as a potential HEDM species and because of its possible role in the ozone deficit problem in atmospheric chemistry. We have studied the pathway for decomposition from the D(2d) minimum and also have found the approximate location of the singlet triplet crossing. The barrier to decomposition is found to be about 9 kcal/mol and is not limited by the singlet triplet crossing. For cyclic O3 we have focused on the crossings between the lowest five surfaces (X(1)A(1), s(1)A(1), (1)A(2), (1)B(1), and (1)B(2)) to provide some insight into ways to form cyclic O3 photochemically. The crossing region between the X(1)A(1) and 2(1)A(1) surfaces is in agreement with the work of Xantheas et al. The calculations show that vertical excitation from the ground state to the (1)A(2) state leads to a crossing with the (1)A(1) manifold near the crossing region of the X(1)A(1) and 2(1)A(1) surfaces. We have studied the decomposition pathways for cubane to benzene plus acetylene and to cyclooctatetraene. We have also studied the ground and excited states for the photochemical ring closure step. The state which closes to cubane can be described as a double triplet pi to pi* excitation with respect to the ground state. Thus, this state has only a small oscillator strength with respect to the ground state. However, there is a singlet pi to pi* state at nearly the same energy and excitation to this state followed by intersystem crossing could lead to the triplet pi to pi* state.

Adsorption of thiophene on silica-supported Mo clusters

NASA Astrophysics Data System (ADS)

Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

2010-07-01

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the capture zone model. The temperature dependence of S0( Ts) consists of two regions consistent with molecular adsorption of thiophene at low temperatures and its decomposition above 250 K. Fitting S0( Ts) curves allows one to determine the bond activation energy for the first elementary decomposition step of C 4H 4S, which amounts to (79 ± 2) kJ/mol and (52 ± 4) kJ/mol for small and large Mo clusters, respectively. Thus, larger clusters are more active for decomposing C 4H 4S than are smaller clusters.

Additive effect on reductive decomposition and binding of carbonate-based solvent toward solid electrolyte interphase formation in lithium-ion battery.

PubMed

Ushirogata, Keisuke; Sodeyama, Keitaro; Okuno, Yukihiro; Tateyama, Yoshitaka

2013-08-14

The solid-electrolyte interphase (SEI) formed through the reductive decomposition of solvent molecules plays a crucial role in the stability and capability of a lithium-ion battery (LIB). Here we investigated the effects of adding vinylene carbonate (VC) to ethylene carbonate (EC) solvent, a typical electrolyte in LIBs, on the reductive decomposition. We focused on both thermodynamics and kinetics of the possible processes and used density functional theory-based molecular dynamics with explicit solvent and Blue-moon ensemble technique for the free energy change. We considered Li(+) in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effects. In addition to clarifying the equilibrium properties, we evaluated the free energy changes along several EC or VC decomposition pathways under one-electron (1e) reduction condition. Two-electron (2e) reduction and attacks of anion radicals to intact molecules were also examined. The present results completely reproduce the gaseous products observed in the experiments. We also found a new mechanism involving the VC additive: the VC additive preferentially reacts with the EC anion radical to suppress the 2e reduction of EC and enhance the initial SEI formation, contrary to the conventional scenario in which VC additive is sacrificially reduced and its radical oligomerization becomes the source of SEI. Because our mechanism needs only 1e reduction, the irreversible capacity at the SEI formation will decrease, which is also consistent with the experimental observations. These results reveal the primary role of VC additive in the EC solvent.

Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

PubMed

Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

2013-10-14

Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect.

Decomposition Pathways of Titanium Isopropoxide Ti(OiPr)4: New Insights from UV-Photodissociation Experiments and Quantum Chemical Calculations.

PubMed

Ershov, Kirill S; Kochubei, Sergei A; Kiselev, Vitaly G; Baklanov, Alexey V

2018-02-01

The UV-photodissociation at 266 nm of a widely used TiO 2 precursor, titanium tetraisopropoxide (Ti(O i Pr) 4 , TTIP), was studied under molecular-beam conditions. Using the MS-TOF technique, atomic titanium and titanium(II) oxide (TiO) were detected among the most abundant photofragments. Experimental results were rationalized with the aid of quantum chemical calculations (DLPNO-CCSD(T) and DFT). Contrary to the existing data in the literature, the new four-centered acetone-elimination reaction was found to be the primary decomposition process of TTIP. According to computational results, the effective activation barrier of this channel was ∼49 kcal/mol, which was ∼13 kcal/mol lower than that of the competing propylene elimination. The former process, followed by the dissociative loss of an H atom, was a dominating channel of TTIP unimolecular decay. The sequential loss of isopropoxy moieties via these two-step processes was supposed to produce the experimentally observed titanium atoms. In turn, the combination of these reactions with propylene elimination can lead to another detected species, TiO. These results indicate that the existing mechanisms of TTIP thermal and photoinitiated decomposition in the chemical-vapor deposition (CVD) of titanium dioxide should be reconsidered.

Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model.

PubMed

Mai, Tam V-T; Duong, Minh V; Nguyen, Hieu T; Lin, Kuang C; Huynh, Lam K

2017-04-27

An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol -1 . This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.

Kinetics of thermal decomposition of some biomasses in an inert environment. An investigation of the effect of lead loaded by biosorption.

PubMed

Martín-Lara, María Ángeles; Iáñez-Rodríguez, Irene; Blázquez, Gabriel; Quesada, Lucía; Pérez, Antonio; Calero, Mónica

2017-12-01

The thermal behavior of some types of raw and lead-polluted biomasses typical in south Spain was studied by non-isothermal thermogravimetry. Experiments were carried out in nitrogen atmosphere at three heating rates (5, 10 and 20°C/min). The results of thermogravimetric tests carried out proved that the presence of lead did not change the main degradation pathways of selected biomass (almond shell (AS) and olive pomace (OP)). However, from a point of view of mass loss, lead-polluted samples showed higher decomposition temperatures and decomposition at higher rate. The determination of activation energies was performed by isoconversional methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman (FR). In general, lead-polluted samples showed lower activation energies than raw ones. Then, Coast-Redfern method was applied to determine kinetic function. The kinetic function that seems to determine the mechanism of thermal degradation of main components of all samples was nth order reaction. Finally, a model based on three parallel reactions (for three pseudocomponents) that fit to nth order reactions was evaluated. This model was appropriate to predict the pyrolysis behavior of the raw and lead-polluted samples in all pyrolysis conditions studied. Copyright © 2017 Elsevier Ltd. All rights reserved.

The old 3-oxoadipate pathway revisited: new insights in the catabolism of aromatics in the saprophytic fungus Aspergillus nidulans.

PubMed

Martins, Tiago M; Hartmann, Diego O; Planchon, Sébastien; Martins, Isabel; Renaut, Jenny; Silva Pereira, Cristina

2015-01-01

Aspergilli play major roles in the natural turnover of elements, especially through the decomposition of plant litter, but the end catabolism of lignin aromatic hydrocarbons remains largely unresolved. The 3-oxoadipate pathway of their degradation combines the catechol and the protocatechuate branches, each using a set of specific genes. However, annotation for most of these genes is lacking or attributed to poorly- or un-characterised families. Aspergillus nidulans can utilise as sole carbon/energy source either benzoate or salicylate (upstream aromatic metabolites of the protocatechuate and the catechol branches, respectively). Using this cultivation strategy and combined analyses of comparative proteomics, gene mining, gene expression and characterisation of particular gene-replacement mutants, we precisely assigned most of the steps of the 3-oxoadipate pathway to specific genes in this fungus. Our findings disclose the genetically encoded potential of saprophytic Ascomycota fungi to utilise this pathway and provide means to untie associated regulatory networks, which are vital to heightening their ecological significance. Copyright © 2014 Elsevier Inc. All rights reserved.

Pi2 detection using Empirical Mode Decomposition (EMD)

NASA Astrophysics Data System (ADS)

Mieth, Johannes Z. D.; Frühauff, Dennis; Glassmeier, Karl-Heinz

2017-04-01

Empirical Mode Decomposition has been used as an alternative method to wavelet transformation to identify onset times of Pi2 pulsations in data sets of the Scandinavian Magnetometer Array (SMA). Pi2 pulsations are magnetohydrodynamic waves occurring during magnetospheric substorms. Almost always Pi2 are observed at substorm onset in mid to low latitudes on Earth's nightside. They are fed by magnetic energy release caused by dipolarization processes. Their periods lie between 40 to 150 seconds. Usually, Pi2 are detected using wavelet transformation. Here, Empirical Mode Decomposition (EMD) is presented as an alternative approach to the traditional procedure. EMD is a young signal decomposition method designed for nonlinear and non-stationary time series. It provides an adaptive, data driven, and complete decomposition of time series into slow and fast oscillations. An optimized version using Monte-Carlo-type noise assistance is used here. By displaying the results in a time-frequency space a characteristic frequency modulation is observed. This frequency modulation can be correlated with the onset of Pi2 pulsations. A basic algorithm to find the onset is presented. Finally, the results are compared to classical wavelet-based analysis. The use of different SMA stations furthermore allows the spatial analysis of Pi2 onset times. EMD mostly finds application in the fields of engineering and medicine. This work demonstrates the applicability of this method to geomagnetic time series.

A TV-constrained decomposition method for spectral CT

NASA Astrophysics Data System (ADS)

Guo, Xiaoyue; Zhang, Li; Xing, Yuxiang

2017-03-01

Spectral CT is attracting more and more attention in medicine, industrial nondestructive testing and security inspection field. Material decomposition is an important issue to a spectral CT to discriminate materials. Because of the spectrum overlap of energy channels, as well as the correlation of basis functions, it is well acknowledged that decomposition step in spectral CT imaging causes noise amplification and artifacts in component coefficient images. In this work, we propose materials decomposition via an optimization method to improve the quality of decomposed coefficient images. On the basis of general optimization problem, total variance minimization is constrained on coefficient images in our overall objective function with adjustable weights. We solve this constrained optimization problem under the framework of ADMM. Validation on both a numerical dental phantom in simulation and a real phantom of pig leg on a practical CT system using dual-energy imaging is executed. Both numerical and physical experiments give visually obvious better reconstructions than a general direct inverse method. SNR and SSIM are adopted to quantitatively evaluate the image quality of decomposed component coefficients. All results demonstrate that the TV-constrained decomposition method performs well in reducing noise without losing spatial resolution so that improving the image quality. The method can be easily incorporated into different types of spectral imaging modalities, as well as for cases with energy channels more than two.

Carbon emissions from decomposition of fire-killed trees following a large wildfire in Oregon, United States

NASA Astrophysics Data System (ADS)

Campbell, John L.; Fontaine, Joseph B.; Donato, Daniel C.

2016-03-01

A key uncertainty concerning the effect of wildfire on carbon dynamics is the rate at which fire-killed biomass (e.g., dead trees) decays and emits carbon to the atmosphere. We used a ground-based approach to compute decomposition of forest biomass killed, but not combusted, in the Biscuit Fire of 2002, an exceptionally large wildfire that burned over 200,000 ha of mixed conifer forest in southwestern Oregon, USA. A combination of federal inventory data and supplementary ground measurements afforded the estimation of fire-caused mortality and subsequent 10 year decomposition for several functionally distinct carbon pools at 180 independent locations in the burn area. Decomposition was highest for fire-killed leaves and fine roots and lowest for large-diameter wood. Decomposition rates varied somewhat among tree species and were only 35% lower for trees still standing than for trees fallen at the time of the fire. We estimate a total of 4.7 Tg C was killed but not combusted in the Biscuit Fire, 85% of which remains 10 years after. Biogenic carbon emissions from fire-killed necromass were estimated to be 1.0, 0.6, and 0.4 Mg C ha-1 yr-1 at 1, 10, and 50 years after the fire, respectively; compared to the one-time pyrogenic emission of nearly 17 Mg C ha-1.

Pathway modeling of microarray data: A case study of pathway activity changes in the testis following in utero exposure to dibutyl phthalate (DBP)

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

Ovacik, Meric A.; Sen, Banalata; Euling, Susan Y.

Pathway activity level analysis, the approach pursued in this study, focuses on all genes that are known to be members of metabolic and signaling pathways as defined by the KEGG database. The pathway activity level analysis entails singular value decomposition (SVD) of the expression data of the genes constituting a given pathway. We explore an extension of the pathway activity methodology for application to time-course microarray data. We show that pathway analysis enhances our ability to detect biologically relevant changes in pathway activity using synthetic data. As a case study, we apply the pathway activity level formulation coupled with significancemore » analysis to microarray data from two different rat testes exposed in utero to Dibutyl Phthalate (DBP). In utero DBP exposure in the rat results in developmental toxicity of a number of male reproductive organs, including the testes. One well-characterized mode of action for DBP and the male reproductive developmental effects is the repression of expression of genes involved in cholesterol transport, steroid biosynthesis and testosterone synthesis that lead to a decreased fetal testicular testosterone. Previous analyses of DBP testes microarray data focused on either individual gene expression changes or changes in the expression of specific genes that are hypothesized, or known, to be important in testicular development and testosterone synthesis. However, a pathway analysis may inform whether there are additional affected pathways that could inform additional modes of action linked to DBP developmental toxicity. We show that Pathway activity analysis may be considered for a more comprehensive analysis of microarray data.« less

Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages.

PubMed

Wang, H; Chen, D; Yuan, G; Ma, X; Dai, X

2013-02-01

In this work, the morphological characteristics of waste polyethylene (PE)/polypropylene (PP) plastics during their pyrolysis process were investigated, and based on their basic image changing patterns representative morphological signals describing the pyrolysis stages were obtained. PE and PP granules and films were used as typical plastics for testing, and influence of impurities was also investigated. During pyrolysis experiments, photographs of the testing samples were taken sequentially with a high-speed infrared camera, and the quantitative parameters that describe the morphological characteristics of these photographs were explored using the "Image Pro Plus (v6.3)" digital image processing software. The experimental results showed that plastics pyrolysis involved four stages: melting, two stages of decomposition which are characterized with bubble formation caused by volatile evaporating, and ash deposition; and each stage was characterized with its own phase changing behaviors and morphological features. Two stages of decomposition are the key step of pyrolysis since they took up half or more of the reaction time; melting step consumed another half of reaction time in experiments when raw materials were heated up from ambient temperatures; and coke-like deposition appeared as a result of decomposition completion. Two morphological signals defined from digital image processing, namely, pixel area of the interested reaction region and bubble ratio (BR) caused by volatile evaporating were found to change regularly with pyrolysis stages. In particular, for all experimental scenarios with plastics films and granules, the BR curves always exhibited a slowly drop as melting started and then a sharp increase followed by a deep decrease corresponding to the first stage of intense decomposition, afterwards a second increase - drop section corresponding to the second stage of decomposition appeared. As ash deposition happened, the BR dropped to zero or very low values. When impurities were involved, the shape of BR curves showed that intense decomposition started earlier but morphological characteristics remained the same. In addition, compared to parameters such as pressure, the BR reflects reaction stages better and its change with pyrolysis process of PE/PP plastics with or without impurities was more intrinsically process correlated; therefore it can be adopted as a signal for pyrolysis process characterization, as well as offering guide to process improvement and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Bimolecular Coupling as a Vector for Decomposition of Fast-Initiating Olefin Metathesis Catalysts.

PubMed

Bailey, Gwendolyn A; Foscato, Marco; Higman, Carolyn S; Day, Craig S; Jensen, Vidar R; Fogg, Deryn E

2018-06-06

The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating, phosphine-free Ru catalysts: the Hoveyda catalyst HII, RuCl 2 (L)(═CHC 6 H 4 - o-O i Pr); the Grela catalyst nG (a derivative of HII with a nitro group para to O i Pr); the Piers catalyst PII, [RuCl 2 (L)(═CHPCy 3 )]OTf; the third-generation Grubbs catalyst GIII, RuCl 2 (L)(py) 2 (═CHPh); and dianiline catalyst DA, RuCl 2 (L)( o-dianiline)(═CHPh), in all of which L = H 2 IMes = N,N'-bis(mesityl)imidazolin-2-ylidene. Prior studies of ethylene metathesis have established that various Ru metathesis catalysts can decompose by β-elimination of propene from the metallacyclobutane intermediate RuCl 2 (H 2 IMes)(κ 2 -C 3 H 6 ), Ru-2. The present work demonstrates that in metathesis of terminal olefins, β-elimination yields only ca. 25-40% propenes for HII, nG, PII, or DA, and none for GIII. The discrepancy is attributed to competing decomposition via bimolecular coupling of methylidene intermediate RuCl 2 (H 2 IMes)(═CH 2 ), Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently stabilized adducts of Ru-1, RuCl 2 (H 2 IMes)L n (═CH 2 ) (L n = py n' ; n' = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and were isolated by precipitating at low temperature (-116 or -78 °C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl 2 (H 2 IMes)L n . A mechanism is proposed based on kinetic studies and molecular-level computational analysis. Bimolecular coupling emerges as an important contributor to the instability of Ru-1, and a potentially major pathway for decomposition of fast-initiating, phosphine-free metathesis catalysts.

Dechlorination of polychlorinated biphenyls by iron and its oxides.

PubMed

Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

2015-10-01

The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Aridity and decomposition processes in complex landscapes

NASA Astrophysics Data System (ADS)

Ossola, Alessandro; Nyman, Petter

2015-04-01

Decomposition of organic matter is a key biogeochemical process contributing to nutrient cycles, carbon fluxes and soil development. The activity of decomposers depends on microclimate, with temperature and rainfall being major drivers. In complex terrain the fine-scale variation in microclimate (and hence water availability) as a result of slope orientation is caused by differences in incoming radiation and surface temperature. Aridity, measured as the long-term balance between net radiation and rainfall, is a metric that can be used to represent variations in water availability within the landscape. Since aridity metrics can be obtained at fine spatial scales, they could theoretically be used to investigate how decomposition processes vary across complex landscapes. In this study, four research sites were selected in tall open sclerophyll forest along a aridity gradient (Budyko dryness index ranging from 1.56 -2.22) where microclimate, litter moisture and soil moisture were monitored continuously for one year. Litter bags were packed to estimate decomposition rates (k) using leaves of a tree species not present in the study area (Eucalyptus globulus) in order to avoid home-field advantage effects. Litter mass loss was measured to assess the activity of macro-decomposers (6mm litter bag mesh size), meso-decomposers (1 mm mesh), microbes above-ground (0.2 mm mesh) and microbes below-ground (2 cm depth, 0.2 mm mesh). Four replicates for each set of bags were installed at each site and bags were collected at 1, 2, 4, 7 and 12 months since installation. We first tested whether differences in microclimate due to slope orientation have significant effects on decomposition processes. Then the dryness index was related to decomposition rates to evaluate if small-scale variation in decomposition can be predicted using readily available information on rainfall and radiation. Decomposition rates (k), calculated fitting single pool negative exponential models, generally decreased with increasing aridity with k going from 0.0025 day-1 on equatorial (dry) facing slopes to 0.0040 day-1 on polar (wet) facing slopes. However, differences in temperature as a result of morning vs afternoon sun on east and west aspects, respectively, (not captured in the aridity metric) resulted in poor prediction of decomposition for the sites located in the intermediate aridity range. Overall the results highlight that relatively small differences in microclimate due to slope orientation can have large effects on decomposition. Future research will aim to refine the aridity metric to better resolve small scale variation in surface temperature which is important when up-scaling decomposition processes to landscapes.

Influence of Macrophyte Decomposition on Growth Rate and Community Structure of Okefenokee Swamp Bacterioplankton †

PubMed Central

Murray, Robert E.; Hodson, Robert E.

1986-01-01

Dissolved substances released during decomposition of the white water lily (Nymphaea odorata) can alter the growth rate of Okefenokee Swamp bacterioplankton. In microcosm experiments dissolved compounds released from senescent Nymphaea leaves caused a transient reduction in the abundance and activity of water column bacterioplankton, followed by a period of intense bacterial growth. Rates of [3H]thymidine incorporation and turnover of dissolved d-glucose were depressed by over 85%, 3 h after the addition of Nymphaea leachates to microcosms containing Okefenokee Swamp water. Bacterial activity subsequently recovered; after 20 h [3H]thymidine incorporation in leachate-treated microcosms was 10-fold greater than that in control microcosms. The recovery of activity was due to a shift in the composition of the bacterial population toward resistance to the inhibitory compounds present in Nymphaea leachates. Inhibitory compounds released during the decomposition of aquatic macrophytes thus act as selective agents which alter the community structure of the bacterial population with respect to leachate resistance. Soluble compounds derived from macrophyte decomposition influence the rate of bacterial secondary production and the availability of microbial biomass to microconsumers. Images PMID:16346986

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Tensor gauge condition and tensor field decomposition

NASA Astrophysics Data System (ADS)

Zhu, Ben-Chao; Chen, Xiang-Song

2015-10-01

We discuss various proposals of separating a tensor field into pure-gauge and gauge-invariant components. Such tensor field decomposition is intimately related to the effort of identifying the real gravitational degrees of freedom out of the metric tensor in Einstein’s general relativity. We show that as for a vector field, the tensor field decomposition has exact correspondence to and can be derived from the gauge-fixing approach. The complication for the tensor field, however, is that there are infinitely many complete gauge conditions in contrast to the uniqueness of Coulomb gauge for a vector field. The cause of such complication, as we reveal, is the emergence of a peculiar gauge-invariant pure-gauge construction for any gauge field of spin ≥ 2. We make an extensive exploration of the complete tensor gauge conditions and their corresponding tensor field decompositions, regarding mathematical structures, equations of motion for the fields and nonlinear properties. Apparently, no single choice is superior in all aspects, due to an awkward fact that no gauge-fixing can reduce a tensor field to be purely dynamical (i.e. transverse and traceless), as can the Coulomb gauge in a vector case.

High-Fidelity, Computational Modeling of Non-Equilibrium Discharges for Combustion Applications

DTIC Science & Technology

2013-10-01

gradient reconstruction)  4th order RK time integration  Domain decomposition parallel enabled Plasma chemistry mechanism 22  Methane-air... plasma chemistry mechanism  Species and pathways relevant to plasma time scale (~10’s ns)  26 Species : E, O, N2 , O2 , H , N2+ , O2+ , N4+ , O4...Photoionization (3-term Helmholtz equation model) 0.0067 0.0447 0.0346 0.1121 0.3059 0.5994 Plasma chemistry mechanism used in studies 81

"Dark" Singlet Oxygen and Electron Paramagnetic Resonance Spin Trapping as Convenient Tools to Assess Photolytic Drug Degradation.

PubMed

Persich, Peter; Hostyn, Steven; Joie, Céline; Winderickx, Guy; Pikkemaat, Jeroen; Romijn, Edwin P; Maes, Bert U W

2017-05-01

Forced degradation studies are an important tool for a systematic assessment of decomposition pathways and identification of reactive sites in active pharmaceutical ingredients (APIs). Two methodologies have been combined in order to provide a deeper understanding of singlet oxygen-related degradation pathways of APIs under light irradiation. First, we report that a "dark" singlet oxygen test enables the investigation of drug reactivity toward singlet oxygen independently of photolytic irradiation processes. Second, the photosensitizing properties of the API producing the singlet oxygen was proven and quantified by spin trapping and electron paramagnetic resonance analysis. A combination of these techniques is an interesting addition to the forced degradation portfolio as it can be used for (1) revealing unexpected degradation pathways of APIs due to singlet oxygen, (2) clarifying photolytic drug-drug interactions in fixed-dose combinations, and (3) synthesizing larger quantities of hardly accessible oxidative drug degradants. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

A thermochemical-biochemical hybrid processing of lignocellulosic biomass for producing fuels and chemicals.

PubMed

Shen, Yanwen; Jarboe, Laura; Brown, Robert; Wen, Zhiyou

2015-12-01

Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing. Copyright © 2015 Elsevier Inc. All rights reserved.

Using AI Planning Techniques to Automatically Generate Image Processing Procedures: A Preliminary Report

NASA Technical Reports Server (NTRS)

Chien, S.

1994-01-01

This paper describes work on the Multimission VICAR Planner (MVP) system to automatically construct executable image processing procedures for custom image processing requests for the JPL Multimission Image Processing Lab (MIPL). This paper focuses on two issues. First, large search spaces caused by complex plans required the use of hand encoded control information. In order to address this in a manner similar to that used by human experts, MVP uses a decomposition-based planner to implement hierarchical/skeletal planning at the higher level and then uses a classical operator based planner to solve subproblems in contexts defined by the high-level decomposition.

X-ray photoelectron spectroscopy and paramagnetic resonance evidence for shock-induced intramolecular bond breaking in some energetic solids

NASA Astrophysics Data System (ADS)

Owens, F. J.; Sharma, J.

1980-03-01

Solid samples of 1,3,5, trinitro 1,3,5, triazacyclohexane (RDX), trinitrotoluene (TNT), and ammonium nitrate were subjected to shock pulses of strength and duration less than the threshold to cause detonation. The recovered shocked samples were studied by x-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The results of these measurements indicate that the shock pulse either broke or altered the internal bonds of the molecules of the solid. The results of the shock decomposition are compared with measurements of the uv and slow thermal decomposition of these materials using the same experimental techniques.

Leaf litter decomposition rates increase with rising mean annual temperature in Hawaiian tropical montane wet forests

PubMed Central

Bothwell, Lori D.; Giardina, Christian P.; Litton, Creighton M.

2014-01-01

Decomposing litter in forest ecosystems supplies nutrients to plants, carbon to heterotrophic soil microorganisms and is a large source of CO2 to the atmosphere. Despite its essential role in carbon and nutrient cycling, the temperature sensitivity of leaf litter decay in tropical forest ecosystems remains poorly resolved, especially in tropical montane wet forests where the warming trend may be amplified compared to tropical wet forests at lower elevations. We quantified leaf litter decomposition rates along a highly constrained 5.2 °C mean annual temperature (MAT) gradient in tropical montane wet forests on the Island of Hawaii. Dominant vegetation, substrate type and age, soil moisture, and disturbance history are all nearly constant across this gradient, allowing us to isolate the effect of rising MAT on leaf litter decomposition and nutrient release. Leaf litter decomposition rates were a positive linear function of MAT, causing the residence time of leaf litter on the forest floor to decline by ∼31 days for each 1 °C increase in MAT. Our estimate of the Q10 temperature coefficient for leaf litter decomposition was 2.17, within the commonly reported range for heterotrophic organic matter decomposition (1.5–2.5) across a broad range of ecosystems. The percentage of leaf litter nitrogen (N) remaining after six months declined linearly with increasing MAT from ∼88% of initial N at the coolest site to ∼74% at the warmest site. The lack of net N immobilization during all three litter collection periods at all MAT plots indicates that N was not limiting to leaf litter decomposition, regardless of temperature. These results suggest that leaf litter decay in tropical montane wet forests may be more sensitive to rising MAT than in tropical lowland wet forests, and that increased rates of N release from decomposing litter could delay or prevent progressive N limitation to net primary productivity with climate warming. PMID:25493213

Electron induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5, a potential heterobimetallic precursor for focused electron beam induced deposition (FEBID).

PubMed

Unlu, Ilyas; Spencer, Julie A; Johnson, Kelsea R; Thorman, Rachel M; Ingólfsson, Oddur; McElwee-White, Lisa; Fairbrother, D Howard

2018-03-14

Electron-induced surface reactions of (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 were explored in situ under ultra-high vacuum conditions using X-ray photoelectron spectroscopy and mass spectrometry. The initial step involves electron-stimulated decomposition of adsorbed (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 molecules, accompanied by the desorption of an average of five CO ligands. A comparison with recent gas phase studies suggests that this precursor decomposition step occurs by a dissociative ionization (DI) process. Further electron irradiation decomposes the residual CO groups and (η 5 -C 5 H 5 , Cp) ligand, in the absence of any ligand desorption. The decomposition of CO ligands leads to Mn oxidation, while electron stimulated Cp decomposition causes all of the associated carbon atoms to be retained in the deposit. The lack of any Fe oxidation is ascribed to either the presence of a protective carbonaceous matrix around the Fe atoms created by the decomposition of the Cp ligand, or to desorption of both CO ligands bound to Fe in the initial decomposition step. The selective oxidation of Mn in the absence of any Fe oxidation suggests that the fate of metal atoms in mixed-metal precursors for focused electron beam induced deposition (FEBID) will be sensitive to the nature and number of ligands in the immediate coordination sphere. In related studies, the composition of deposits created from (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 under steady state deposition conditions, representative of those used to create nanostructures in electron microscopes, were measured and found to be qualitatively consistent with predictions from the UHV surface science studies.

Enhancing our View of the Reservoir: New Insights into Deepwater Gulf of Mexico fields using Frequency Decomposition

NASA Astrophysics Data System (ADS)

Murat, M.

2017-12-01

Color-blended frequency decomposition is a seismic attribute that can be used to educe or draw out and visualize geomorphological features enabling a better understanding of reservoir architecture and connectivity for both exploration and field development planning. Color-blended frequency decomposition was applied to seismic data in several areas of interest in the Deepwater Gulf of Mexico. The objective was stratigraphic characterization to better define reservoir extent, highlight depositional features, identify thicker reservoir zones and examine potential connectivity issues due to stratigraphic variability. Frequency decomposition is a technique to analyze changes in seismic frequency caused by changes in the reservoir thickness, lithology and fluid content. This technique decomposes or separates the seismic frequency spectra into discrete bands of frequency limited seismic data using digital filters. The workflow consists of frequency (spectral) decomposition, RGB color blending of three frequency slices, and horizon or stratal slicing of the color blended frequency data for interpretation. Patterns were visualized and identified in the data that were not obvious on standard stacked seismic sections. These seismic patterns were interpreted and compared to known geomorphological patterns and their environment of deposition. From this we inferred the distribution of potential reservoir sand versus non-reservoir shale and even finer scale details such as the overall direction of the sediment transport and relative thickness. In exploratory areas, stratigraphic characterization from spectral decomposition is used for prospect risking and well planning. Where well control exists, we can validate the seismic observations and our interpretation and use the stratigraphic/geomorphological information to better inform decisions on the need for and placement of development wells.

A data-driven method to enhance vibration signal decomposition for rolling bearing fault analysis

NASA Astrophysics Data System (ADS)

Grasso, M.; Chatterton, S.; Pennacchi, P.; Colosimo, B. M.

2016-12-01

Health condition analysis and diagnostics of rotating machinery requires the capability of properly characterizing the information content of sensor signals in order to detect and identify possible fault features. Time-frequency analysis plays a fundamental role, as it allows determining both the existence and the causes of a fault. The separation of components belonging to different time-frequency scales, either associated to healthy or faulty conditions, represents a challenge that motivates the development of effective methodologies for multi-scale signal decomposition. In this framework, the Empirical Mode Decomposition (EMD) is a flexible tool, thanks to its data-driven and adaptive nature. However, the EMD usually yields an over-decomposition of the original signals into a large number of intrinsic mode functions (IMFs). The selection of most relevant IMFs is a challenging task, and the reference literature lacks automated methods to achieve a synthetic decomposition into few physically meaningful modes by avoiding the generation of spurious or meaningless modes. The paper proposes a novel automated approach aimed at generating a decomposition into a minimal number of relevant modes, called Combined Mode Functions (CMFs), each consisting in a sum of adjacent IMFs that share similar properties. The final number of CMFs is selected in a fully data driven way, leading to an enhanced characterization of the signal content without any information loss. A novel criterion to assess the dissimilarity between adjacent CMFs is proposed, based on probability density functions of frequency spectra. The method is suitable to analyze vibration signals that may be periodically acquired within the operating life of rotating machineries. A rolling element bearing fault analysis based on experimental data is presented to demonstrate the performances of the method and the provided benefits.

Subcalcic diopsides from kimberlites: Chemistry, exsolution microstructures, and thermal history

USGS Publications Warehouse

McCallister, R.H.; Nord, G.L.

1981-01-01

Twenty-six subcalcic diopside megacrysts (Ca/(Ca+ Mg)) = 0.280-0.349, containing approximately 10 mol% jadeite, from 15 kimberlite bodies in South Africa, Botswana, Tanzania, and Lesotho, have been characterized by electron microprobe analysis, X-ray-precession photography, and transmission electron microscopy. Significant exsolution of pigeonite was observed only in those samples for which Ca/(Ca+Mg)???0.320. The exsolution microstructure consists of coherent (001) lamellae with wavelengths ranging from 20 to 31 nm and compositional differences between the hosts and lamellae ranging from 10 to 30 mol% wollastonite. These observations suggest that the exsolution reaction mechanism was spinodal decomposition and that the megacrysts have been quenched at various stages of completion of the decomposition process. Annealing experiments in evacuated SiO2 glass tubes at 1,150?? C for 128 hours failed to homogenize microstructure, whereas, at 5 kbar and 1,150?? C for only 7.25 hours, the two lattices were homogenized. This "pressure effect" suggests that spinodal decomposition in the kimberlitic subcalcic diopside megacrysts can only occur at depths less than ???15 km; the cause of the effect may be the jadeite component in the pyroxene. "Apparent quench" temperatures for the exsolution process in the megacrysts range from 1,250?? C to 990?? C, suggesting that decomposition must have commenced at temperatures of more than ???1,000?? C. These P-T limits lead to the conclusion that, in those kimberlites where spinodal decomposition has occurred in subcalcic diopside megacrysts, such decomposition occurred at shallow levels (<15 km) and, at the present erosion level, temperatures must have been greater than 1,000?? C. ?? 1981 Springer-Verlag.

Possibility of H2O2 decomposition in thin liquid films on Mars

NASA Astrophysics Data System (ADS)

Kereszturi, Akos; Gobi, Sandor

2014-11-01

In this work the pathways and possibilities of H2O2 decomposition on Mars in microscopic liquid interfacial water were analyzed by kinetic calculations. Thermal and photochemical driven decomposition, just like processes catalyzed by various metal oxides, is too slow compared to the annual duration while such microscopic liquid layers exist on Mars today, to produce substantial decomposition. The most effective analyzed process is catalyzed by Fe ions, which could decompose H2O2 under pH<4.5 with a half life of 1-2 days. This process might be important during volcanically influenced periods when sulfur release produces acidic pH, and rotational axis tilt change driven climatic changes also influence the volatile circulation and spatial occurrence just like the duration of thin liquid layer. Under current conditions, using the value of 200 K as the temperature in interfacial water (at the southern hemisphere), and applying Phoenix lander's wet chemistry laboratory results, the pH is not favorable for Fe mobility and this kind of decomposition. Despite current conditions (especially pH) being unfavorable for H2O2 decomposition, microscopic scale interfacial liquid water still might support the process. By the reaction called heterogeneous catalysis, without acidic pH and mobile Fe, but with minerals surfaces containing Fe decomposition of H2O2 with half life of 20 days can happen. This duration is still longer but not several orders than the existence of springtime interfacial liquid water on Mars today. This estimation is relevant for activation energy controlled reaction rates. The other main parameter that may influence the reaction rate is the diffusion speed. Although the available tests and theoretical calculations do not provide firm values for the diffusion speed in such a “2-dimensional” environment, using relevant estimations this parameter in the interfacial liquid layer is smaller than in bulk water. But the 20 days' duration mentioned above is still relevant, as the activation energy driven reaction rate is the main limiting factor in the decomposition and not the diffusion speed. The duration of dozen(s) days is still longer but not with orders of magnitude than the expected duration for the existence of springtime interfacial liquid water on Mars today. The results suggest such decomposition may happen today, however, because of our limited knowledge on chemical processes in thin interfacial liquid layers, this possibility waits for confirmation - and also points to the importance of conducting laboratory tests to validate the possible process. Although some tests were already realized for diffusion in an almost 2-dimensional liquid, the same is not true for activation energy, where only the value from the “normal” measurements was applied. Even if H2O2 decomposition is too slow today, the analysis of such a process is important, as under volcanic influence more effective decomposition might take place in thin interfacial liquids close to the climate of today if released sulfur produces pH<4.5. Large quantity and widespread occurrence of bulk liquid phase are not expected in the Amazonian period, but interfacial liquid water probably appeared regularly, and its locations, especially during volcanically active periods, might make certain sites than others more interesting for astrobiology with the lower concentration of oxidizing H2O2.

Who Benefits from Which Reading Intervention in the Primary Years? Match the Intervention with the Reading Profile

ERIC Educational Resources Information Center

Munro, John

2017-01-01

Reading difficulties may have multiple causes. Effective approaches to reading intervention need to target the specific causes for individual readers. The Early Reading Intervention Knowledge program comprises three intervention pathways: a phonological-phonemic pathway, a phonic-orthographic pathway, and an oral language pathway. This study…

Geometrical flexibility of platinum nanoclusters: impacts on catalytic decomposition of ethylene glycol.

PubMed

Mahmoodinia, Mehdi; Trinh, Thuat T; Åstrand, Per-Olof; Tran, Khanh-Quang

2017-11-01

Catalytic decomposition of ethylene glycol on the Pt 13 cluster was studied as a model system for hydrogen production from a lignocellulosic material. Ethylene glycol was chosen as a starting material because of two reasons, it is the smallest oxygenate with a 1 : 1 carbon to oxygen ratio and it contains the C-H, O-H, C-C, and C-O bonds also present in biomass. Density functional theory calculations were employed for predictions of reaction pathways for C-H, O-H, C-C and C-O cleavages, and Brønsted-Evans-Polanyi relationships were established between the final state and the transition state for all mechanisms. The results show that Pt 13 catalyzes the cleavage reactions of ethylene glycol more favourably than a Pt surface. The flexibility of Pt 13 clusters during the reactions is the key factor in reducing the activation barrier. Overall, the results demonstrate that ethylene glycol and thus biomass can be efficiently converted into hydrogen using platinum nanoclusters as catalysts.

Effect decomposition in the presence of an exposure-induced mediator-outcome confounder

PubMed Central

VanderWeele, Tyler J.; Vansteelandt, Stijn; Robins, James M.

2014-01-01

Methods from causal mediation analysis have generalized the traditional approach to direct and indirect effects in the epidemiologic and social science literature by allowing for interaction and non-linearities. However, the methods from the causal inference literature have themselves been subject to a major limitation in that the so-called natural direct and indirect effects that are employed are not identified from data whenever there is a variable that is affected by the exposure, which also confounds the relationship between the mediator and the outcome. In this paper we describe three alternative approaches to effect decomposition that give quantities that can be interpreted as direct and indirect effects, and that can be identified from data even in the presence of an exposure-induced mediator-outcome confounder. We describe a simple weighting-based estimation method for each of these three approaches, illustrated with data from perinatal epidemiology. The methods described here can shed insight into pathways and questions of mediation even when an exposure-induced mediator-outcome confounder is present. PMID:24487213

Decomposition pathways of polytetrafluoroethylene by co-grinding with strontium/calcium oxides.

PubMed

Qu, Jun; He, Xiaoman; Zhang, Qiwu; Liu, Xinzhong; Saito, Fumio

2017-06-01

Waste polytetrafluoroethylene (PTFE) could be easily decomposed by co-grinding with inorganic additive such as strontium oxide (SrO), strontium peroxide (SrO 2 ) and calcium oxide (CaO) by using a planetary ball mill, in which the fluorine was transformed into nontoxic inorganic fluoride salts such as strontium fluoride (SrF 2 ) or calcium fluoride (CaF 2 ). Depending on the kind of additive as well as the added molar ratio, however, the reaction mechanism of the decomposition was found to change, with different compositions of carbon compounds formed. CO gas, the mixture of strontium carbonate (SrCO 3 ) and carbon, only SrCO 3 were obtained as reaction products respectively with equimolar SrO, excess SrO and excess SrO 2 to the monomer unit CF 2 of PTFE were used. Excess amount of CaO was needed to effectively decompose PTFE because of its lower reactivity compared with strontium oxide, but it promised practical applications due to its low cost.

Distribution of apparent activation energy counterparts during thermo - And thermo-oxidative degradation of Aronia melanocarpa (black chokeberry).

PubMed

Janković, Bojan; Marinović-Cincović, Milena; Janković, Marija

2017-09-01

Kinetics of degradation for Aronia melanocarpa fresh fruits in argon and air atmospheres were investigated. The investigation was based on probability distributions of apparent activation energy of counterparts (ε a ). Isoconversional analysis results indicated that the degradation process in an inert atmosphere was governed by decomposition reactions of esterified compounds. Also, based on same kinetics approach, it was assumed that in an air atmosphere, the primary compound in degradation pathways could be anthocyanins, which undergo rapid chemical reactions. A new model of reactivity demonstrated that, under inert atmospheres, expectation values for ε a occured at levels of statistical probability. These values corresponded to decomposition processes in which polyphenolic compounds might be involved. ε a values obeyed laws of binomial distribution. It was established that, for thermo-oxidative degradation, Poisson distribution represented a very successful approximation for ε a values where there was additional mechanistic complexity and the binomial distribution was no longer valid. Copyright © 2017 Elsevier Ltd. All rights reserved.

GHGs and air pollutants embodied in China's international trade: Temporal and spatial index decomposition analysis.

PubMed

Liu, Zhengyan; Mao, Xianqiang; Song, Peng

2017-01-01

Temporal index decomposition analysis and spatial index decomposition analysis were applied to understand the driving forces of the emissions embodied in China's exports and net exports during 2002-2011, respectively. The accumulated emissions embodied in exports accounted for approximately 30% of the total emissions in China; although the contribution of the sectoral total emissions intensity (technique effect) declined, the scale effect was largely responsible for the mounting emissions associated with export, and the composition effect played a largely insignificant role. Calculations of the emissions embodied in net exports suggest that China is generally in an environmentally inferior position compared with its major trade partners. The differences in the economy-wide emission intensities between China and its major trade partners were the biggest contribution to this reality, and the trade balance effect played a less important role. However, a lower degree of specialization in pollution intensive products in exports than in imports helped to reduce slightly the emissions embodied in net exports. The temporal index decomposition analysis results suggest that China should take effective measures to optimize export and supply-side structure and reduce the total emissions intensity. According to spatial index decomposition analysis, it is suggested that a more aggressive import policy was useful for curbing domestic and global emissions, and the transfer of advanced production technologies and emission control technologies from developed to developing countries should be a compulsory global environmental policy option to mitigate the possible leakage of pollution emissions caused by international trade.

The Relative Importance of Methanogenesis in the Decomposition of Organic Matter in Northern Peatlands

NASA Technical Reports Server (NTRS)

Corbett, J. Elizabeth; Tfaily, Malak M.; Burdige, David J.; Glaser, Paul H.; Chanton, Jeffrey P.

2015-01-01

Using an isotope-mass balance approach and assuming the equimolar production of CO2 and CH4 from methanogenesis (e.g., anaerobic decomposition of cellulose), we calculate that the proportion of total CO2 production from methanogenesis varies from 37 to 83% across a variety of northern peatlands. In a relative sense, methanogenesis was a more important pathway for decomposition in bogs (80 +/- 13% of CO2 production) than in fens (64 +/- 5.7% of CO2 production), but because fens contain more labile substrates they may support higher CH4 production overall. The concentration of CO2 produced from methanogenesis (CO2-meth) can be considered equivalent to CH4 concentration before loss due to ebullition, plant-mediated transport, or diffusion. Bogs produced slightly less CO2-meth than fens (2.9 +/- 1.3 and 3.7 +/- 1.4 mmol/L, respectively). Comparing the quantity of CH4 present to CO2-meth, fens lost slightly more CH4 than bogs (89 +/- 2.8% and 82 +/- 5.3%, respectively) likely due to the presence of vascular plant roots. In collapsed permafrost wetlands, bog moats produced half the amount of CO2-meth (0.8 +/- 0.2mmol/L) relative to midbogs (1.6 +/- 0.6 mmol/L) and methanogenesis was less important (42 +/- 6.6% of total CO2 production relative to 55 +/- 8.1%).We hypothesize that the lower methane production potential in collapsed permafrost wetlands occurs because recently thawed organic substrates are being first exposed to the initial phases of anaerobic decomposition following collapse and flooding. Bog moats lost a comparable amount of CH4 as midbogs (63 +/- 7.0% and 64 +/- 9.3%).

Pyrolysis of furan in a microreactor

NASA Astrophysics Data System (ADS)

Urness, Kimberly N.; Guan, Qi; Golan, Amir; Daily, John W.; Nimlos, Mark R.; Stanton, John F.; Ahmed, Musahid; Ellison, G. Barney

2013-09-01

A silicon carbide microtubular reactor has been used to measure branching ratios in the thermal decomposition of furan, C4H4O. The pyrolysis experiments are carried out by passing a dilute mixture of furan (approximately 0.01%) entrained in a stream of helium through the heated reactor. The SiC reactor (0.66 mm i.d., 2 mm o.d., 2.5 cm long) operates with continuous flow. Experiments were performed with a reactor inlet pressure of 100-300 Torr and a wall temperature between 1200 and 1600 K; characteristic residence times in the reactor are 60-150 μs. The unimolecular decomposition pathway of furan is confirmed to be: furan (+ M) rightleftharpoons α-carbene or β-carbene. The α-carbene fragments to CH2=C=O + HC≡CH while the β-carbene isomerizes to CH2=C=CHCHO. The formyl allene can isomerize to CO + CH3C≡CH or it can fragment to H + CO + HCCCH2. Tunable synchrotron radiation photoionization mass spectrometry is used to monitor the products and to measure the branching ratio of the two carbenes as well as the ratio of [HCCCH2]/[CH3C≡CH]. The results of these pyrolysis experiments demonstrate a preference for 80%-90% of furan decomposition to occur via the β-carbene. For reactor temperatures of 1200-1400 K, no propargyl radicals are formed. As the temperature rises to 1500-1600 K, at most 10% of the decomposition of CH2=C=CHCHO produces H + CO + HCCCH2 radicals. Thermodynamic conditions in the reactor have been modeled by computational fluid dynamics and the experimental results are compared to the predictions of three furan pyrolysis mechanisms. Uncertainty in the pressure-dependency of the initiation reaction rates is a possible a source of discrepancy between experimental results and theoretical predictions.

Importance of soil thermal dynamics on land carbon sequestration in Northern Eurasia during the 21st century

NASA Astrophysics Data System (ADS)

Kicklighter, David; Monier, Erwan; Sokolov, Andrei; Zhuang, Qianlai; Melillo, Jerry

2015-04-01

Recent modeling studies have suggested that carbon sinks in pan-arctic ecosystems may be weakening partially as a result of warming-induced increases in soil organic matter (SOM) decomposition and the exposure of previously frozen SOM to decomposition. This weakening of carbon sinks is likely to continue in the future as vast amount of carbon in permafrost soils is vulnerable to thaw. Here, we examine the importance of considering soil thermal dynamics when determining the effects of climate change and land-use change on carbon dynamics in Northern Eurasia during the 21st century. This importance is assessed by comparing results for a "business as usual" scenario between a version of the Terrestrial Ecosystem Model that does not consider soil thermal dynamics (TEM 4.4) and a version that does consider these dynamics (TEM 6.0). In this scenario, which is similar to the IPCC Representative Concentration Pathways (RCP) 8.5 scenario, the net area covered by food crops and pastures in Northern Eurasia is assumed to remain relatively constant over the 21st century, but the area covered by secondary forests is projected to double as a result of timber harvest and the abandonment of land associated with displacement of agricultural land. Enhanced decomposition from the newly exposed SOM from permafrost thaw also increases nitrogen availability for plant production so that the loss of carbon from the enhanced decomposition is partially compensated by enhanced uptake and storage of atmospheric carbon dioxide in vegetation. Our results indicate that consideration of soil thermal dynamics have a large influence on how simulated terrestrial carbon dynamics in Northern Eurasia respond to changes in climate, atmospheric chemistry (e.g., carbon dioxide fertilization, ozone pollution, nitrogen deposition) and disturbances.

The relative importance of methanogenesis in the decomposition of organic matter in northern peatlands

NASA Astrophysics Data System (ADS)

Corbett, J. Elizabeth; Tfaily, Malak M.; Burdige, David J.; Glaser, Paul H.; Chanton, Jeffrey P.

2015-02-01

Using an isotope-mass balance approach and assuming the equimolar production of CO2 and CH4 from methanogenesis (e.g., anaerobic decomposition of cellulose), we calculate that the proportion of total CO2 production from methanogenesis varies from 37 to 83% across a variety of northern peatlands. In a relative sense, methanogenesis was a more important pathway for decomposition in bogs (80 ± 13% of CO2 production) than in fens (64 ± 5.7% of CO2 production), but because fens contain more labile substrates they may support higher CH4 production overall. The concentration of CO2 produced from methanogenesis (CO2-meth) can be considered equivalent to CH4 concentration before loss due to ebullition, plant-mediated transport, or diffusion. Bogs produced slightly less CO2-meth than fens (2.9 ± 1.3 and 3.7 ± 1.4 mmol/L, respectively). Comparing the quantity of CH4 present to CO2-meth, fens lost slightly more CH4 than bogs (89 ± 2.8% and 82 ± 5.3%, respectively) likely due to the presence of vascular plant roots. In collapsed permafrost wetlands, bog moats produced half the amount of CO2-meth (0.8 ± 0.2 mmol/L) relative to midbogs (1.6 ± 0.6 mmol/L) and methanogenesis was less important (42 ± 6.6% of total CO2 production relative to 55 ± 8.1%). We hypothesize that the lower methane production potential in collapsed permafrost wetlands occurs because recently thawed organic substrates are being first exposed to the initial phases of anaerobic decomposition following collapse and flooding. Bog moats lost a comparable amount of CH4 as midbogs (63 ± 7.0% and 64 ± 9.3%).

Production of ammonia from plasma-catalytic decomposition of urea: Effects of carrier gas composition.

PubMed

Fan, Xing; Li, Jian; Qiu, Danqi; Zhu, Tianle

2018-04-01

Effects of carrier gas composition (N 2 /air) on NH 3 production, energy efficiency regarding NH 3 production and byproducts formation from plasma-catalytic decomposition of urea were systematically investigated using an Al 2 O 3 -packed dielectric barrier discharge (DBD) reactor at room temperature. Results show that the presence of O 2 in the carrier gas accelerates the conversion of urea but leads to less generation of NH 3 . The final yield of NH 3 in the gas phase decreased from 70.5%, 78.7%, 66.6% and 67.2% to 54.1%, 51.7%, 49.6% and 53.4% for applied voltages of 17, 19, 21 and 23kV, respectively when air was used as the carrier gas instead of N 2 . From the viewpoint of energy savings, however, air carrier gas is better than N 2 due to reduced energy consumption and increased energy efficiency for decomposition of a fixed amount of urea. Carrier gas composition has little influence on the major decomposition pathways of urea under the synergetic effects of plasma and Al 2 O 3 catalyst to give NH 3 and CO 2 as the main products. Compared to a small amount of N 2 O formed with N 2 as the carrier gas, however, more byproducts including N 2 O and NO 2 in the gas phase and NH 4 NO 3 in solid deposits were produced with air as the carrier gas, probably due to the unproductive consumption of NH 3 , the possible intermediate HNCO and even urea by the abundant active oxygen species and nitrogen oxides generated in air-DBD plasma. Copyright © 2017. Published by Elsevier B.V.

CARBON BALANCE OF THE CONTINUOUS PERMAFROST ZONE OF RUSSIA

EPA Science Inventory

An increase in the atmospheric concentration of CO2 is projected to cause climate warming. arming of the permafrost environment could change the balance between carbon accumulation and decomposition processes and substantially disrupt the equilibrium of the carbon cycle. arming m...

Transport, anoxia and energy control on anaerobic respiration and methanogenesis in anoxic peat soils

NASA Astrophysics Data System (ADS)

Bonaiuti, Simona; Blodau, Christian; Knorr, Klaus-Holger

2017-04-01

In deep and permanently water saturated peat deposits, extremely low diffusive transport and concomitant build-up of metabolic end-products, i.e of dissolved inorganic carbon (DIC) and methane (CH4), have been found to slow-down anaerobic respiration and methanogenesis. Such accumulation of DIC and CH4 lowers the Gibbs free energy yield of terminal respiration and methanogenesis, which can inhibit the course of anaerobic metabolic processes. In particular, this affects terminal steps of the breakdown of organic carbon (C), such as methanogenesis, acetogenesis and fermentation processes, which occur near thermodynamic minimum energy thresholds. This effect is thus of critical importance for the long-term C sequestration, as the slow-down of decomposition ultimately regulates the long-term fate of C in deep peat deposits. The exact controls of this observed slow-down of organic matter mineralization are not yet fully understood. Moreover, altered patterns of water or gas transport due to predicted changes in climate may affect these controls in peat soils. Therefore, the aim of this study was to investigate how burial of peat leads to an inactivation of anaerobic decomposition and to investigate the effects of advective water transport and persistently anoxic conditions on anaerobic decomposition, temporal evolution of thermodynamic energy yields to methanogenesis and methanogenic pathways. To this end, we conducted a column experiment with homogenized, ombrotrophic peat over a period of 300 days at 20˚ C. We tested i) a control treatment under diffusive transport only, ii) an advective flow treatment with a flow of 10 mm d-1, and iv) an anoxic treatment to evaluate changes in decomposition in absence of oxygen in the unsaturated zone of the cores. A slow-down of anaerobic respiration and methanogenesis generally set in at larger depths after 150 days at CH4 concentrations of 0.6-0.9 mmol L-1 and DIC concentrations of 6-12 mmol L-1. This effect occurred at higher concentration levels and faster than previously observed. Advective water transport effectively extended the zone of methanogenesis down to 40 cm depth until inhibiting conditions were reached, although net turnover at greater depths was not affected. Strictly anoxic conditions in the unsaturated zone, where diffusive transport is high, had little effect on accelerating anaerobic decomposition. The slow-down of net production rates of CO2 and CH4 agreed well with the decline over time of Gibbs free energies available to methanogenesis, supporting a thermodynamic constraint on decomposition in deeper peat deposits. Keywords: Peatlands; Anaerobic decomposition; Methanogenesis; Production rates; Advection; Anoxia; Thermodynamic calculations.

[The changing gaps of life expectancy on genders in urban cities of China, from 2005 to 2010].

PubMed

Shen, Jie; Jiang, Qing-wu

2013-07-01

To analyze the gender difference of life expectancy in urban people of China and to explore both age-specific and cause-specific contributions to the changing differences in life expectancy on genders. Data on life expectancy (male and female) and mortality were obtained from the"Annual Statistics of public health in China". Male-female gender difference was analyzed by decomposition methodologies, including age-specific decomposition and the cause-specific decomposition. Women had lived much longer than men in the Chinese urban citizens, with remarkable gains in life expectancy since 2005. Difference in gender reached a peak in 2007, with the gap of 5.3 years. Differences on mortality between men and women in the 60-79 age groups made the largest contribution (42%-47%) to the gap of 6 years on life expectancy in genders. With the widening of the gaps in gender on life expectancy between 2005 and 2007, faster declining of mortality among groups of women in age 0-1 age and over 75 years old groups made the largest contributions. Between 2007 and 2008, along with the reduction of gaps in gender, all the age groups except the 1-15 and 50-55 year-olds showed negative efforts. In 2009-2010, the widening gaps in gender on life expectancy were caused by the positive effect in the 60-70 age group. Among all the causes of death, cancer (1.638-2.019 years), circulatory diseases (1.271-1.606 years), respiratory diseases (0.551-0.800 years) made the largest contributions to the gender gap. 33%-38% of the gaps in gender were caused by cancer and among all the cancers, among which lung cancer contributed 0.6 years to the overall gap. Contribution of cancers to the gender gap was reducing, but when time went on it was mostly influenced by the narrowing effect caused by liver cancer on the gap in gender. Traffic accidents and suicidal issues were the external causes that influencing the gender gap and contributing 10.60%-15.78% to the overall differentials. Public health efforts in reducing the excess mortalities for cancer, circulatory and respiratory diseases, suicide, among men in particular, will further narrow the gender gap on life expectancy in the urban cities of China.

Metagenomic analysis of a permafrost microbial community reveals a rapid response to thaw

USGS Publications Warehouse

MacKelprang, R.; Waldrop, M.P.; Deangelis, K.M.; David, M.M.; Chavarria, K.L.; Blazewicz, S.J.; Rubin, E.M.; Jansson, J.K.

2011-01-01

Permafrost contains an estimated 1672????????Pg carbon (C), an amount roughly equivalent to the total currently contained within land plants and the atmosphere. This reservoir of C is vulnerable to decomposition as rising global temperatures cause the permafrost to thaw. During thaw, trapped organic matter may become more accessible for microbial degradation and result in greenhouse gas emissions. Despite recent advances in the use of molecular tools to study permafrost microbial communities, their response to thaw remains unclear. Here we use deep metagenomic sequencing to determine the impact of thaw on microbial phylogenetic and functional genes, and relate these data to measurements of methane emissions. Metagenomics, the direct sequencing of DNA from the environment, allows the examination of whole biochemical pathways and associated processes, as opposed to individual pieces of the metabolic puzzle. Our metagenome analyses reveal that during transition from a frozen to a thawed state there are rapid shifts in many microbial, phylogenetic and functional gene abundances and pathways. After one week of incubation at 5 ??C, permafrost metagenomes converge to be more similar to each other than while they are frozen. We find that multiple genes involved in cycling of C and nitrogen shift rapidly during thaw. We also construct the first draft genome from a complex soil metagenome, which corresponds to a novel methanogen. Methane previously accumulated in permafrost is released during thaw and subsequently consumed by methanotrophic bacteria. Together these data point towards the importance of rapid cycling of methane and nitrogen in thawing permafrost. ?? 2011 Macmillan Publishers Limited. All rights reserved.

Enhanced photocatalytic performance and degradation pathway of Rhodamine B over hierarchical double-shelled zinc nickel oxide hollow sphere heterojunction

NASA Astrophysics Data System (ADS)

Zhang, Ying; Zhou, Jiabin; Cai, Weiquan; Zhou, Jun; Li, Zhen

2018-02-01

In this study, hierarchical double-shelled NiO/ZnO hollow spheres heterojunction were prepared by calcination of the metallic organic frameworks (MOFs) as a sacrificial template in air via a one-step solvothermal method. Additionally, the photocatalytic activity of the as-prepared samples for the degradation of Rhodamine B (RhB) under UV-vis light irradiation were also investigated. NiO/ZnO microsphere comprised a core and a shell with unique hierarchically porous structure. The photocatalytic results showed that NiO/ZnO hollow spheres exhibited excellent catalytic activity for RhB degradation, causing complete decomposition of RhB (200 mL of 10 g/L) under UV-vis light irradiation within 3 h. Furthermore, the degradation pathway was proposed on the basis of the intermediates during the photodegradation process using liquid chromatography analysis coupled with mass spectroscopy (LC-MS). The improvement in photocatalytic performance could be attributed to the p-n heterojunction in the NiO/ZnO hollow spheres with hierarchically porous structure and the strong double-shell binding interaction, which enhances adsorption of the dye molecules on the catalyst surface and facilitates the electron/hole transfer within the framework. The degradation mechanism of pollutant is ascribed to the hydroxyl radicals (rad OH), which is the main oxidative species for the photocatalytic degradation of RhB. This work provides a facile and effective approach for the fabrication of porous metal oxides heterojunction with high photocatalytic activity and thus can be potentially used in the environmental purification.

How nitrogen sources influence Mortierella alpina aging: From the lipid droplet proteome to the whole-cell proteome and metabolome.

PubMed

Yu, Yadong; Zhang, Lei; Li, Tao; Wu, Na; Jiang, Ling; Ji, Xiaojun; Huang, He

2018-05-15

Arachidonic acid (ARA) is a valuable polyunsaturated fatty acid produced by Mortierella alpina. Although some strategies such as nitrogen supplementation have shown the potential to affect the aging of M. alpina in ways which enable it to produce more ARA, the underlying mechanism remains elusive. Herein, we conducted a systematical analysis of the lipid droplet proteome, as well as the whole-cell proteome and metabolome, in order to elucidate how and why two different nitrogen sources (KNO 3 and urea) affect the aging of M. alpina and the corresponding ARA concentration. We found that KNO 3 promoted the ARA concentration, while urea accelerated lipid consumption and stimulated the decomposition of mycelia. Although both KNO 3 and urea activated carbohydrate metabolic pathways, KNO 3 exerted a stronger promoting effect on the pentose phosphate pathway and induced the lipid droplets to participate in the citrate-pyruvate cycle. The activities of malic enzyme and isocitrate dehydrogenase were also promoted more by KNO 3 . These pathways provided additional substrates and reducing power for ARA synthesis and ROS elimination. Accordingly, since urea showed a weaker promotion of the related pathways, it caused a depression of the antioxidant system and a consequent increase of ROS. These findings facilitate the design of nitrogen supplementation strategies to achieve higher ARA concentrations, and provide guidance for deciphering the mechanisms of similar aging phenomena in other oleaginous microorganisms. Polyunsaturated fatty acids such as arachidonic acid (ARA) are valuable nutrients, which play important roles in preventing numerous diseases and facilitating development. Although it has been found for years that ARA production will be increased in the aging process of Mortierella alpina (M. alpina) and nitrogen sources are involved in this process, the underlying mechanism for this phenomenon remains unknown. In this work, we used the subcellular proteomics, whole-cell proteomics and metabolomics methods to explore the mechanisms by which two different nitrogen (KNO 3 and urea) affected the aging process of M. alpina. Finally, we gave some new insights for the mechanisms mentioned above. This finding will fuel the technology developments for the ARA production using microbes. Copyright © 2018. Published by Elsevier B.V.

Methanogenic pathway and community structure in a thermophilic anaerobic digestion process of organic solid waste.

PubMed

Sasaki, Daisuke; Hori, Tomoyuki; Haruta, Shin; Ueno, Yoshiyuki; Ishii, Masaharu; Igarashi, Yasuo

2011-01-01

The methanogenic pathway and microbial community in a thermophilic anaerobic digestion process of organic solid waste were investigated in a continuous-flow stirred-tank reactor using artificial garbage slurry as a feedstock. The decomposition pathway of acetate, a significant precursor of CH(4) and a key intermediate metabolite in the anaerobic digestion process, was analyzed by using stable isotopes. A tracer experiment using (13)C-labeled acetate revealed that approximately 80% of the acetate was decomposed via a non-aceticlastic oxidative pathway, whereas the remainder was converted to methane via an aceticlastic pathway. Archaeal 16S rRNA analyses demonstrated that the hydrogenotrophic methanogens Methanoculleus spp. accounted for >90% of detected methanogens, and the aceticlastic methanogens Methanosarcina spp. were the minor constituents. The clone library targeting bacterial 16S rRNA indicated the predominance of the novel Thermotogales bacterium (relative abundance: ~53%), which is related to anaerobic acetate oxidizer Thermotoga lettingae TMO, although the sequence similarity was low. Uncultured bacteria that phylogenetically belong to municipal solid waste cluster I were also predominant in the microflora (~30%). These results imply that the microbial community in the thermophilic degrading process of organic solid waste consists exclusively of unidentified bacteria, which efficiently remove acetate through a non-aceticlastic oxidative pathway. Copyright © 2010 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Nitrogen Cycling Potential of a Grassland Litter Microbial Community

PubMed Central

Berlemont, Renaud; Martiny, Adam C.; Martiny, Jennifer B. H.

2015-01-01

Because microorganisms have different abilities to utilize nitrogen (N) through various assimilatory and dissimilatory pathways, microbial composition and diversity likely influence N cycling in an ecosystem. Terrestrial plant litter decomposition is often limited by N availability; however, little is known about the microorganisms involved in litter N cycling. In this study, we used metagenomics to characterize the potential N utilization of microbial communities in grassland plant litter. The frequencies of sequences associated with eight N cycling pathways differed by several orders of magnitude. Within a pathway, the distributions of these sequences among bacterial orders differed greatly. Many orders within the Actinobacteria and Proteobacteria appeared to be N cycling generalists, carrying genes from most (five or six) of the pathways. In contrast, orders from the Bacteroidetes were more specialized and carried genes for fewer (two or three) pathways. We also investigated how the abundance and composition of microbial N cycling genes differed over time and in response to two global change manipulations (drought and N addition). For many pathways, the abundance and composition of N cycling taxa differed over time, apparently reflecting precipitation patterns. In contrast to temporal variability, simulated global change had minor effects on N cycling potential. Overall, this study provides a blueprint for the genetic potential of N cycle processes in plant litter and a baseline for comparisons to other ecosystems. PMID:26231641

Decomposition of the polycyclic nitramine explosive, CL-20, by Fe(0).

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Halasz, Annamaria; Corbeanu, Aurelian; Hawari, Jalal

2004-12-15

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), C6H6N12O12, is an emerging energetic chemical that may replace RDX, but its degradation pathways are not well-known. In the present study, zerovalent iron was used to degrade CL-20 with the aim of determining its products and degradation pathways. In the absence of O2, CL-20 underwent a rapid decomposition with the concurrent formation of nitrite to ultimately produce nitrous oxide, ammonium, formate, glyoxal, and glycolate. LC/MS (ES-) showed the presence of several key products carrying important information on the initial reactions involved in the degradation of CL-20. For instance, a doubly denitrated intermediate of CL-20 was detected together with the mono- and dinitroso derivatives of the energetic chemical. Two other intermediates with [M-H]- at 392 and 376 Da, matching empirical formulas of C6H7N11O10 and C6H7N11O9, respectively, were detected. Using 15N-labeled CL-20, the two intermediates were tentatively identified as the denitrohydrogenated products of CL-20 and its mononitroso derivative, respectively. The present experimental findings suggest that CL-20 degraded via at least two initial routes: one involving denitration and the second involving sequential reduction of the N-NO2 to the corresponding nitroso (N-NO) derivatives prior to denitration and ring cleavage.

Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes.

PubMed

Bokare, Alok D; Choi, Wonyong

2014-06-30

Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO(•)) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe(2+) or Fe(3+) form), metal oxides (e.g., Fe2O3, Fe3O4), and zero-valent metal (Fe(0)) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H2O2 into HO(•) through conventional Fenton-like pathways. The in situ formation of H2O2 and decomposition into HO(•) can be also achieved using electron transfer mechanism in zero-valent aluminum/O2 system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H2O2 activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Deamidation of Protonated Asparagine-Valine Investigated by a Combined Spectroscopic, Guided Ion Beam, and Theoretical Study.

PubMed

Kempkes, L J M; Boles, G C; Martens, J; Berden, G; Armentrout, P B; Oomens, J

2018-03-08

Peptide deamidation of asparaginyl residues is a spontaneous post-translational modification that is believed to play a role in aging and several diseases. It is also a well-known small-molecule loss channel in the MS/MS spectra of protonated peptides. Here we investigate the deamidation reaction, as well as other decomposition pathways, of the protonated dipeptide asparagine-valine ([AsnVal + H] + ) upon low-energy activation in a mass spectrometer. Using a combination of infrared ion spectroscopy, guided ion beam tandem mass spectrometry, and theoretical calculations, we have been able to identify product ion structures and determine the energetics and mechanisms for decomposition. Deamidation proceeds via ammonia loss from the asparagine side chain, initiated by a nucleophilic attack of the peptide bond oxygen on the γ-carbon of the Asn side chain. This leads to the formation of a furanone ring containing product ion characterized by a threshold energy of 129 ± 5 kJ/mol (15 kJ/mol higher in energy than dehydration of [AsnVal + H] + , the lowest energy dissociation channel available to the system). Competing formation of a succinimide ring containing product, as has been observed for protonated asparagine-glycine ([AsnGly + H] + ) and asparagine-alanine ([AsnAla + H] + ), was not observed here. Quantum-chemical modeling of the reaction pathways confirms these subtle differences in dissociation behavior. Measured reaction thresholds are in agreement with predicted theoretical reaction energies computed at several levels of theory.

Decomposition of dimethylamine gas with dielectric barrier discharge.

PubMed

Ye, Zhaolian; Zhao, Jie; Huang, Hong ying; Ma, Fei; Zhang, Renxi

2013-09-15

The decomposition of dimethylamine (DMA) with gas under high flow rate was investigated with dielectric barrier discharge (DBD) technology. Different parameters including removal efficiency, energy yield, carbon balance and CO2 selectivity, secondary products, as well as pathways and mechanisms of DMA degradation were studied. The experimental results showed that removal efficiency of DMA depended on applied voltage and gas flow rate, but had no obvious correlation with initial concentration. Excellent energy performance was obtained using present DBD technology for DMA abatement. When experiment conditions were controlled at: gas flow rate of 14.9 m(3)/h, initial concentration of 2104 mg/m(3), applied voltage of 4.8 kV, removal efficiency of DMA and energy yield can reach 85.2% and 953.9 g/kWh, respectively. However, carbon balance (around 40%) was not ideal due to shorter residence time (about 0.1s), implying that some additional conditions should be considered to improve the total oxidation of DMA. Moreover, secondary products in outlet gas stream were detected via gas chromatogram-mass spectrum and the amounts of NO3(-) and NO2(-) were analyzed by ion chromatogram. The obtained data demonstrated that NOx might be suppressed due to reductive NH radical form DMA dissociation. The likely reaction pathways and mechanisms for the removal of DMA were suggested based on products analysis. Experimental results demonstrated the application potential of DBD as a clean technology for organic nitrogen-containing gas elimination from gas streams. Copyright © 2013 Elsevier B.V. All rights reserved.

Insights from a refined decomposition of cloud feedbacks

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

Zelinka, Mark D.; Zhou, Chen; Klein, Stephen A.

Decomposing cloud feedback into components due to changes in several gross cloud properties provides valuable insights into its physical causes. Here we present a refined decomposition that separately considers changes in free tropospheric and low cloud properties, better connecting feedbacks to individual governing processes and avoiding ambiguities present in a commonly used decomposition. It reveals that three net cloud feedback components are robustly nonzero: positive feedbacks from increasing free tropospheric cloud altitude and decreasing low cloud cover and a negative feedback from increasing low cloud optical depth. Low cloud amount feedback is the dominant contributor to spread in net cloudmore » feedback but its anticorrelation with other components damps overall spread. Furthermore, the ensemble mean free tropospheric cloud altitude feedback is roughly 60% as large as the standard cloud altitude feedback because it avoids aliasing in low cloud reductions. Implications for the “null hypothesis” climate sensitivity from well-understood and robustly simulated feedbacks are discussed.« less

Insights from a refined decomposition of cloud feedbacks

DOE PAGES

Zelinka, Mark D.; Zhou, Chen; Klein, Stephen A.

2016-09-05

Decomposing cloud feedback into components due to changes in several gross cloud properties provides valuable insights into its physical causes. Here we present a refined decomposition that separately considers changes in free tropospheric and low cloud properties, better connecting feedbacks to individual governing processes and avoiding ambiguities present in a commonly used decomposition. It reveals that three net cloud feedback components are robustly nonzero: positive feedbacks from increasing free tropospheric cloud altitude and decreasing low cloud cover and a negative feedback from increasing low cloud optical depth. Low cloud amount feedback is the dominant contributor to spread in net cloudmore » feedback but its anticorrelation with other components damps overall spread. Furthermore, the ensemble mean free tropospheric cloud altitude feedback is roughly 60% as large as the standard cloud altitude feedback because it avoids aliasing in low cloud reductions. Implications for the “null hypothesis” climate sensitivity from well-understood and robustly simulated feedbacks are discussed.« less

Curatorial implications of Ophyra capensis (Order Diptera, Family Muscidae) puparia recovered from the body of the Blessed Antonio Patrizi, Monticiano, Italy (Middle Ages).

PubMed

Morrow, Johnica J; Baldwin, Diesel A; Higley, Leon; Piombino-Mascali, Dario; Reinhard, Karl J

2015-11-01

The discovery of dipteran remains on mummified individuals can lead to either cause for curatorial concern or to a better understanding of the individual's post-mortem environment. The present study analyzed insect remains associated with the body of a unique medieval mummy of religious significance, that of the Blessed Antonio Patrizi da Monticiano. A total of 79 puparia were examined and all were identified as Ophyra capensis (Diptera: Muscidae). Additionally, a desiccated moth (Lepidoptera: Tineidae) was encountered. Puparia of O. capensis would be associated with normal decomposition shortly after the death of the mummified individual, and not an infestation beginning during more recent years. Similarly, the tineid moth found would likely be related with decomposition of cloth associated with the remains. These findings illustrate how collection and identification of insects associated with human remains can distinguish between historical decomposition versus issues of modern curatorial concern. Copyright © 2015 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

NASA Astrophysics Data System (ADS)

Dhaundiyal, Alok; Singh, Suraj B.; Hanon, Muammel M.; Rawat, Rekha

2018-02-01

A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO), Kissinger-Akahira-Sonuse (KAS) and Kissinger, and model-fitting (Coats Redfern). The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method) and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

Evidence for alkali metal formation at a cathode interface of organic electroluminescent devices by thermal decomposition of alkali metal carboxylates during their vapor deposition

NASA Astrophysics Data System (ADS)

Ganzorig, Chimed; Fujihira, Masamichi

2004-11-01

This study examines the possibility of thermal decomposition of Na salts of acetate, benzoate, and fluoride during vacuum vapor deposition using a quartz crystal microbalance to measure negative frequency shift (Δf) caused by increasing mass deposited from the same amount of source materials. Cs acetate is also examined. We compare the negative frequency shift-source current (Δf -I) curves of the Na salts with those of organic materials such as tris(8-hydroxyquinoline)aluminum and N ,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine. CH3COONa and C6H5COONa exhibit much lower Δf than the organic materials. CH3COOCs gives much larger Δf than CH3COONa due to the higher atomic weight of Cs. These exhibit clear evidence for alkali metal formation by thermal decomposition during vapor deposition of alkali metal carboxylates.

Microstructural changes of a thermally aged stainless steel submerged arc weld overlay cladding of nuclear reactor pressure vessels

NASA Astrophysics Data System (ADS)

Takeuchi, T.; Kameda, J.; Nagai, Y.; Toyama, T.; Matsukawa, Y.; Nishiyama, Y.; Onizawa, K.

2012-06-01

The effect of thermal aging on microstructural changes in stainless steel submerged arc weld-overlay cladding of reactor pressure vessels was investigated using atom probe tomography (APT). In as-received materials subjected to post-welding heat treatments (PWHTs), with a subsequent furnace cooling, a slight fluctuation of the Cr concentration was observed due to spinodal decomposition in the δ-ferrite phase but not in the austenitic phase. Thermal aging at 400 °C for 10,000 h caused not only an increase in the amplitude of spinodal decomposition but also the precipitation of G phases with composition ratios of Ni:Si:Mn = 16:7:6 in the δ-ferrite phase. The degree of the spinodal decomposition in the submerged arc weld sample was similar to that in the electroslag weld one reported previously. We also observed a carbide on the γ-austenite and δ-ferrite interface. There were no Cr depleted zones around the carbide.

First-principles study on the initial decomposition process of CH3NH3PbI3

NASA Astrophysics Data System (ADS)

Xue, Yuanbin; Shan, Yueyue; Xu, Hu

2017-09-01

Hybrid perovskites are promising materials for high-performance photovoltaics. Unfortunately, hybrid perovskites readily decompose in particular under humid conditions, and the mechanisms of this phenomenon have not yet been fully understood. In this work, we systematically studied the possible mechanisms and the structural properties during the initial decomposition process of MAPbI3 (MA = CH3NH3+) using first-principles calculations. The theoretical results show that it is energetically favorable for PbI2 to nucleate and crystalize from the MAPbI3 matrix ahead of other decomposition products. Additionally, the structural instability is an intrinsic property of MAPbI3, regardless of whether the system is exposed to humidity. We find that H2O could facilitate the desorption of gaseous components, acting as a catalyst to transfer the H+ ion. These results provide insight into the cause of the instability of MAPbI3 and may improve our understanding of the properties of hybrid perovskites.

Nanostructuring one-dimensional and amorphous lithium peroxide for high round-trip efficiency in lithium-oxygen batteries.

PubMed

Dutta, Arghya; Wong, Raymond A; Park, Woonghyeon; Yamanaka, Keisuke; Ohta, Toshiaki; Jung, Yousung; Byon, Hye Ryung

2018-02-14

The major challenge facing lithium-oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide.

An unusual pattern of decomposition associated with suicidal electrocution in a bath.

PubMed

Fernando, Tarini; Winskog, Calle; Byard, Roger W

2013-07-01

A 51-year-old man was found dead face down and partially submerged in a bathtub alongside two hairdryers. The hairdryers had continued to work, as the victim had bypassed the electrical board of the house prior to dropping them into the water. This had resulted in death due to electrocution, with subsequent heating of the bath water causing marked putrefaction and softening of the immersed body parts. The back and feet, which were not submerged, were preserved. The degree of anterior decomposition was not in keeping with the postmortem interval; however, regional decomposition with sparing of the back and feet provided a clue at autopsy as to the sequence of events. Individuals with training in, or knowledge of, electrical circuitry are capable of modifying domestic wiring so that safety switches and/or fuses can be bypassed ensuring that electrical devices will continue to function even while under water. © 2013 American Academy of Forensic Sciences.

Degradation of sulfamethazine by gamma irradiation in the presence of hydrogen peroxide.

PubMed

Liu, Yuankun; Wang, Jianlong

2013-04-15

The gamma irradiation-induced degradation of sulfamethazine (SMT) in aqueous solution in the presence of hydrogen peroxide (H2O2) was investigated. The initial SMT concentration was 20mg/L and it was irradiated in the presence of extra H2O2 with initial concentration of 0, 10 and 30 mg/L. The results showed that gamma irradiation was effective for removing SMT in aqueous solution and its degradation conformed to the pseudo first-order kinetics under the applied conditions. When initial H2O2 concentration was in the range of 0-30 mg/L, higher concentration of H2O2 was more effective for the decomposition and mineralization of SMT. However, the removal of total organic carbon (TOC) was not as effective as that of SMT. Total nitrogen (TN) was not removed even at absorbed dose of 5 kGy, which was highest dose applied in this study. Major decomposition products of SMT, including degradation intermediates, organic acids and some inorganic ions were detected by high performance liquid chromatography (HPLC) and ion chromatography (IC). Sulfate (SO4(2-)), formic acid (HCOOH), acetic acid (CH3COOH), 4-aminophenol, 4-nitrophenol were identified in the irradiated solutions. Possible pathways for SMT decomposition by gamma irradiation in aqueous solution were proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

Degradation and intermediates of diclofenac as instructive example for decomposition of recalcitrant pharmaceuticals by hydroxyl radicals generated with pulsed corona plasma in water.

PubMed

Banaschik, Robert; Jablonowski, Helena; Bednarski, Patrick J; Kolb, Juergen F

2018-01-15

Seven recalcitrant pharmaceutical residues (diclofenac, 17α-ethinylestradiol, carbamazepine, ibuprofen, trimethoprim, diazepam, diatrizoate) were decomposed by pulsed corona plasma generated directly in water. The detailed degradation pathway was investigated for diclofenac and 21 intermediates could be identified in the degradation cascade. Hydroxyl radicals have been found primarily responsible for decomposition steps. By spin trap enhanced electron paramagnetic resonance spectroscopy (EPR), OH-adducts and superoxide anion radical adducts were detected and could be distinguished applying BMPO as a spin trap. The increase of concentrations of adducts follows qualitatively the increase of hydrogen peroxide concentrations. Hydrogen peroxide is eventually consumed in Fenton-like processes but the concentration is continuously increasing to about 2mM for a plasma treatment of 70min. Degradation of diclofenac is inversely following hydrogen peroxide concentrations. No qualitative differences between byproducts formed during plasma treatment or due to degradation via Fenton-induced processes were observed. Findings on degradation kinetics of diclofenac provide an instructive understanding of decomposition rates for recalcitrant pharmaceuticals with respect to their chemical structure. Accordingly, conclusions can be drawn for further development and a first risk assessment of the method which can also be applied towards other AOPs that rely on the generation of hydroxyl radicals. Copyright © 2017 Elsevier B.V. All rights reserved.

Density functional theory (DFT) study of the gas-phase decomposition of the Cd[((i)Pr)2PSSe] 2 single-source precursor for the CVD of binary and ternary cadmium chalcogenides.

PubMed

Opoku, Francis; Asare-Donkor, Noah Kyame; Adimado, Anthony A

2014-11-01

The chemistry of group II-VI semiconductors has spurred considerable interest in decomposition reaction mechanisms and has been exploited for various technological applications. In this work, computational chemistry was employed to investigate the possible gas-phase decomposition pathways of the mixed Cd[((i)Pr)2PSSe]2 single-source precursor for the chemical vapour deposition of cadmium chalcogenides as thin films. The geometries of the species involved were optimised by employing density functional theory at the MO6/LACVP* level. The results indicate that the steps that lead to CdS formation on the singlet potential energy surface are favoured kinetically over those that lead to CdSe and ternary CdSe(x)S(1-x) formation. On the doublet PES, the steps that lead to CdSe formation are favoured kinetically over those that lead to CdS and CdSe(x)S(1-x) formation. However, thermodynamically, the steps that lead to ternary CdSe(x)S(1-x) formation are more favourable than those that lead to CdSe and CdS formation on both the singlet and the doublet PESs. Density functional theory calculations revealed that the first steps exhibit huge activation barriers, meaning that the thermodynamically favourable process takes a very long time to initiate.

Dissolved Organic Carbon Cycling and Transformation Dynamics in A Northern Forested Peatland

NASA Astrophysics Data System (ADS)

Tfaily, M. M.; Lin, X.; Chanton, P. R.; Steinweg, J.; Esson, K.; Kostka, J. E.; Cooper, W. T.; Schadt, C. W.; Hanson, P. J.; Chanton, J.

2013-12-01

Peatlands sequester one-third of all soil carbon and currently act as major sinks of atmospheric carbon dioxide. The ability to predict or simulate the fate of stored carbon in response to climatic disruption remains hampered by our limited understanding of the controls of carbon turnover and the composition and functioning of peatland microbial communities. A combination of advanced analytical chemistry and microbiology approaches revealed that organic matter reactivity and microbial community dynamics were closely coupled in an extensive field dataset compiled at the S1 bog site established for the SPRUCE program, Marcell Experimental Forest (MEF). The molecular composition and decomposition pathways of dissolved organic carbon (DOC) were contrasted using parallel factor (PARAFAC)-modeled excitation emission fluorescence spectroscopy (EEMS) and FT-ICR MS. The specific UV absorbance (SUVA) at 254 nm was calculated as an indicator of aromaticity. Fluorescence intensity ratios (BIX and FI) were used to infer the relative contributions from solid phase decomposition and microbial production. Distributions of bulk DOC, its stable (δ13C) and radioactive (Δ14C) isotopic composition were also utilized to infer information on its dynamics and transformation processes. Strong vertical stratification was observed in organic matter composition, the distribution of mineralization products (CO2, CH4), respiration rates, and decomposition pathways, whereas smaller variations were observed between sites. A decline in the aromaticity of pore water DOC was accompanied by an increase in microbially-produced DOC. Solid phase peat, on the other hand, became more humified and highly aromatic with depth. These observations were consistent with radiocarbon data that showed that the radiocarbon signatures of microbial respiration products in peat porewaters more closely resemble those of DOC rather than solid peat, indicating that carbon from recent photosynthesis is fueling the majority of the decomposition, even in the subsurface. Stable isotope geochemistry paralleled with vertical changes in methanogen community composition to reveal a mid-depth maximum in acetoclastic methanogenesis, while hydrogenotrophic methanogenesis appears to dominate deeper peat layers. Archaea increased in relative abundance with depth, comprising up to 60 % of the microbial community in the deep peat below 75 cm depth. The Crenarchaeota, Archaea that are not known to produce methane, are suggested to play a critical role in the carbon cycle of deeper peat layers. This is corroborated by evidence from a C isotope mass balance, which indicates that processes other than methanogenesis (fermentation, anaerobic respiration) predominate in the deep peat leading to dominance of CO2 production at depth.

TiO2 photocatalytic degradation and transformation of oxazaphosphorine drugs in an aqueous environment.

PubMed

Lai, Webber Wei-Po; Lin, Hank Hui-Hsiang; Lin, Angela Yu-Chen

2015-04-28

This study investigated the TiO2 photocatalytic degradation and transformation of the oxazaphosphorines ifosfamide (IFO), cyclophosphamide (CP) and trofosfamide (TRO). Under the optimum conditions of TiO2=100mg/L, IFO=100μg/L and solution pH=5.5, IFO was completely removed within 10min (k=0.433min(-1)). The results indicated that OHfree radicals generated by valence holes in the bulk solution were the predominant species for the degradation of IFO. At higher initial concentrations of oxazaphosphorines (20mg/L), >50% of TOC remained after 6h of reaction time, indicating that parent compounds were transformed to byproducts, which exhibit higher Microtox acute toxicities; chlorinated byproducts were likely the source of toxicity. Photocatalytic degradation pathways of the three oxazaphosphorines were proposed. IFO, CP and TRO follow very similar pathways and bond-breaking processes: ketonization and breaking of the CCl bond, the PN bond and the CN bond (N-dechloroethylation). Chloride (Cl(-)) release is likely the first and primary step in the decomposition process. Several of the identified byproducts were also metabolites, which implies that photocatalytic oxidation proceeds through pathways that are similar to metabolic pathways. Copyright © 2015 Elsevier B.V. All rights reserved.

Anaerobic soil disinfestation impact on nutrient dynamics in fresh-market tomato

USDA-ARS?s Scientific Manuscript database

Anaerobic soil disinfestation (ASD) is considered a promising sustainable alternative to chemical soil fumigation (CSF). Suitable for both organic and conventional growing systems. The soil amendment with organic material and its anaerobic decomposition cause a temporary variation of the soil redox...

Atomic decomposition of the protein solvation free energy and its application to amyloid-beta protein in water

NASA Astrophysics Data System (ADS)

Chong, Song-Ho; Ham, Sihyun

2011-07-01

We report the development of an atomic decomposition method of the protein solvation free energy in water, which ascribes global change in the solvation free energy to local changes in protein conformation as well as in hydration structure. So far, empirical decomposition analyses based on simple continuum solvation models have prevailed in the study of protein-protein interactions, protein-ligand interactions, as well as in developing scoring functions for computer-aided drug design. However, the use of continuum solvation model suffers serious drawbacks since it yields the protein free energy landscape which is quite different from that of the explicit solvent model and since it does not properly account for the non-polar hydrophobic effects which play a crucial role in biological processes in water. Herein, we develop an exact and general decomposition method of the solvation free energy that overcomes these hindrances. We then apply this method to elucidate the molecular origin for the solvation free energy change upon the conformational transitions of 42-residue amyloid-beta protein (Aβ42) in water, whose aggregation has been implicated as a primary cause of Alzheimer's disease. We address why Aβ42 protein exhibits a great propensity to aggregate when transferred from organic phase to aqueous phase.

In vitro decomposition of Sphagnum by some microfungi resembles white rot of wood.

PubMed

Rice, Adrianne V; Tsuneda, Akihiko; Currah, Randolph S

2006-06-01

The abilities of some ascomycetes (Myxotrichaceae) from a Sphagnum bog in Alberta to degrade cellulose, phenolics, and Sphagnum tissue were compared with those of two basidiomycetes. Most Myxotrichaceae degraded cellulose and tannic acid, and removed cell-wall components simultaneously from Sphagnum tissues, whereas the basidiomycetes degraded cellulose and insoluble phenolics, and preferentially removed the polyphenolic matrix from Sphagnum cell walls. Mass losses from Sphagnum varied from up to 50% for some ascomycetes to a maximum of 35% for the basidiomycetes. The decomposition of Sphagnum by the Myxotrichaceae was analogous to the white rot of wood and indicates that these fungi have the potential to cause significant mineralization of carbon in bogs.

Hybrid empirical mode decomposition- ARIMA for forecasting exchange rates

NASA Astrophysics Data System (ADS)

Abadan, Siti Sarah; Shabri, Ani; Ismail, Shuhaida

2015-02-01

This paper studied the forecasting of monthly Malaysian Ringgit (MYR)/ United State Dollar (USD) exchange rates using the hybrid of two methods which are the empirical model decomposition (EMD) and the autoregressive integrated moving average (ARIMA). MYR is pegged to USD during the Asian financial crisis causing the exchange rates are fixed to 3.800 from 2nd of September 1998 until 21st of July 2005. Thus, the chosen data in this paper is the post-July 2005 data, starting from August 2005 to July 2010. The comparative study using root mean square error (RMSE) and mean absolute error (MAE) showed that the EMD-ARIMA outperformed the single-ARIMA and the random walk benchmark model.

Combinatorial algorithms for design of DNA arrays.

PubMed

Hannenhalli, Sridhar; Hubell, Earl; Lipshutz, Robert; Pevzner, Pavel A

2002-01-01

Optimal design of DNA arrays requires the development of algorithms with two-fold goals: reducing the effects caused by unintended illumination (border length minimization problem) and reducing the complexity of masks (mask decomposition problem). We describe algorithms that reduce the number of rectangles in mask decomposition by 20-30% as compared to a standard array design under the assumption that the arrangement of oligonucleotides on the array is fixed. This algorithm produces provably optimal solution for all studied real instances of array design. We also address the difficult problem of finding an arrangement which minimizes the border length and come up with a new idea of threading that significantly reduces the border length as compared to standard designs.

Dealing with noise and physiological artifacts in human EEG recordings: empirical mode methods

NASA Astrophysics Data System (ADS)

Runnova, Anastasiya E.; Grubov, Vadim V.; Khramova, Marina V.; Hramov, Alexander E.

2017-04-01

In the paper we propose the new method for removing noise and physiological artifacts in human EEG recordings based on empirical mode decomposition (Hilbert-Huang transform). As physiological artifacts we consider specific oscillatory patterns that cause problems during EEG analysis and can be detected with additional signals recorded simultaneously with EEG (ECG, EMG, EOG, etc.) We introduce the algorithm of the proposed method with steps including empirical mode decomposition of EEG signal, choosing of empirical modes with artifacts, removing these empirical modes and reconstructing of initial EEG signal. We show the efficiency of the method on the example of filtration of human EEG signal from eye-moving artifacts.

Comprehensive detection of genes causing a phenotype using phenotype sequencing and pathway analysis.

PubMed

Harper, Marc; Gronenberg, Luisa; Liao, James; Lee, Christopher

2014-01-01

Discovering all the genetic causes of a phenotype is an important goal in functional genomics. We combine an experimental design for detecting independent genetic causes of a phenotype with a high-throughput sequencing analysis that maximizes sensitivity for comprehensively identifying them. Testing this approach on a set of 24 mutant strains generated for a metabolic phenotype with many known genetic causes, we show that this pathway-based phenotype sequencing analysis greatly improves sensitivity of detection compared with previous methods, and reveals a wide range of pathways that can cause this phenotype. We demonstrate our approach on a metabolic re-engineering phenotype, the PEP/OAA metabolic node in E. coli, which is crucial to a substantial number of metabolic pathways and under renewed interest for biofuel research. Out of 2157 mutations in these strains, pathway-phenoseq discriminated just five gene groups (12 genes) as statistically significant causes of the phenotype. Experimentally, these five gene groups, and the next two high-scoring pathway-phenoseq groups, either have a clear connection to the PEP metabolite level or offer an alternative path of producing oxaloacetate (OAA), and thus clearly explain the phenotype. These high-scoring gene groups also show strong evidence of positive selection pressure, compared with strictly neutral selection in the rest of the genome.

Marsh soil responses to tidal water nitrogen additions contribute to creek bank fracturing and slumping

EPA Science Inventory

Large-scale dissolved nutrient enrichment can cause a reduction in belowground biomass, increased water content of soils, and increased microbial decomposition, which has been linked with slumping of low marsh Spartina vegetation into creeks, and ultimately marsh loss. Our study ...

Group 12 Thiolates: Syntheses, Characterization and Decomposition Pathways

DTIC Science & Technology

1994-03-08

Stadard Form 298 (Rev 2-89) P ,e~cnwd by ANSI Std 1319. 1 94 3 1 1 180 92_1_ OFFICE OF NAVAL RESEARCH GRANT N00014-92-J-1820 R&T Code 4135035---01...Malik, M. Motevalli. P . O’Brian, Organometallics 10, 730 (1991). 3. M. Bochmann, K. J. Webb. M. Harman. M. B. Hursthouse, Angew. Chem. Int. Engl. Ed...29, 100 (1990). 4. M. Bochmann. K. J. Webb. M. B. Hursthouse, M. Mazid, J. Chem. Soc., Dalton Trans. 1991, 2317. 5. J. G. Brennan. T. Siegrist, P . J

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE PAGES

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; ...

2016-07-05

Cycloheptatrienyl (tropyl) radical, C 7H 7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. In this study, the pyrolysis products resulting from C 7H 7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C 7H 7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals domore » not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C 7H 7) radicals but rather only benzyl (C 6H 5CH 2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C 6H 5CH 2, C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2. Finally, analysis of the temperature dependence for the pyrolysis of the isotopic species (C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

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

Buckingham, Grant T.; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401; Porterfield, Jessica P.

2016-07-07

Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize tomore » benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

Pyrogenic carbon erosion: implications for stock and persistence of pyrogenic carbon in soil

NASA Astrophysics Data System (ADS)

Abney, Rebecca B.; Berhe, Asmeret Asefaw

2018-03-01

Pyrogenic carbon (PyC) constitutes an important pool of soil organic matter, particularly for its reactivity and because of its assumed long residence times in soil. In the past, research on the dynamics of PyC in the soil system has focused on quantifying stock and mean residence time of PyC in soil, as well as determining both PyC stabilization mechanisms and loss pathways. Much of this research has focused on decomposition as the most important loss pathway for PyC from soil. However, the low density of PyC and its high concentration on the soil surface after fire indicates that a significant proportion of PyC formed or deposited on the soil surface is likely laterally transported away from the site of production by wind and water erosion. Here, we present a synthesis of available data and literature to compare the magnitude of the water-driven erosional PyC flux with other important loss pathways, including leaching and decomposition, of PyC from soil. Furthermore, we use a simple first-order kinetic model of soil PyC dynamics to assess the effect of erosion and deposition on residence time of PyC in eroding landscapes. Current reports of PyC mean residence time (MRT) range from 250 to 660 years. Using a specific example-based model system, we find that ignoring the role of erosion may lead to the under- or over-estimation of PyC MRT on the centennial time scale. Furthermore, we find that, depending on the specific landform positions, timescales considered, and initial concentrations of PyC in soil, ignoring the role of erosion in distributing PyC across a landscape can lead to discrepancies in PyC concentrations on the order of several hundred g PyC m-2. Erosion is an important PyC flux that can act as a significant control on the stock and residence time of PyC in the soil system.

Decomposition of complex microbial behaviors into resource-based stress responses

PubMed Central

Carlson, Ross P.

2009-01-01

Motivation: Highly redundant metabolic networks and experimental data from cultures likely adapting simultaneously to multiple stresses can complicate the analysis of cellular behaviors. It is proposed that the explicit consideration of these factors is critical to understanding the competitive basis of microbial strategies. Results: Wide ranging, seemingly unrelated Escherichia coli physiological fluxes can be simply and accurately described as linear combinations of a few ecologically relevant stress adaptations. These strategies were identified by decomposing the central metabolism of E.coli into elementary modes (mathematically defined biochemical pathways) and assessing the resource investment cost–benefit properties for each pathway. The approach capitalizes on the inherent tradeoffs related to investing finite resources like nitrogen into different pathway enzymes when the pathways have varying metabolic efficiencies. The subset of ecologically competitive pathways represented 0.02% of the total permissible pathways. The biological relevance of the assembled strategies was tested against 10 000 randomly constructed pathway subsets. None of the randomly assembled collections were able to describe all of the considered experimental data as accurately as the cost-based subset. The results suggest these metabolic strategies are biologically significant. The current descriptions were compared with linear programming (LP)-based flux descriptions using the Euclidean distance metric. The current study's pathway subset described the experimental fluxes with better accuracy than the LP results without having to test multiple objective functions or constraints and while providing additional ecological insight into microbial behavior. The assembled pathways seem to represent a generalized set of strategies that can describe a wide range of microbial responses and hint at evolutionary processes where a handful of successful metabolic strategies are utilized simultaneously in different combinations to adapt to diverse conditions. Contact: rossc@biofilms.montana.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:19008248

GHGs and air pollutants embodied in China’s international trade: Temporal and spatial index decomposition analysis

PubMed Central

Liu, Zhengyan; Mao, Xianqiang; Song, Peng

2017-01-01

Temporal index decomposition analysis and spatial index decomposition analysis were applied to understand the driving forces of the emissions embodied in China’s exports and net exports during 2002–2011, respectively. The accumulated emissions embodied in exports accounted for approximately 30% of the total emissions in China; although the contribution of the sectoral total emissions intensity (technique effect) declined, the scale effect was largely responsible for the mounting emissions associated with export, and the composition effect played a largely insignificant role. Calculations of the emissions embodied in net exports suggest that China is generally in an environmentally inferior position compared with its major trade partners. The differences in the economy-wide emission intensities between China and its major trade partners were the biggest contribution to this reality, and the trade balance effect played a less important role. However, a lower degree of specialization in pollution intensive products in exports than in imports helped to reduce slightly the emissions embodied in net exports. The temporal index decomposition analysis results suggest that China should take effective measures to optimize export and supply-side structure and reduce the total emissions intensity. According to spatial index decomposition analysis, it is suggested that a more aggressive import policy was useful for curbing domestic and global emissions, and the transfer of advanced production technologies and emission control technologies from developed to developing countries should be a compulsory global environmental policy option to mitigate the possible leakage of pollution emissions caused by international trade. PMID:28441399

Impacts of soil petroleum contamination on nutrient release during litter decomposition of Hippophae rhamnoides.

PubMed

Zhang, Xiaoxi; Liu, Zengwen; Luc, Nhu Trung; Yu, Qi; Liu, Xiaobo; Liang, Xiao

2016-03-01

Petroleum exploitation causes contamination of shrub lands close to oil wells. Soil petroleum contamination affects nutrient release during the litter decomposition of shrubs, which influences nutrient recycling and the maintenance of soil fertility. Hence, this contamination may reduce the long-term growth and stability of shrub communities and consequently, the effects of phytoremediation. Fresh foliar litter of Hippophae rhamnoides, a potential phytoremediating species, was collected for this study. The litter was placed in litterbags and then buried in different petroleum-polluted soil media (the petroleum concentrations were 15, 30, and 45 g kg(-1) dry soil, which were considered as slightly, moderately and seriously polluted soil, respectively) for a decomposition test. The impacts of petroleum contamination on the release of nutrients (including N, P, K, Cu, Zn, Fe, Mn, Ca and Mg) were assessed. The results showed that (1) after one year of decomposition, the release of all nutrients was accelerated in the slightly polluted soil. In the moderately polluted soil, P release was accelerated, while Cu, Zn and Mn release was inhibited. In the seriously polluted soil, Cu and Zn release was accelerated, while the release of the other nutrients was inhibited. (2) The effect of petroleum on nutrient release from litter differed in different periods during decomposition; this was mainly due to changes in soil microorganisms and enzymes under the stress of petroleum contamination. (3) To maintain the nutrient cycling and the soil fertility of shrub lands, H. rhamnoides is only suitable for phytoremediation of soils containing less than 30 g kg(-1) of petroleum.

F4 , E6 and G2 exceptional gauge groups in the vacuum domain structure model

NASA Astrophysics Data System (ADS)

Shahlaei, Amir; Rafibakhsh, Shahnoosh

2018-03-01

Using a vacuum domain structure model, we calculate trivial static potentials in various representations of F4 , E6, and G2 exceptional groups by means of the unit center element. Due to the absence of the nontrivial center elements, the potential of every representation is screened at far distances. However, the linear part is observed at intermediate quark separations and is investigated by the decomposition of the exceptional group to its maximal subgroups. Comparing the group factor of the supergroup with the corresponding one obtained from the nontrivial center elements of S U (3 ) subgroup shows that S U (3 ) is not the direct cause of temporary confinement in any of the exceptional groups. However, the trivial potential obtained from the group decomposition into the S U (3 ) subgroup is the same as the potential of the supergroup itself. In addition, any regular or singular decomposition into the S U (2 ) subgroup that produces the Cartan generator with the same elements as h1, in any exceptional group, leads to the linear intermediate potential of the exceptional gauge groups. The other S U (2 ) decompositions with the Cartan generator different from h1 are still able to describe the linear potential if the number of S U (2 ) nontrivial center elements that emerge in the decompositions is the same. As a result, it is the center vortices quantized in terms of nontrivial center elements of the S U (2 ) subgroup that give rise to the intermediate confinement in the static potentials.

Photoelectron Spectroscopy of Nitrogen Containing Molecules of Biological and Industrial Interest

NASA Astrophysics Data System (ADS)

Pinto, Rui Montenegro Val-do-Rio

The work presented herein is based on the gas-phase spectroscopic characterization of several molecules of high nitrogen content which are relevant to organic synthesis, industry and fundamental research on molecular physics. It is mainly an experimental enterprise on selected organic azides and tetrazoles, with heavy support on theoretical results from readily available computational methods. Part of the work relies on the design and construction of scientific apparatus, which substantially improve the existing equipment and extend the limits of the experiment. The electronic structure and gas-phase thermal decomposition of methyl 2-azidopropionate (M2AP, N3CH3CHCO2CH 3), benzyl azide (BA, C6H5CH2N 3), 2-, 3- and 4- methyl benzyl azide (2-, 3- and 4-MBA, CH3C 6H4CH2N3), 5-aminotetrazole (5ATZ, NH2CN4H), and 5-methyltetrazole (5MTZ, CH3CN 4H) are investigated through photoelectron spectroscopy, using either He(I) (21.22 eV) or synchrotron radiation in the Xray range. Relevant information obtained from mass spectrometry and matrix-isolation infrared spectroscopy is used to complement characterization of the samples. Regarding each molecules' thermal decomposition, pathways are proposed which account for the observed end products. Conformational analysis is performed, and the special case of annular tautomerism is addressed in the tetrazole compounds. High-temperature pyrolysis work is performed in collaboration with the University of Southampton, and XPS analysis using synchrotron radiation is performed at Elettra, the multidisciplinary synchrotron light laboratory in Trieste, Italy. Experimental findings are rationalized using different computational methods, based on post-Hartree-Fock approaches: many-body perturbation theory (MPn), configuration interaction (CI) and Green's function methods (OVGF, P3), as well as density functional theory (DFT), are used extensively to obtain optimized molecular geometries, ionization energies, orbital contours, relative energies, vibrational frequencies, and to assess possible pathways for thermal or electron impact fragmentation. Composite methods (G n and CBS) are used to estimate to kcal mol-1 accuracy the energy balance between reactants, transition structures and products in the overall decomposition process of the specified molecules.

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

Parl, Angelika; Mitchell, Sabrina L.; Clay, Hayley B.

Highlights: •The function of the mitochondria fatty acid synthesis pathway is partially unknown. •Overexpression of the pathway causes transcriptional activation through PPARs. •Knock down of the pathway attenuates that activation. •The last enzyme in the pathway regulates its own transcription. •Products of the mtFASII pathway are able to drive nuclear transcription. -- Abstract: Mammalian cells contain two fatty acid synthesis pathways, the cytosolic FASI pathway, and the mitochondrial FASII pathway. The selection behind the conservation of the mitochondrial pathway is not completely understood, given the presence of the cytosolic FAS pathway. In this study, we show through heterologous gene reportermore » systems and PCR-based arrays that overexpression of MECR, the last step in the mtFASII pathway, causes modulation of gene expression through the PPAR pathway. Electromobility shift assays (EMSAs) demonstrate that overexpression of MECR causes increased binding of PPARs to DNA, while cell fractionation and imaging studies show that MECR remains localized to the mitochondria. Interestingly, knock down of the mtFASII pathway lessens the effect of MECR on this transcriptional modulation. Our data are most consistent with MECR-mediated transcriptional activation through products of the mtFASII pathway, although we cannot rule out MECR acting as a coactivator. Further investigation into the physiological relevance of this communication will be necessary to better understand some of the phenotypic consequences of deficits in this pathway observed in animal models and human disease.« less

Modeling the survivability of brucella to exposure of Ultraviolet radiation and temperature

NASA Astrophysics Data System (ADS)

Howe, R.

Accumulated summation of daily Ultra Violet-B (UV-B = 290? to 320 ? ) data? from The USDA Ultraviolet Radiation Monitoring Program show good correlation (R^2 = 77%) with daily temperature data during the five month period from February through June, 1998. Exposure of disease organisms, such as brucella to the effects of accumulated UV-B radiation, can be modeled for a 5 month period from February through June, 1998. Estimates of a lethal dosage for brucell of UV-B in the environment is dependent on minimum/maximum temperature and Solar Zenith Angle for the time period. The accumulated increase in temperature over this period also effects the decomposition of an aborted fetus containing brucella. Decomposition begins at some minimum daily temperature at 27 to 30 degrees C and peaks at 39 to 40C. It is useful to view the summation of temperature as a threshold for other bacteria growth, so that accumulated temperature greater than some value causes decomposition through competition with other bacteria and brucella die from the accumulated effects of UV-B, temperature and organism competition. Results of a study (Cook 1998) to determine survivability of brucellosis in the environment through exposure of aborted bovine fetuses show no one cause can be attributed to death of the disease agent. The combination of daily increase in temperature and accumulated UV-B radiation reveal an inverse correlation to survivability data and can be modeled as an indicator of brucella survivability in the environment in arid regions.

Methamphetamine generates peroxynitrite and produces dopaminergic neurotoxicity in mice: protective effects of peroxynitrite decomposition catalyst.

PubMed

Imam, S Z; Crow, J P; Newport, G D; Islam, F; Slikker, W; Ali, S F

1999-08-07

Methamphetamine (METH)-induced dopaminergic neurotoxicity is believed to be produced by oxidative stress and free radical generation. The present study was undertaken to investigate if METH generates peroxynitrite and produces dopaminergic neurotoxicity. We also investigated if this generation of peroxynitrite can be blocked by a selective peroxynitrite decomposition catalyst, 5, 10,15, 20-tetrakis(N-methyl-4'-pyridyl)porphyrinato iron III (FeTMPyP) and protect against METH-induced dopaminergic neurotoxicity. Administration of METH resulted in the significant formation of 3-nitrotyrosine (3-NT), an in vivo marker of peroxynitrite generation, in the striatum and also caused a significant increase in the body temperature. METH injection also caused a significant decrease in the concentration of dopamine (DA), 3, 4-dihydroxyphenylacetic acid (DOPAC), and homovanillic acid (HVA) by 76%, 53% and 40%, respectively, in the striatum compared with the control group. Treatment with FeTMPyP blocked the formation of 3-NT by 66% when compared with the METH group. FeTMPyP treatment also provided significant protection against the METH-induced hyperthermia and depletion of DA, DOPAC and HVA. Administration of FeTMPyP alone neither resulted in 3-NT formation nor had any significant effect on DA or its metabolite concentrations. These findings indicate that peroxynitrite plays a role in METH-induced dopaminergic neurotoxicity and also suggests that peroxynitrite decomposition catalysts may be beneficial for the management of psychostimulant abuse. Copyright 1999 Published by Elsevier Science B.V.

Temperature effect on mineralization of SOM, plant litter and priming: modified by soil type?

NASA Astrophysics Data System (ADS)

Azzaroli Bleken, Marina; Berland Frøseth, Randi

2015-04-01

The purpose of this study was to provide improved temperature response functions to be used in models of soil organic carbon (SOC) and litter mineralization, with focus on the winter period. Our working hypothesis were: 1) decomposition of SOM and plant residue occurs also at temperature close to the freezing point; 2) the effect of temperature on SOC decomposition is stronger in clayey than in sandy soil; 3) decomposition and response to temperature of added plant litter is not affected by soil type. A silty clay loam (27% clay, 3% sand) and a sandy loam (6% clay, 51% sand) with similar weather and cultivation history were pre-incubated at about 15° C for about 4.5 months. Clover leaves labelled with 13C were added to half of the samples, and soil with and without clover was incubated for 142 days at 0, 4, 8.5 or 15 °C. Mineralization of SOC and clover leaves was observed also at 0° C. In the absence of added plant material, SOC decomposition followed a first order reaction which was twice as fast in the sandy soil as in the clay soil. The decomposition rate of clover leaves was also higher in the sandy soil than in the clay soil. However, the influence of temperature on SOC and on clover decomposition was the same in both soils. In presence of plant material, there was a positive priming effect on SOC, which initially correlated with decomposition of plant litter. There was a progressively lower priming effect at higher temperatures, particularly in the sandy soil, that could be understood as substrates exhaustion in a restricted volume of influence around the added clover leaves. We provide parameterised Arrhenius and alternative modifying linear temperature functions together with decay rates at reference temperature, which can be used for predicting decay rates of SOC per se and of the labile pool of clover leaves. We also show the superiority of these functions compared to the use of Q10 as temperature factor. Further, we suggest approaches for modelling the priming effect caused by plant litter. Reference: Frøseth RB, Bleken MA(2015) Effect of low temperature and soil type on the decomposition rate of soil organic carbon and clover leaves, and related priming effect. Soil Biology and Biochemistry 80:156-166.

Photodecomposition of dyes on Fe-C-TiO(2) photocatalysts under UV radiation supported by photo-Fenton process.

PubMed

Tryba, B; Piszcz, M; Grzmil, B; Pattek-Janczyk, A; Morawski, A W

2009-02-15

Fe-C-TiO(2) photocatalysts were prepared by mechanical mixing of commercial anatase TiO(2) precursor with FeC(2)O(4) and heating at 500-800 degrees C under argon flow. These photocatalysts were tested for dyes decomposition: Methylene Blue (MB), Reactive Black (RB) and Acid Red (AR). The preliminary adsorption of dyes on the photocatalysts surface was performed. Modification of anatase by FeC(2)O(4) caused reducing of zeta potential of the photocatalyst surface from +12 to -7mV and decreasing of their adsorption ability towards RB and AR, which were negatively charged, -46.8 and -39.7, respectively. Therefore, unmodified TiO(2) showed the highest degree of RB and AR decompositions in the combination of dyes adsorption and UV irradiation. Methylene Blue, which had zeta potential of +4.3 in the aqueous solution was poorly adsorbed on all the tested photocatalysts and also slowly decomposed under UV irradiation. The high rate of dyes decomposition was noted on Fe-C-TiO(2) photocatalysts under UV irradiation with addition of H(2)O(2). It was observed, that at lower temperatures of heat treatment such as 500 degrees C higher content of carbon is remained in the sample, blocking the built in of iron into the TiO(2) lattice. This iron is reactive in the photo-Fenton process resulting in high production of OH radicals and also high activity of the photocatalyst. At higher temperatures of heat treatment, less active FeTiO(3) phase is formed, therefore Fe-C-TiO(2) sample prepared at 800 degrees C showed low photocatalytic activity for dyes decomposition. Fe-C-TiO(2) photocatalysts are active under visible light irradiation, however, the efficiency of a dye decomposition is lower than under UV light. In a dark Fenton process there is observed an insignificant generation of OH radicals and very little decomposition of a dye, what suggests the powerful of photo-Fenton process in the dyes decomposition.

[Dynamics of microbial biomass carbon and nitrogen during foliar litter decomposition under artificial forest gap in Pinus massoniana plantation.

PubMed

Zhang, Ming Jin; Chen, Liang Hua; Zhang, Jian; Yang, Wan Qin; Liu, Hua; Li, Xun; Zhang, Yan

2016-03-01

Nowadays large areas of plantations have caused serious ecological problems such as soil degradation and biodiversity decline. Artificial tending thinning and construction of mixed forest are frequently used ways when we manage plantations. To understand the effect of this operation mode on nutrient cycle of plantation ecosystem, we detected the dynamics of microbial bio-mass carbon and nitrogen during foliar litter decomposition of Pinus massoniana and Toona ciliate in seven types of gap in different sizes (G 1 : 100 m 2 , G 2 : 225 m 2 , G 3 : 400 m 2 , G 4 : 625 m 2 , G 5 : 900 m 2 , G 6 : 1225 m 2 , G 7 : 1600 m 2 ) of 42-year-old P. massoniana plantations in a hilly area of the upper Yang-tze River. The results showed that small and medium-sized forest gaps(G 1 -G 5 ) were more advantageous for the increment of microbial biomass carbon and nitrogen in the process of foliar litter decomposition. Along with the foliar litter decomposition during the experiment (360 d), microbial biomass carbon (MBC), microbial biomass nitrogen (MBN) in P. massoniana foliar litter and MBN in T. ciliata foliar litter first increased and then decreased, and respectively reached the maxima 9.87, 0.22 and 0.80 g·kg -1 on the 180 th d. But the peak (44.40 g·kg -1 ) of MBC in T. ciliata foliar litter appeared on the 90 th d. Microbial biomass carbon and nitrogen in T. ciliate was significantly higher than that of P. massoniana during foliar litter decomposition. Microbial biomass carbon and nitrogen in foliar litter was not only significantly associated with average daily temperature and the water content of foliar litter, but also closely related to the change of the quality of litter. Therefore, in the thinning, forest gap size could be controlled in the range of from 100 to 900 m 2 to facilitate the increase of microbial biomass carbon and nitrogen in the process of foliar litter decomposition, accelerate the decomposition of foliar litter and improve soil fertility of plantations.

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Single Pd Atoms on θ-Al2O3 (010) Surface do not Catalyze NO Oxidation.

PubMed

Narula, Chaitanya K; Allard, Lawrence F; Moses-DeBusk, Melanie; Stocks, G Malcom; Wu, Zili

2017-04-03

New convenient wet-chemistry synthetic routes have made it possible to explore catalytic activities of a variety of single supported atoms, however, the single supported atoms on inert substrates (e.g. alumina) are limited to adatoms and cations of Pt, Pd, and Ru. Previously, we have found that single supported Pt atoms are remarkable NO oxidation catalysts. In contrast, we report that Pd single atoms are completely inactive for NO oxidation. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show the absence of nitrate formation on catalyst. To explain these results, we explored modified Langmuir-Hinshelwood type pathways that have been proposed for oxidation reactions on single supported atom. In the first pathway, we find that there is energy barrier for the release of NO 2 which prevent NO oxidation. In the second pathway, our results show that there is no driving force for the formation of O=N-O-O intermediate or nitrate on single supported Pd atoms. The decomposition of nitrate, if formed, is an endothermic event.

Enhancement of nitric oxide decomposition efficiency achieved with lanthanum-based perovskite-type catalyst.

PubMed

Pan, Kuan Lun; Chen, Mei Chung; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

2016-06-01

Direct decompositions of nitric oxide (NO) by La0.7Ce0.3SrNiO4, La0.4Ba0.4Ce0.2SrNiO4, and Pr0.4Ba0.4Ce0.2SrNiO4 are experimentally investigated, and the catalysts are tested with different operating parameters to evaluate their activities. Experimental results indicate that the physical and chemical properties of La0.7Ce0.3SrNiO4 are significantly improved by doping with Ba and partial substitution with Pr. NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4 are 32% and 68%, respectively, at 400 °C with He as carrier gas. As the temperature is increased to 600 °C, NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4, respectively, reach 100% with the inlet NO concentration of 1000 ppm while the space velocity is fixed at 8000 hr(-1). Effects of O2, H2O(g), and CO2 contents and space velocity on NO decomposition are also explored. The results indicate that NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4, respectively, are slightly reduced as space velocity is increased from 8000 to 20,000 hr(-1) at 500 °C. In addition, the activities of both catalysts (La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4) for NO decomposition are slightly reduced in the presence of 5% O2, 5% CO2, or 5% H2O(g). For durability test, with the space velocity of 8000 hr(-1) and operating temperature of 600 °C, high N2 yield is maintained throughout the durability test of 60 hr, revealing the long-term stability of Pr0.4Ba0.4Ce0.2SrNiO4 for NO decomposition. Overall, Pr0.4Ba0.4Ce0.2SrNiO4 shows good catalytic activity for NO decomposition. Nitrous oxide (NO) not only causes adverse environmental effects such as acid rain, photochemical smog, and deterioration of visibility and water quality, but also harms human lungs and respiratory system. Pervoskite-type catalysts, including La0.7Ce0.3SrNiO4, La0.4Ba0.4Ce0.2SrNiO4, and Pr0.4Ba0.4Ce0.2SrNiO4, are applied for direct NO decomposition. The results show that NO decomposition can be enhanced as La0.7Ce0.3SrNiO4 is substituted with Ba and/or Pr. At 600 °C, NO decomposition efficiencies achieved with La0.4Ba0.4Ce0.2SrNiO4 and Pr0.4Ba0.4Ce0.2SrNiO4 reach 100%, demonstrating high activity and good potential for direct NO decomposition. Effects of O2, H2O(g), and CO2 contents on catalytic activities are also evaluated and discussed.

Hierarchical modularization of biochemical pathways using fuzzy-c means clustering.

PubMed

de Luis Balaguer, Maria A; Williams, Cranos M

2014-08-01

Biological systems that are representative of regulatory, metabolic, or signaling pathways can be highly complex. Mathematical models that describe such systems inherit this complexity. As a result, these models can often fail to provide a path toward the intuitive comprehension of these systems. More coarse information that allows a perceptive insight of the system is sometimes needed in combination with the model to understand control hierarchies or lower level functional relationships. In this paper, we present a method to identify relationships between components of dynamic models of biochemical pathways that reside in different functional groups. We find primary relationships and secondary relationships. The secondary relationships reveal connections that are present in the system, which current techniques that only identify primary relationships are unable to show. We also identify how relationships between components dynamically change over time. This results in a method that provides the hierarchy of the relationships among components, which can help us to understand the low level functional structure of the system and to elucidate potential hierarchical control. As a proof of concept, we apply the algorithm to the epidermal growth factor signal transduction pathway, and to the C3 photosynthesis pathway. We identify primary relationships among components that are in agreement with previous computational decomposition studies, and identify secondary relationships that uncover connections among components that current computational approaches were unable to reveal.

No adverse effect of genetically modified antifungal wheat on decomposition dynamics and the soil fauna community--a field study.

PubMed

Duc, Caroline; Nentwig, Wolfgang; Lindfeld, Andreas

2011-01-01

The cultivation of genetically modified (GM) plants has raised several environmental concerns. One of these concerns regards non-target soil fauna organisms, which play an important role in the decomposition of organic matter and hence are largely exposed to GM plant residues. Soil fauna may be directly affected by transgene products or indirectly by pleiotropic effects such as a modified plant metabolism. Thus, ecosystem services and functioning might be affected negatively. In a litterbag experiment in the field we analysed the decomposition process and the soil fauna community involved. Therefore, we used four experimental GM wheat varieties, two with a race-specific antifungal resistance against powdery mildew (Pm3b) and two with an unspecific antifungal resistance based on the expression of chitinase and glucanase. We compared them with two non-GM isolines and six conventional cereal varieties. To elucidate the mechanisms that cause differences in plant decomposition, structural plant components (i.e. C∶N ratio, lignin, cellulose, hemicellulose) were examined and soil properties, temperature and precipitation were monitored. The most frequent taxa extracted from decaying plant material were mites (Cryptostigmata, Gamasina and Uropodina), springtails (Isotomidae), annelids (Enchytraeidae) and Diptera (Cecidomyiidae larvae). Despite a single significant transgenic/month interaction for Cecidomyiidae larvae, which is probably random, we detected no impact of the GM wheat on the soil fauna community. However, soil fauna differences among conventional cereal varieties were more pronounced than between GM and non-GM wheat. While leaf residue decomposition in GM and non-GM wheat was similar, differences among conventional cereals were evident. Furthermore, sampling date and location were found to greatly influence soil fauna community and decomposition processes. The results give no indication of ecologically relevant adverse effects of antifungal GM wheat on the composition and the activity of the soil fauna community.

Comparative effects of sulfuric and nitric acid rain on litter decomposition and soil microbial community in subtropical plantation of Yangtze River Delta region.

PubMed

Liu, Xin; Zhang, Bo; Zhao, Wenrui; Wang, Ling; Xie, Dejin; Huo, Wentong; Wu, Yanwen; Zhang, Jinchi

2017-12-01

Acid rain is mainly caused by dissolution of sulfur dioxide and nitrogen oxides in the atmosphere, and has a significant negative effect on ecosystems. The relative composition of acid rain is changing gradually from sulfuric acid rain (SAR) to nitric acid rain (NAR) with the rapidly growing amount of nitrogen deposition. In this study, we investigated the impact of simulated SAR and NAR on litter decomposition and the soil microbial community over four seasons since March 2015. Results first showed that the effects of acid rain on litter decomposition and soil microbial were positive in the early period of the experiment, except for SAR on soil microbes. Second, soil pH with NAR decreased more rapidly with the amount of acid rain increased in summer than with SAR treatments. Only strongly acid rain (both SAR and NAR) was capable of depressing litter decomposition and its inhibitory effect was stronger on leaf than on fine root litter. Meanwhile, NAR had a higher inhibitory effect on litter decomposition than SAR. Third, in summer, autumn and winter, PLFAs were negatively impacted by the increased acidity level resulting from both SAR and NAR. However, higher acidity level of NAR (pH=2.5) had the strongest inhibitory impact on soil microbial activity, especially in summer. In addition, Gram-negative bacteria (cy19:0) and fungi (18:1ω9) were more sensitive to both SAR and NAR, and actinomycetes was more sensitive to SAR intensity. Finally, soil total carbon, total nitrogen and pH were the most important soil property factors affecting soil microbial activity, and high microbial indices (fungi/bacteria) with high soil pH. Our results suggest that the ratio of SO 4 2- to NO 3 - in acid rain is an important factor which could affect litter decomposition and soil microbial in subtropical forest of China. Copyright © 2017. Published by Elsevier B.V.

Semi-empirical modelling for forest above ground biomass estimation using hybrid and fully PolSAR data

NASA Astrophysics Data System (ADS)

Tomar, Kiledar S.; Kumar, Shashi; Tolpekin, Valentyn A.; Joshi, Sushil K.

2016-05-01

Forests act as sink of carbon and as a result maintains carbon cycle in atmosphere. Deforestation leads to imbalance in global carbon cycle and changes in climate. Hence estimation of forest biophysical parameter like biomass becomes a necessity. PolSAR has the ability to discriminate the share of scattering element like surface, double bounce and volume scattering in a single SAR resolution cell. Studies have shown that volume scattering is a significant parameter for forest biophysical characterization which mainly occurred from vegetation due to randomly oriented structures. This random orientation of forest structure causes shift in orientation angle of polarization ellipse which ultimately disturbs the radar signature and shows overestimation of volume scattering and underestimation of double bounce scattering after decomposition of fully PolSAR data. Hybrid polarimetry has the advantage of zero POA shift due to rotational symmetry followed by the circular transmission of electromagnetic waves. The prime objective of this study was to extract the potential of Hybrid PolSAR and fully PolSAR data for AGB estimation using Extended Water Cloud model. Validation was performed using field biomass. The study site chosen was Barkot Forest, Uttarakhand, India. To obtain the decomposition components, m-alpha and Yamaguchi decomposition modelling for Hybrid and fully PolSAR data were implied respectively. The RGB composite image for both the decomposition techniques has generated. The contribution of all scattering from each plot for m-alpha and Yamaguchi decomposition modelling were extracted. The R2 value for modelled AGB and field biomass from Hybrid PolSAR and fully PolSAR data were found 0.5127 and 0.4625 respectively. The RMSE for Hybrid and fully PolSAR between modelled AGB and field biomass were 63.156 (t ha-1) and 73.424 (t ha-1) respectively. On the basis of RMSE and R2 value, this study suggests Hybrid PolSAR decomposition modelling to retrieve scattering element for AGB estimation from forest.

No Adverse Effect of Genetically Modified Antifungal Wheat on Decomposition Dynamics and the Soil Fauna Community – A Field Study

PubMed Central

Duc, Caroline; Nentwig, Wolfgang; Lindfeld, Andreas

2011-01-01

The cultivation of genetically modified (GM) plants has raised several environmental concerns. One of these concerns regards non-target soil fauna organisms, which play an important role in the decomposition of organic matter and hence are largely exposed to GM plant residues. Soil fauna may be directly affected by transgene products or indirectly by pleiotropic effects such as a modified plant metabolism. Thus, ecosystem services and functioning might be affected negatively. In a litterbag experiment in the field we analysed the decomposition process and the soil fauna community involved. Therefore, we used four experimental GM wheat varieties, two with a race-specific antifungal resistance against powdery mildew (Pm3b) and two with an unspecific antifungal resistance based on the expression of chitinase and glucanase. We compared them with two non-GM isolines and six conventional cereal varieties. To elucidate the mechanisms that cause differences in plant decomposition, structural plant components (i.e. C∶N ratio, lignin, cellulose, hemicellulose) were examined and soil properties, temperature and precipitation were monitored. The most frequent taxa extracted from decaying plant material were mites (Cryptostigmata, Gamasina and Uropodina), springtails (Isotomidae), annelids (Enchytraeidae) and Diptera (Cecidomyiidae larvae). Despite a single significant transgenic/month interaction for Cecidomyiidae larvae, which is probably random, we detected no impact of the GM wheat on the soil fauna community. However, soil fauna differences among conventional cereal varieties were more pronounced than between GM and non-GM wheat. While leaf residue decomposition in GM and non-GM wheat was similar, differences among conventional cereals were evident. Furthermore, sampling date and location were found to greatly influence soil fauna community and decomposition processes. The results give no indication of ecologically relevant adverse effects of antifungal GM wheat on the composition and the activity of the soil fauna community. PMID:22043279

Sarcomere protein gene mutations and inherited heart disease: a beta-cardiac myosin heavy chain mutation causing endocardial fibroelastosis and heart failure.

PubMed

Kamisago, Mitsuhiro; Schmitt, Joachim P; McNamara, Dennis; Seidman, Christine; Seidman, J G

2006-01-01

Inherited human cardiomyopathies often lead to heart failure. A common feature of these conditions is that affected individuals can express the disease causing mutations for many years without showing clinical signs of the disease. Previous studies have demonstrated that sarcomere protein gene mutations can cause either dilated cardiomyopathy or hypertrophic cardiomyopathy. Here we demonstrate that the Arg442His missense mutation in beta-cardiac myosin heavy chain (betaMHC) causes dilated cardiomyopathy, endocardial fibroelastosis and heart failure at a very early age. Using standard genetic engineering tools we and others have made murine models by introducing human disease causing mutations into mice. The central hypothesis of these studies has been that by identifying the pathophysiological pathways activated by these mutations we can define enzymatic activities that are modified during the disease process and which may be involved in pathways that involve more common forms of cardiac disease. Murine models bearing different mutant myosins are being used to address whether each disease causing mutant betaMHC activates the same or different cellular pathways. Dissecting the molecular pathways modulated by mutations in sarcomere protein genes as well as other genes has already demonstrated that there are multiple pathways leading to cardiac remodelling and heart failure. Defining the mechanisms by which mutations in the same genes activate different cellular pathways remains an important question.

Comparing Alternative Effect Decomposition Methods: The Role of Literacy in Mediating Educational Effects on Mortality.

PubMed

Nguyen, Thu T; Tchetgen Tchetgen, Eric J; Kawachi, Ichiro; Gilman, Stephen E; Walter, Stefan; Glymour, M Maria

2016-09-01

Inverse odds ratio weighting, a newly proposed tool to evaluate mediation in exposure-disease associations, may be valuable for a host of research questions, but little is known about its performance in real data. We compare this approach to a more conventional Baron and Kenny type of decomposition on an additive hazards scale to estimate total, direct, and indirect effects using the example of the role of literacy in mediating the effects of education on mortality. Health and Retirement Study participants born in the United States between 1900 and 1947 were interviewed biennially for up to 12 years (N = 17,054). Literacy was measured with a brief vocabulary assessment. Decomposition estimates were derived based on Aalen additive hazards models. A 1 standard deviation difference in educational attainment (3 years) was associated with 6.7 fewer deaths per 1000 person-years (β = -6.7, 95% confidence interval [CI]: -7.9, -5.4). Of this decrease, 1.3 fewer deaths (β = -1.3, 95% CI: -4.0, 1.2) were attributed to the literacy pathway (natural indirect), representing 19% of the total effect. Baron and Kenny estimates were consistent with inverse odds ratio weighting estimates but were less variable (natural indirect effect: -1.2 [95% CI: -1.7, -0.69], representing 18% of total effect). In a cohort of older Americans, literacy partially mediated the effect of education on mortality. See Video Abstract at http://links.lww.com/EDE/B78.

γ-Fe{sub 2}O{sub 3} nanoparticles: An easily recoverable effective photo-catalyst for the degradation of rose bengal and methylene blue dyes in the waste-water treatment plant

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

Dutta, Amit Kumar; Maji, Swarup Kumar; Adhikary, Bibhutosh, E-mail: bibhutoshadhikary@yahoo.in

2014-01-01

Graphical abstract: - Highlights: • γ-Fe{sub 2}O{sub 3} NPs from a single-source precursor and characterized by XRD, TEM, UV–vis spectra. • The NPs were tested as effective photocatalyst toward degradation of RB and MB dyes. • The possible pathway of the photocatalytic decomposition process has been discussed. • The active species, OH·, was detected by TA photoluminescence probing techniques. - Abstract: γ-Fe{sub 2}O{sub 3} nanoparticles (NPs) were synthesized from a single-source precursor complex [Fe{sub 3}O(C{sub 6}H{sub 5}COO){sub 6}(H{sub 2}O){sub 3}]NO{sub 3} by a simple thermal decomposition process and have been characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM)more » and UV–vis spectroscopic techniques. The NPs were highly pure and well crystallized having hexagonal morphology with an average particle size of 35 nm. The prepared γ-Fe{sub 2}O{sub 3} (maghemite) NPs show effective photo-catalytic activity toward the degradation of rose bengal (RB) and methylene blue (MB) dyes under visible light irradiation and can easily be recoverable in the presence of magnetic field for successive re-uses. The possible photo-catalytic decomposition mechanism is discussed through the detection of hydroxyl radical (OH·) by terephthalic acid photo-luminescence probing technique.« less

Stabilizing bidirectional associative memory with Principles in Independent Component Analysis and Null Space (PICANS)

NASA Astrophysics Data System (ADS)

LaRue, James P.; Luzanov, Yuriy

2013-05-01

A new extension to the way in which the Bidirectional Associative Memory (BAM) algorithms are implemented is presented here. We will show that by utilizing the singular value decomposition (SVD) and integrating principles of independent component analysis (ICA) into the nullspace (NS) we have created a novel approach to mitigating spurious attractors. We demonstrate this with two applications. The first application utilizes a one-layer association while the second application is modeled after the several hierarchal associations of ventral pathways. The first application will detail the way in which we manage the associations in terms of matrices. The second application will take what we have learned from the first example and apply it to a cascade of a convolutional neural network (CNN) and perceptron this being our signal processing model of the ventral pathways, i.e., visual systems.

A mechanistical study on non-equilibrium reaction pathways in solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) upon interaction with ionizing radiation

NASA Astrophysics Data System (ADS)

Kaiser, Ralf I.; Maksyutenko, Pavlo

2015-07-01

Thin films of homogeneously mixed nitromethane (CH3NO2) and D3-nitromethane (CD3NO2) ices were exposed to energetic electrons and Lyman α photons. The isotopically mixed reaction products were probed in situ via reflectron time-of-flight mass spectrometry coupled with pulsed photoionization during temperature programmed desorption. This study provides compelling evidence on three high energy pathways, which have not been observed under collisionless conditions in the gas phase. These are decomposition of nitromethane (CH3NO2) via atomic oxygen loss to nitrosomethane (CH3NO), fragmentation of nitromethane (CH3NO2) and/or methylnitrite (CH3ONO) via carbene (CH2) loss, and carbonsbnd hydrogen bond rupture processes in nitromethane (CH3NO2) and/or methylnitrite (CH3ONO).

Measuring and decomposing socioeconomic inequality in healthcare delivery: A microsimulation approach with application to the Palestinian conflict-affected fragile setting.

PubMed

Abu-Zaineh, Mohammad; Mataria, Awad; Moatti, Jean-Paul; Ventelou, Bruno

2011-01-01

Socioeconomic-related inequalities in healthcare delivery have been extensively studied in developed countries, using standard linear models of decomposition. This paper seeks to assess equity in healthcare delivery in the particular context of the occupied Palestinian territory: the West Bank and the Gaza Strip, using a new method of decomposition based on microsimulations. Besides avoiding the 'unavoidable price' of linearity restriction that is imposed by the standard methods of decomposition, the microsimulation-based decomposition enables to circumvent the potentially contentious role of heterogeneity in behaviours and to better disentangle the various sources driving inequality in healthcare utilisation. Results suggest that the worse-off do have a disproportinately greater need for all levels of care. However with the exception of primary-level, utilisation of all levels of care appears to be significantly higher for the better-off. The microsimulation method has made it possible to identify the contributions of factors driving such pro-rich patterns. While much of the inequality in utilisation appears to be caused by the prevailing socioeconomic inequalities, detailed analysis attributes a non-trivial part (circa 30% of inequalities) to heterogeneity in healthcare-seeking behaviours across socioeconomic groups of the population. Several policy recommendations for improving equity in healthcare delivery in the occupied Palestinian territory are proposed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Effect of variable rates of daily sampling of fly larvae on decomposition and carrion insect community assembly: implications for forensic entomology field study protocols.

PubMed

Michaud, Jean-Philippe; Moreau, Gaétan

2013-07-01

Experimental protocols in forensic entomology successional field studies generally involve daily sampling of insects to document temporal changes in species composition on animal carcasses. One challenge with that method has been to adjust the sampling intensity to obtain the best representation of the community present without affecting the said community. To this date, little is known about how such investigator perturbations affect decomposition-related processes. Here, we investigated how different levels of daily sampling of fly eggs and fly larvae affected, over time, carcass decomposition rate and the carrion insect community. Results indicated that a daily sampling of <5% of the egg and larvae volumes present on a carcass, a sampling intensity believed to be consistent with current accepted practices in successional field studies, had little effect overall. Higher sampling intensities, however, slowed down carcass decomposition, affected the abundance of certain carrion insects, and caused an increase in the volume of eggs laid by dipterans. This study suggests that the carrion insect community not only has a limited resilience to recurrent perturbations but that a daily sampling intensity equal to or <5% of the egg and larvae volumes appears adequate to ensure that the system is representative of unsampled conditions. Hence we propose that this threshold be accepted as best practice in future forensic entomology successional field studies.

Ultrasonic technique for imaging tissue vibrations: preliminary results.

PubMed

Sikdar, Siddhartha; Beach, Kirk W; Vaezy, Shahram; Kim, Yongmin

2005-02-01

We propose an ultrasound (US)-based technique for imaging vibrations in the blood vessel walls and surrounding tissue caused by eddies produced during flow through narrowed or punctured arteries. Our approach is to utilize the clutter signal, normally suppressed in conventional color flow imaging, to detect and characterize local tissue vibrations. We demonstrate the feasibility of visualizing the origin and extent of vibrations relative to the underlying anatomy and blood flow in real-time and their quantitative assessment, including measurements of the amplitude, frequency and spatial distribution. We present two signal-processing algorithms, one based on phase decomposition and the other based on spectral estimation using eigen decomposition for isolating vibrations from clutter, blood flow and noise using an ensemble of US echoes. In simulation studies, the computationally efficient phase-decomposition method achieved 96% sensitivity and 98% specificity for vibration detection and was robust to broadband vibrations. Somewhat higher sensitivity (98%) and specificity (99%) could be achieved using the more computationally intensive eigen decomposition-based algorithm. Vibration amplitudes as low as 1 mum were measured accurately in phantom experiments. Real-time tissue vibration imaging at typical color-flow frame rates was implemented on a software-programmable US system. Vibrations were studied in vivo in a stenosed femoral bypass vein graft in a human subject and in a punctured femoral artery and incised spleen in an animal model.

Flexible Mediation Analysis With Multiple Mediators.

PubMed

Steen, Johan; Loeys, Tom; Moerkerke, Beatrijs; Vansteelandt, Stijn

2017-07-15

The advent of counterfactual-based mediation analysis has triggered enormous progress on how, and under what assumptions, one may disentangle path-specific effects upon combining arbitrary (possibly nonlinear) models for mediator and outcome. However, current developments have largely focused on single mediators because required identification assumptions prohibit simple extensions to settings with multiple mediators that may depend on one another. In this article, we propose a procedure for obtaining fine-grained decompositions that may still be recovered from observed data in such complex settings. We first show that existing analytical approaches target specific instances of a more general set of decompositions and may therefore fail to provide a comprehensive assessment of the processes that underpin cause-effect relationships between exposure and outcome. We then outline conditions for obtaining the remaining set of decompositions. Because the number of targeted decompositions increases rapidly with the number of mediators, we introduce natural effects models along with estimation methods that allow for flexible and parsimonious modeling. Our procedure can easily be implemented using off-the-shelf software and is illustrated using a reanalysis of the World Health Organization's Large Analysis and Review of European Housing and Health Status (WHO-LARES) study on the effect of mold exposure on mental health (2002-2003). © The Author(s) 2017. Published by Oxford University Press on behalf of the Johns Hopkins Bloomberg School of Public Health. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

PubMed

Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-07-09

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

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

Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-01-01

Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40more » nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.« less

Ethylene decomposition over Pt(100): A mechanism study from first principle calculation

NASA Astrophysics Data System (ADS)

Wang, Yuchun; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2016-12-01

First principle based density functional theory was used to calculate the complete step-by-step decomposition network of ethylene (C2H4) over Pt(100) as a model for understanding the carbon deposition of olefin hydrocarbon over transition metal surface. We discussed the structural and energetic properties of all the Csbnd H and Csbnd C bond cleavage reactions in order to fully understand the formation pathway of carbon monomer. It is easier for Csbnd H bond cleavage reactions to take place, as the activation barrier of these reactions is relatively lower than that of Csbnd C bond cleavage as a whole. However, vinyl (CH2CH) is likely to be the precursor of Csbnd C bond scission, as the activation barrier of Csbnd C bond cleavage reaction of CH2CH is much lower than that of CH2CH dehydrogenation and the reaction is exothermic by 0.15 eV. CC was another form of depositional carbon on Pt(100), as it is easy to form but difficult to decompose. Finally we proposed six possible routes of carbon monomer formation.

Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant.

PubMed

Hao, Feifei; Guo, Weilin; Wang, Anqi; Leng, Yanqiu; Li, Helian

2014-03-01

Ammonium perfluorooctanoate (APFO) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. The decomposition of APFO in aqueous solution with a combination of persulfate oxidant and ultrasonic irradiation was investigated. The effects of operating parameters, such as ultrasonic power, persulfate concentration, APFO concentration, and initial media pH on APFO degradation were discussed. In the absence of persulfate, 35.5% of initial APFO in 46.4 μmol/L solution under ultrasound irradiation, was decomposed rapidly after 120 min with the defluorination ratio reaching 6.73%. In contrast, when 10 mmol/L persulfate was used, 51.2% of initial APFO (46.4 μmol/L) was decomposed and the defluorination ratio reached 11.15% within 120 min reaction time. Enhancement of the decomposition of APFO can be explained by acceleration of substrate decarboxylation, induced by sulfate radical anions formed from the persulfate during ultrasonic irradiation. The SO4(-•)/APFO reactions at the bubble-water interface appear to be the primary pathway for the sonochemical degradation of the perfluorinated surfactants. Copyright © 2013 Elsevier B.V. All rights reserved.

Composition control and localization of S2- in CdSSe quantum dots grown from Li4[Cd10Se4(SPh)16].

PubMed

Lovingood, Derek D; Oyler, Ryan E; Strouse, Geoffrey F

2008-12-17

The development of ternary nanoscale materials with controlled cross-sectional doping is an important step for the use of chemically prepared quantum dots for nanoscale engineering applications. We report cross-sectional, elemental doping with the formation of an alloyed CdSSe nanocrystal from the thermal decomposition of Li(4)[Cd(10)Se(4)(SPh)(16)]. The sulfur incorporation arises from surface-mediated phenylthiolate degradation on the growing quantum dot surface. In the alloy, we identify a pure CdSe nucleus of approximately 1.5 nm, consistent with the predictions of nucleation theory. As the particle grows, S(2-) incorporation increases until the CdSSe reaches approximately 4 nm, where a marked reduction in phenylthiolate content on the nanocrystal is observed by CP-MAS NMR spectroscopy, implying that rapid decomposition of the phenylthiolate arises with subsequent enhanced S(2-) incorporation at the level of the stoichiometry of the reaction (namely approximately 60%). The use of molecular clusters to allow controlled defect ion incorporation can open new pathways to more complex nanomaterials.

Edaravone attenuates brain damage in rats after acute CO poisoning through inhibiting apoptosis and oxidative stress.

PubMed

Li, Qin; Bi, Ming Jun; Bi, Wei Kang; Kang, Hai; Yan, Le Jing; Guo, Yun-Liang

2016-03-01

Acute carbon monoxide (CO) poisoning is the most common cause of death from poisoning all over the world and may result in neuropathologic and neurophysiologic changes. Acute brain damage and delayed encephalopathy are the most serious complication, yet their pathogenesis is poorly understood. The present study aimed to evaluate the neuroprotective effects of Edaravone against apoptosis and oxidative stress after acute CO poisoning. The rat model of CO poisoning was established in a hyperbaric oxygen chamber by exposed to CO. Ultrastructure changes were observed by transmission electron microscopy (TEM). TUNEL stain was used to assess apoptosis. Immunohistochemistry and immunofluorescence double stain were used to evaluate the expression levels of heme oxygenase-1 (HO-1) and nuclear factor erythroid 2-related factor 2 (Nrf-2) protein and their relationship. By dynamically monitored the carboxyhemoglobin (HbCO) level in blood, we successfully established rat model of severe CO poisoning. Ultrastructure changes, including chromatin condensation, cytoplasm dissolution, vacuoles formation, nucleus membrane and cell organelles decomposition, could be observed after CO poisoning. Edaravone could improve the ultrastructure damage. CO poisoning could induce apoptosis. Apoptotic cells were widely distributed in cortex, striatum and hippocampus. Edaravone treatment attenuated neuronal apoptosis as compared with the poisoning group (P < 0.01). Basal expressions of HO-1 and Nrf-2 proteins were found in normal brain tissue. CO poisoning could activate HO-1/Nrf-2 pathway, start oxidative stress response. After the administration of Edaravone, the expression of HO-1 and Nrf-2 significantly increased (P < 0.01). These findings suggest that Edaravone may inhibit apoptosis, activate the Keapl-Nrf/ARE pathway, and thus improve the ultrastructure damage and neurophysiologic changes following acute CO poisoning. © 2014 Wiley Periodicals, Inc.

Infrared and reflectron time-of-flight mass spectroscopic study on the synthesis of glycolaldehyde in methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) ices exposed to ionization radiation.

PubMed

Maity, Surajit; Kaiser, Ralf I; Jones, Brant M

2014-01-01

We present conclusive evidence on the formation of glycolaldehyde (HOCH2CHO) synthesized within astrophysically relevant ices of methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) upon exposure to ionizing radiation at 5.5 K. The radiation induced chemical processes of the ices were monitored on line and in situ via infrared spectroscopy which was complimented by temperature programmed desorption studies post irradiation, utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon fragment free photoionization (ReTOF-PI) at 10.49 eV. Specifically, glycolaldehyde was observed via the v14 band and further enhanced with the associated frequency shifts of the carbonyl stretching mode observed in irradiated isotopologue ice mixtures. Furthermore, experiments conducted with mixed isotopic ices of methanol-carbon monoxide (13CH3OH-CO, CH3(18)OH-CO, CD3OD-13CO and CH3OH-C18O) provide solid evidence of at least three competing reaction pathways involved in the formation of glycolaldehyde via non-equilibrium chemistry, which were identified as follows: (i) radical-radical recombination of HCO and CH2OH formed via decomposition of methanol--the "two methanol pathway"; (ii) via the reaction of one methanol unit (CH2OH from the decomposition of CH3OH) with one carbon monoxide unit (HCO from the hydrogenation of CO)--the "one methanol, one carbon monoxide pathway"; and (iii) formation via hydrogenation of carbon monoxide resulting in radicals of HCO and CH2OH--the "two carbon monoxide pathway". In addition, temperature programmed desorption studies revealed an increase in the amount of glycolaldehyde formed, suggesting further thermal chemistry of trapped radicals within the ice matrix. Sublimation of glycolaldehyde during the warm up was also monitored via ReTOF-PI and validated via the mutual agreement of the associated isotopic frequency shifts within the infrared band positions and the identical sublimation profiles obtained from the ReTOF spectra and infrared spectroscopy of the corresponding isotopes. In addition, an isomer of glycolaldehyde (ethene-1,2-diol) was tentatively assigned. Confirmation of the identified pathways based on infrared spectroscopy was also obtained from the observed ion signals corresponding to isotopomers of glycolaldehyde. These coupled techniques provide clear, concise evidence of the formation of a complex and astrobiologically important organic, glycolaldehyde, relevant to the icy mantles observed in the interstellar medium.

Factors affecting the water odor caused by chloramines during drinking water disinfection.

PubMed

Wang, An-Qi; Lin, Yi-Li; Xu, Bin; Hu, Chen-Yan; Gao, Ze-Chen; Liu, Zhi; Cao, Tong-Cheng; Gao, Nai-Yun

2018-10-15

Chloramine disinfection is one of the most common disinfection methods in drinking water treatment. In this study, the temporal variability of water odors during monochloramine auto-decomposition was investigated to elucidate the characteristics of odor problems caused by adopting chloramine disinfection in tap water. Odor intensities and dominant odorant contributions were determined using the flavor profile analysis (FPA) and odor active value (OAV), respectively. During auto-decomposition of monochloramine, Cl 2 /N molar ratio, pH, temperature, and the presence of NOM all affected odor intensity and odor temporal variation in drinking water. In general, decreasing pH from 8.5 to 6.0 led to increasing perceived odor intensity due to the formation of dichloramine. The major odorants responsible for chlorinous odor under acidic and non-acidic conditions were dichloramine and monochloramine, respectively. Chloraminated water with a Cl 2 /N molar ratio of 0.6 or NOM concentration <2 mg-C L -1 inhibited odor intensity. Furthermore, the influence of rechlorination on chlorinous odor intensity for chloraminated water should not be neglected. The results of this study will be beneficial for the control of chlorinous odors caused by chloramine disinfection in drinking water. Copyright © 2018 Elsevier B.V. All rights reserved.

The influence of cyclomaltooligosaccharides (cyclodextrins) on the enzymatic decomposition of l-phenylalanine catalyzed by phenylalanine ammonia-lyase.

PubMed

Gubica, Tomasz; Pełka, Agnieszka; Pałka, Katarzyna; Temeriusz, Andrzej; Kańska, Marianna

2011-09-27

Cyclomaltohexaose (α-cyclodextrin) and cyclomaltoheptaose (β-cyclodextrin) as well as their four methyl ether derivatives, that is, hexakis(2,3-di-O-methyl)cyclomaltohexaose, hexakis(2,3,6-tri-O-methyl)cyclomaltohexaose, heptakis(2,3-di-O-methyl)cyclomaltoheptaose, and heptakis(2,3,6-tri-O-methyl)cyclomaltoheptaose were investigated as the additives in the course of enzymatic decomposition of l-phenylalanine catalyzed by phenylalanine ammonia-lyase. Only a few of those additives behaved like classical inhibitors of the enzymatic reaction under investigation because the values of the Michaelis constants that were obtained, as well as the maximum velocity values depended mostly atypically on the concentrations of those additives. In most cases cyclodextrins caused mixed inhibition, both competitive and noncompetitive, but they also acted as activators for selected concentrations. This atypical behaviour of cyclodextrins is caused by three different and independent effects. The inhibitory effect of cyclodextrins is connected with the decrease of substrate concentration and unfavourable influence on the flexibility of the enzyme molecules. On the other hand, the activating effect is connected with the decrease of product concentration (the product is an inhibitor of the enzymatic reaction under investigation). All these effects are caused by the ability of the cyclodextrins to form inclusion complexes. Copyright © 2011 Elsevier Ltd. All rights reserved.

High-Dimensional Sparse Factor Modeling: Applications in Gene Expression Genomics

PubMed Central

Carvalho, Carlos M.; Chang, Jeffrey; Lucas, Joseph E.; Nevins, Joseph R.; Wang, Quanli; West, Mike

2010-01-01

We describe studies in molecular profiling and biological pathway analysis that use sparse latent factor and regression models for microarray gene expression data. We discuss breast cancer applications and key aspects of the modeling and computational methodology. Our case studies aim to investigate and characterize heterogeneity of structure related to specific oncogenic pathways, as well as links between aggregate patterns in gene expression profiles and clinical biomarkers. Based on the metaphor of statistically derived “factors” as representing biological “subpathway” structure, we explore the decomposition of fitted sparse factor models into pathway subcomponents and investigate how these components overlay multiple aspects of known biological activity. Our methodology is based on sparsity modeling of multivariate regression, ANOVA, and latent factor models, as well as a class of models that combines all components. Hierarchical sparsity priors address questions of dimension reduction and multiple comparisons, as well as scalability of the methodology. The models include practically relevant non-Gaussian/nonparametric components for latent structure, underlying often quite complex non-Gaussianity in multivariate expression patterns. Model search and fitting are addressed through stochastic simulation and evolutionary stochastic search methods that are exemplified in the oncogenic pathway studies. Supplementary supporting material provides more details of the applications, as well as examples of the use of freely available software tools for implementing the methodology. PMID:21218139

Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

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

Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn; The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081; Deng, Xiangong

2016-07-15

Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) weremore » prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.« less

Comparison of hybrid spectral-decomposition artificial neural network models for understanding climatic forcing of groundwater levels

NASA Astrophysics Data System (ADS)

Abrokwah, K.; O'Reilly, A. M.

2017-12-01

Groundwater is an important resource that is extracted every day because of its invaluable use for domestic, industrial and agricultural purposes. The need for sustaining groundwater resources is clearly indicated by declining water levels and has led to modeling and forecasting accurate groundwater levels. In this study, spectral decomposition of climatic forcing time series was used to develop hybrid wavelet analysis (WA) and moving window average (MWA) artificial neural network (ANN) models. These techniques are explored by modeling historical groundwater levels in order to provide understanding of potential causes of the observed groundwater-level fluctuations. Selection of the appropriate decomposition level for WA and window size for MWA helps in understanding the important time scales of climatic forcing, such as rainfall, that influence water levels. Discrete wavelet transform (DWT) is used to decompose the input time-series data into various levels of approximate and details wavelet coefficients, whilst MWA acts as a low-pass signal-filtering technique for removing high-frequency signals from the input data. The variables used to develop and validate the models were daily average rainfall measurements from five National Atmospheric and Oceanic Administration (NOAA) weather stations and daily water-level measurements from two wells recorded from 1978 to 2008 in central Florida, USA. Using different decomposition levels and different window sizes, several WA-ANN and MWA-ANN models for simulating the water levels were created and their relative performances compared against each other. The WA-ANN models performed better than the corresponding MWA-ANN models; also higher decomposition levels of the input signal by the DWT gave the best results. The results obtained show the applicability and feasibility of hybrid WA-ANN and MWA-ANN models for simulating daily water levels using only climatic forcing time series as model inputs.

Examining an underappreciated control on lignin decomposition in soils? Effects of reactive manganese species on intact plant cell walls

NASA Astrophysics Data System (ADS)

Keiluweit, M.; Bougoure, J.; Pett-Ridge, J.; Kleber, M.; Nico, P. S.

2011-12-01

Lignin comprises a dominant proportion of carbon fluxes into the soil (representing up to 50% of plant litter and roots). Two lines of evidence suggest that manganese (Mn) acts as a strong controlling factor on the residence time of lignin in soil ecosystems. First, Mn content is highly correlated with litter decomposition in temperate and boreal forest soil ecosystems and, second, microbial agents of lignin degradation have been reported to rely on reactive Mn(III)-complexes to specifically oxidize lignin. However, few attempts have been made to isolate the mechanisms responsible for the apparent Mn-dependence of lignin decomposition in soils. Here we tested the hypothesis that Mn(III)-oxalate complexes may act as a perforating 'pretreatment' for structurally intact plant cell walls. We propose that these diffusible oxidizers are small enough to penetrate and react with non-porous ligno-cellulose in cell walls. This process was investigated by reacting single Zinnia elegans tracheary elements with Mn(III)-oxalate complexes in a continuous flow-through microreactor. The uniformity of cultured tracheary elements allowed us to examine Mn(III)-induced changes in cell wall chemistry and ultrastructure on the micro-scale using fluorescence and electron microscopy as well as synchrotron-based infrared and X-ray spectromicroscopy. Our results show that Mn(III)-complexes substantially oxidize specific lignin components of the cell wall, solubilize decomposition products, severely undermine the cell wall integrity, and cause cell lysis. We conclude that Mn(III)-complexes induce oxidative damage in plant cell walls that renders ligno-cellulose substrates more accessible for microbial lignin- and cellulose-decomposing enzymes. Implications of our results for the rate limiting impact of soil Mn speciation and availability on litter decomposition in forest soils will be discussed.

Experiments on the role of water in petroleum formation

NASA Astrophysics Data System (ADS)

Lewan, M. D.

1997-09-01

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330°C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350°C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n-alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C 5 to C 35) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO 2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D 2O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H + activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the generation of exogenous hydrogen and excess oxygen as CO 2. One reaction series involves water oxidizing existing carbonyl groups to form hydrogen and car☐yl groups, with the latter forming CO 2 by decar☐ylation with increasing thermal stress. Another reaction series involves either hydrogen or oxygen in dissolved water molecules directly interacting with unpaired electrons to form a hydrogen-terminated free-radical site or an oxygenated functional group, respectively. The latter is expected to be susceptible to oxidation by other dissolved water molecules to generate additional hydrogen and CO 2. In addition to water acting as an exogenous source of hydrogen, it is also essential to the generation of an expelled saturate-enriched oil that is similar to natural crude oil. This role of water is demonstrated by the lack of an expelled oil in an experiment where a liquid Ga sbnd In alloy is substituted for liquid water. Experiments conducted with high salinity water and high water/rock ratios indicate that selective aqueous solubility of hydrocarbons is not responsible for the expelled oil generated in hydrous pyrolysis experiments. Similarly, a hydrous pyrolysis experiment conducted with isolated kerogen indicates that expelled oil in hydrous pyrolysis is not the result of preferential sorption of polar organic components by the mineral matrix of a source rock. It is envisaged that dissolved water in the bitumen network of a source rock causes an immiscible saturate-enriched oil to become immiscible with the thermally decomposing polar-enriched bitumen. The overall geochemical implication of these results is that it is essential to consider the role of water in experimental studies designed to understand natural rates of petroleum generation, expulsion mechanisms of primary migration, thermal stability of crude oil, reaction kinetics of biomarker transformations, and thermal maturity indicators in sedimentary basins.

Experiments on the role of water in petroleum formation

USGS Publications Warehouse

Lewan, M.D.

1997-01-01

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330??C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350??C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n-alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C5 to C35) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D2O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H+ activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the generation of exogenous hydrogen and excess oxygen as CO2. One reaction series involves water oxidizing existing carbonyl groups to form hydrogen and carboxyl groups, with the latter forming CO2 by decarboxylation with increasing thermal stress. Another reaction series involves either hydrogen or oxygen in dissolved water molecules directly interacting with unpaired electrons to form a hydrogen-terminated free-radical site or an oxygenated functional group, respectively. The latter is expected to be susceptible to oxidation by other dissolved water molecules to generate additional hydrogen and CO2. In addition to water acting as an exogenous source of hydrogen, it is also essential to the generation of an expelled saturate-enriched oil that is similar to natural crude oil. This role of water is demonstrated by the lack of an expelled oil in an experiment where a liquid Ga-In alloy is substituted for liquid water. Experiments conducted with high salinity water and high water/rock ratios indicate that selective aqueous solubility of hydrocarbons is not responsible for the expelled oil generated in hydrous pyrolysis experiments. Similarly, a hydrous pyrolysis experiment conducted with isolated kerogen indicates that expelled oil in hydrous pyrolysis is not the result of preferential sorption of polar organic components by the mineral matrix of a source rock. It is envisaged that dissolved water in the bitumen network of a source rock causes an immiscible saturate-enriched oil to become immiscible with the thermally decomposing polar-enriched bitumen. The overall geochemical implication of these results is that it is essential to consider the role of water in experimental studies designed to understand natural rates of petroleum generation, expulsion mechanisms of primary migration, thermal stability of crude oil, reaction kinetics of biomarker transformations, and thermal maturity indicators in sedimentary basins. Copyright ?? 1997 Elsevier Science Ltd.

A new EEMD-based scheme for detection of insect damaged wheat kernels using impact acoustics

USDA-ARS?s Scientific Manuscript database

Internally feeding insects inside wheat kernels cause significant, but unseen economic damage to stored grain. In this paper, a new scheme based on ensemble empirical mode decomposition (EEMD) using impact acoustics is proposed for detection of insect-damaged wheat kernels, based on its capability t...

Influence of climate change factors on carbon dynamics in northern forested peatlands

Treesearch

C.C Trettin; R. Laiho; K. Minkkinen; J. Laine

2005-01-01

Peatlands are carbon-accumulating wetland ecosystems, developed through an imbalance among organic matter production and decomposition processes. Soil saturation is the principal cause of anoxic conditions that constrain organic matter decay. Accordingly, changes in the hydrologic regime will affect the carbon (C) dynamics in forested peatlands. Our objective is to...

Landfill gases and some effects on vegetation

Treesearch

Franklin B. Flower; Ida A. Leone; Edward F. Gilman; John J. Arthur

1977-01-01

Gases moving from refuse landfills through soil were studied in New Jersey. The gases, products of anaerobic decomposition of organic matter in the refuse, caused injury and death of peach trees, ornamentals, and commercial farm crops, and create possible hazards to life and property because of the entrance of combustible gases into residences. Remedial measures are...

Environmental and health risks of chlorine trifluoride (ClF3), an alternative to potent greenhouse gases in the semiconductor industry.

PubMed

Tsai, Wen-Tien

2011-06-15

The first accident involving chlorine trifluoride (ClF(3)) in the history of semiconductor fabrication processes occurred on 28 July 2006 at Hsinchu (Taiwan), resulting in a large release of the highly reactive material and causing the chemical burn to several workers. ClF(3) is used primarily as an in situ cleaning gas in the manufacture of semiconductor silicon-wafer devices in replacement of perfluorocompounds (PFCs) because they have the high potential to contribute significantly to the global warming. This article aimed at reviewing ClF(3) in the physicochemical properties, the industrial uses, and the environmental implications on the basis of its toxicity, reactivity, health hazards and exposure limits. The health hazards of probable decomposition/hydrolysis products from ClF(3) were also evaluated based on their basic physicochemical properties and occupational exposure limits. The occupational exposure assessment was further discussed to understand potentially hazardous risks caused by hydrogen fluoride and fluorides from the decomposition/hydrolysis products of ClF(3). Copyright © 2010 Elsevier B.V. All rights reserved.

Do early life cognitive ability and self-regulation skills explain socio-economic inequalities in academic achievement? An effect decomposition analysis in UK and Australian cohorts.

PubMed

Pearce, Anna; Sawyer, Alyssa C P; Chittleborough, Catherine R; Mittinty, Murthy N; Law, Catherine; Lynch, John W

2016-09-01

Socio-economic inequalities in academic achievement emerge early in life and are observed across the globe. Cognitive ability and "non-cognitive" attributes (such as self-regulation) are the focus of many early years' interventions. Despite this, little research has compared the contributions of early cognitive and self-regulation abilities as separate pathways to inequalities in academic achievement. We examined this in two nationally representative cohorts in the UK (Millennium Cohort Study, n = 11,168; 61% original cohort) and Australia (LSAC, n = 3028; 59% original cohort). An effect decomposition method was used to examine the pathways from socio-economic disadvantage (in infancy) to two academic outcomes: 'low' maths and literacy scores (based on bottom quintile) at age 7-9 years. Risk ratios (RRs, and bootstrap 95% confidence intervals) were estimated with binary regression for each pathway of interest: the 'direct effect' of socio-economic disadvantage on academic achievement (not acting through self-regulation and cognitive ability in early childhood), and the 'indirect effects' of socio-economic disadvantage acting via self-regulation and cognitive ability (separately). Analyses were adjusted for baseline and intermediate confounding. Children from less advantaged families were up to twice as likely to be in the lowest quintile of maths and literacy scores. Around two-thirds of this elevated risk was 'direct' and the majority of the remainder was mediated by early cognitive ability and not self-regulation. For example in LSAC: the RR for the direct pathway from socio-economic disadvantage to poor maths scores was 1.46 (95% CI: 1.17-1.79). The indirect effect of socio-economic disadvantage through cognitive ability (RR = 1.13 [1.06-1.22]) was larger than the indirect effect through self-regulation (1.05 [1.01-1.11]). Similar patterns were observed for both outcomes and in both cohorts. Policies to alleviate social inequality (e.g. child poverty reduction) remain important for closing the academic achievement gap. Early interventions to improve cognitive ability (rather than self-regulation) also hold potential for reducing inequalities in children's academic outcomes. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Intramolecular fluorine migration via four-member cyclic transition states

PubMed

Nguyen; Mayer; Morton

2000-11-17

Gaseous CF(3)(+) interchanges F(+) for O with simple carbonyl compounds. CF(3)(+) reacts with propionaldehyde in the gas phase to produce (CH(3))(2)CF(+) via two competing pathways. Starting with 1-(13)C-propionaldehyde, the major pathway (80%) produces (CH(3))(2)CF(+) with the carbon label in one of the methyl groups. The minor pathway (20%) produces (CH(3))(2)CF(+) with the carbon label in the central position. The relative proportions of these two pathways are measured by (19)F NMR analysis of the neutral CH(3)CF=CH(2) produced by deprotonation of (CH(3))(2)CF(+) at <10(-)(3) Torr in an electron bombardment flow (EBFlow) reactor. Formation of alkene in which carbon is directly bonded to fluorine means that (in the minor product, at least) an F(+) for O transposition occurs via adduct formation followed by 1,3-atom transfer and then isomerization of CH(3)CH(2)CHF(+) to the more stable (CH(3))(2)CF(+). Use of CF(4) as a chemical ionization (CI) reagent gas leads to CF(3)(+) adduct ions for a variety of ketones, in addition to isoelectronic transposition of F(+) for O. Metastable ion decompositions of the adduct ions yield the metathesis products. Decompositions of fluorocycloalkyl cations formed in this manner give evidence for the same kinds of rearrangements as take place in CH(3)CH(2)CHF(+). Density functional calculations confirm that F(+) for O metathesis takes place via addition of CF(3)(+) to the carbonyl oxygen followed by transposition via a four-member cyclic transition state. A computational survey of the effects of different substituents in a series of aldehydes and acyclic ketones reveals no systematic variation of the energy of the transition state as a function of thermochemistry, but the Hammond postulate does appear to be obeyed in terms of progress along the reaction coordinate. Bond lengths corresponding to the central barrier correlate with overall thermochemistry of the F(+) for O interchange, but in a sense opposite to what might have been expected: the transition state becomes more product-like as the metathesis becomes increasingly exothermic. This reversal of the naive interpretation of the Hammond postulate is accounted for by the relative positions of the potential energy wells that precede and follow the central barrier.

Properties of Soil Pore Space Regulate Pathways of Plant Residue Decomposition and Community Structure of Associated Bacteria

PubMed Central

Negassa, Wakene C.; Guber, Andrey K.; Kravchenko, Alexandra N.; Marsh, Terence L.; Hildebrandt, Britton; Rivers, Mark L.

2015-01-01

Physical protection of soil carbon (C) is one of the important components of C storage. However, its exact mechanisms are still not sufficiently lucid. The goal of this study was to explore the influence of soil structure, that is, soil pore spatial arrangements, with and without presence of plant residue on (i) decomposition of added plant residue, (ii) CO2 emission from soil, and (iii) structure of soil bacterial communities. The study consisted of several soil incubation experiments with samples of contrasting pore characteristics with/without plant residue, accompanied by X-ray micro-tomographic analyses of soil pores and by microbial community analysis of amplified 16S–18S rRNA genes via pyrosequencing. We observed that in the samples with substantial presence of air-filled well-connected large (>30 µm) pores, 75–80% of the added plant residue was decomposed, cumulative CO2 emission constituted 1,200 µm C g-1 soil, and movement of C from decomposing plant residue into adjacent soil was insignificant. In the samples with greater abundance of water-filled small pores, 60% of the added plant residue was decomposed, cumulative CO2 emission constituted 2,000 µm C g-1 soil, and the movement of residue C into adjacent soil was substantial. In the absence of plant residue the influence of pore characteristics on CO2 emission, that is on decomposition of the native soil organic C, was negligible. The microbial communities on the plant residue in the samples with large pores had more microbial groups known to be cellulose decomposers, that is, Bacteroidetes, Proteobacteria, Actinobacteria, and Firmicutes, while a number of oligotrophic Acidobacteria groups were more abundant on the plant residue from the samples with small pores. This study provides the first experimental evidence that characteristics of soil pores and their air/water flow status determine the phylogenetic composition of the local microbial community and directions and magnitudes of soil C decomposition processes. PMID:25909444

Properties of soil pore space regulate pathways of plant residue decomposition and community structure of associated bacteria

DOE PAGES

Negassa, Wakene C.; Guber, Andrey K.; Kravchenko, Alexandra N.; ...

2015-07-01

Physical protection of soil carbon (C) is one of the important components of C storage. However, its exact mechanisms are still not sufficiently lucid. The goal of this study was to explore the influence of soil structure, that is, soil pore spatial arrangements, with and without presence of plant residue on (i) decomposition of added plant residue, (ii) CO₂ emission from soil, and (iii) structure of soil bacterial communities. The study consisted of several soil incubation experiments with samples of contrasting pore characteristics with/without plant residue, accompanied by X-ray micro-tomographic analyses of soil pores and by microbial community analysis ofmore » amplified 16S–18S rRNA genes via pyrosequencing. We observed that in the samples with substantial presence of air-filled well-connected large (>30 µm) pores, 75–80% of the added plant residue was decomposed, cumulative CO₂ emission constituted 1,200 µm C g⁻¹ soil, and movement of C from decomposing plant residue into adjacent soil was insignificant. In the samples with greater abundance of water-filled small pores, 60% of the added plant residue was decomposed, cumulative CO₂ emission constituted 2,000 µm C g⁻¹ soil, and the movement of residue C into adjacent soil was substantial. In the absence of plant residue the influence of pore characteristics on CO₂ emission, that is on decomposition of the native soil organic C, was negligible. The microbial communities on the plant residue in the samples with large pores had more microbial groups known to be cellulose decomposers, that is, Bacteroidetes, Proteobacteria, Actinobacteria, and Firmicutes, while a number of oligotrophic Acidobacteria groups were more abundant on the plant residue from the samples with small pores. This study provides the first experimental evidence that characteristics of soil pores and their air/water flow status determine the phylogenetic composition of the local microbial community and directions and magnitudes of soil C decomposition processes.« less

Properties of soil pore space regulate pathways of plant residue decomposition and community structure of associated bacteria.

PubMed

Negassa, Wakene C; Guber, Andrey K; Kravchenko, Alexandra N; Marsh, Terence L; Hildebrandt, Britton; Rivers, Mark L

2015-01-01

Physical protection of soil carbon (C) is one of the important components of C storage. However, its exact mechanisms are still not sufficiently lucid. The goal of this study was to explore the influence of soil structure, that is, soil pore spatial arrangements, with and without presence of plant residue on (i) decomposition of added plant residue, (ii) CO2 emission from soil, and (iii) structure of soil bacterial communities. The study consisted of several soil incubation experiments with samples of contrasting pore characteristics with/without plant residue, accompanied by X-ray micro-tomographic analyses of soil pores and by microbial community analysis of amplified 16S-18S rRNA genes via pyrosequencing. We observed that in the samples with substantial presence of air-filled well-connected large (>30 µm) pores, 75-80% of the added plant residue was decomposed, cumulative CO2 emission constituted 1,200 µm C g(-1) soil, and movement of C from decomposing plant residue into adjacent soil was insignificant. In the samples with greater abundance of water-filled small pores, 60% of the added plant residue was decomposed, cumulative CO2 emission constituted 2,000 µm C g(-1) soil, and the movement of residue C into adjacent soil was substantial. In the absence of plant residue the influence of pore characteristics on CO2 emission, that is on decomposition of the native soil organic C, was negligible. The microbial communities on the plant residue in the samples with large pores had more microbial groups known to be cellulose decomposers, that is, Bacteroidetes, Proteobacteria, Actinobacteria, and Firmicutes, while a number of oligotrophic Acidobacteria groups were more abundant on the plant residue from the samples with small pores. This study provides the first experimental evidence that characteristics of soil pores and their air/water flow status determine the phylogenetic composition of the local microbial community and directions and magnitudes of soil C decomposition processes.

Properties of soil pore space regulate pathways of plant residue decomposition and community structure of associated bacteria

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

Negassa, Wakene C.; Guber, Andrey K.; Kravchenko, Alexandra N.

Physical protection of soil carbon (C) is one of the important components of C storage. However, its exact mechanisms are still not sufficiently lucid. The goal of this study was to explore the influence of soil structure, that is, soil pore spatial arrangements, with and without presence of plant residue on (i) decomposition of added plant residue, (ii) CO₂ emission from soil, and (iii) structure of soil bacterial communities. The study consisted of several soil incubation experiments with samples of contrasting pore characteristics with/without plant residue, accompanied by X-ray micro-tomographic analyses of soil pores and by microbial community analysis ofmore » amplified 16S–18S rRNA genes via pyrosequencing. We observed that in the samples with substantial presence of air-filled well-connected large (>30 µm) pores, 75–80% of the added plant residue was decomposed, cumulative CO₂ emission constituted 1,200 µm C g⁻¹ soil, and movement of C from decomposing plant residue into adjacent soil was insignificant. In the samples with greater abundance of water-filled small pores, 60% of the added plant residue was decomposed, cumulative CO₂ emission constituted 2,000 µm C g⁻¹ soil, and the movement of residue C into adjacent soil was substantial. In the absence of plant residue the influence of pore characteristics on CO₂ emission, that is on decomposition of the native soil organic C, was negligible. The microbial communities on the plant residue in the samples with large pores had more microbial groups known to be cellulose decomposers, that is, Bacteroidetes, Proteobacteria, Actinobacteria, and Firmicutes, while a number of oligotrophic Acidobacteria groups were more abundant on the plant residue from the samples with small pores. This study provides the first experimental evidence that characteristics of soil pores and their air/water flow status determine the phylogenetic composition of the local microbial community and directions and magnitudes of soil C decomposition processes.« less

Using the Binary Phase-Field Crystal Model to Describe Non-Classical Nucleation Pathways in Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Smith, Nathan; Provatas, Nikolas

Recent experimental work has shown that gold nanoparticles can precipitate from an aqueous solution through a non-classical, multi-step nucleation process. This multi-step process begins with spinodal decomposition into solute-rich and solute-poor liquid domains followed by nucleation from within the solute-rich domains. We present a binary phase-field crystal theory that shows the same phenomology and examine various cross-over regimes in the growth and coarsening of liquid and solid domains. We'd like to the thank Canada Research Chairs (CRC) program for funding this work.

Spatial variation in below ground carbon cycling in a pristine peatland, driven by present and past vegetation

NASA Astrophysics Data System (ADS)

Mathijssen, Paul; Knorr, Klaus-Holger; Gałka, Mariusz; Borken, Werner

2017-04-01

Peat carbon cycling is controlled by both large scale factors, such as climate and hydrological setting, and small scale factors, such as microtopography, vegetation, litter quality, and rooting depth. These small scale factors commonly vary within peatlands, causing variation in the carbon balance at different locations within the same site. Understanding the relationship between small scale carbon cycling and vegetation helps us to assess the variation of carbon dynamics of peatlands, because vegetation composition acts as an integrator of factors such as microtopography, hydrology, and nutrient level. Variation in vegetation illustrates spatial variation of these underlying factors. Furthermore, the presence of certain plant species affects carbon cycling directly through litter quality or aeration through root tissues. In order to understand these within-site variations in terms of carbon cycling, we investigated carbon accumulation, decomposition, and biogeochemistry of pore waters along a transect of peat cores with changing vegetation and water levels in an ombrotrophic peatland in southern Patagonia. The transect ran from a Sphagnum magellanicum dominated spot with relatively high water table, to intermediately wet spots with mixed Sphagnum/shrubs vegetation, or dominated by Cyperaceae, eventually to a more elevated and drier spot dominated by cushion plants (mainly Astelia pumila). There were large differences in peat accumulation rates and peat densities, with faster peat growth and lower densities under Sphagnum, but overall carbon accumulation rates were quite similar in the various microenvironments. At most plots C/N ratios decreased with depth, concurrent with increasing humification index derived from FT-IR spectra. But under cushion plants this relation was opposite: more humification with depth, but also C/N ratios increases. This reflected the differing source material at depth under the cushion plants, and that the cushion plant peat layers were formed on top of Sphagnum peat. The divergent source material throughout a peat core makes it difficult to use C/N ratios to indicate peat decomposition rates. Although the low peat density and higher C/N ratios indicate that overall carbon turnover is slow at Sphagnum plots, pore water methane concentrations were elevated. At cushion plant plots, however, higher redox potentials exist until greater depths due to aerenchymous roots, inhibiting methane production and release. Our results demonstrate that large variation exists within pristine bogs, in terms of decomposition patterns, organic matter quality, and carbon turnover pathways, corresponding to variation in surface moisture levels and vegetation. Furthermore, variation in carbon cycling properties are maintained in buried peat layers and reflect more the organic material of that layer, than the current surface carbon dynamics.

Modeling of Laser Material Interactions

NASA Astrophysics Data System (ADS)

Garrison, Barbara

2009-03-01

Irradiation of a substrate by laser light initiates the complex chemical and physical process of ablation where large amounts of material are removed. Ablation has been successfully used in techniques such as nanolithography and LASIK surgery, however a fundamental understanding of the process is necessary in order to further optimize and develop applications. To accurately describe the ablation phenomenon, a model must take into account the multitude of events which occur when a laser irradiates a target including electronic excitation, bond cleavage, desorption of small molecules, ongoing chemical reactions, propagation of stress waves, and bulk ejection of material. A coarse grained molecular dynamics (MD) protocol with an embedded Monte Carlo (MC) scheme has been developed which effectively addresses each of these events during the simulation. Using the simulation technique, thermal and chemical excitation channels are separately studied with a model polymethyl methacrylate system. The effects of the irradiation parameters and reaction pathways on the process dynamics are investigated. The mechanism of ablation for thermal processes is governed by a critical number of bond breaks following the deposition of energy. For the case where an absorbed photon directly causes a bond scission, ablation occurs following the rapid chemical decomposition of material. The study provides insight into the influence of thermal and chemical processes in polymethyl methacrylate and facilitates greater understanding of the complex nature of polymer ablation.

¹H NMR-based metabolic profiling of naproxen-induced toxicity in rats.

PubMed

Jung, Jeeyoun; Park, Minhwa; Park, Hye Jin; Shim, Sun Bo; Cho, Yang Ha; Kim, Jinho; Lee, Ho-Sub; Ryu, Do Hyun; Choi, Donwoong; Hwang, Geum-Sook

2011-01-15

The dose-dependent perturbations in urinary metabolite concentrations caused by naproxen toxicity were investigated using ¹H NMR spectroscopy coupled with multivariate statistical analysis. Histopathologic evaluation of naproxen-induced acute gastrointestinal damage in rats demonstrated a significant dose-dependent effect. Furthermore, principal component analysis (PCA) of ¹H NMR from rat urine revealed a dose-dependent metabolic shift between the vehicle-treated control rats and rats treated with low-dose (10 mg/kg body weight), moderate-dose (50 mg/kg), and high-dose (100 mg/kg) naproxen, coinciding with their gastric damage scores after naproxen administration. The resultant metabolic profiles demonstrate that the naproxen-induced gastric damage exhibited energy metabolism perturbations that elevated their urinary levels of citrate, cis-aconitate, creatine, and creatine phosphate. In addition, naproxen administration decreased choline level and increased betaine level, indicating that it depleted the main protective constituent of the gastric mucosa. Moreover, naproxen stimulated the decomposition of tryptophan into kynurenate, which inhibits fibroblast growth factor-1 and delays ulcer healing. These findings demonstrate that ¹H NMR-based urinary metabolic profiling can facilitate noninvasive and rapid diagnosis of drug side effects and is suitable for elucidating possible biological pathways perturbed by drug toxicity. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

IR femtochemistry on the surface of wide-gap ionic crystals

NASA Astrophysics Data System (ADS)

Laptev, V. B.; Chekalin, S. V.; Dorofeyev, I. A.; Kompanets, V. O.; Pigulsky, S. V.; Ryabov, E. A.

2018-02-01

We have found and studied a phenomenon of the growth of films resulting from decomposition of some organic and silicon-containing molecules adsorbed on the surface of ionic crystals under the action of IR (1.4-5.4 µm) femtosecond radiation of a moderate intensity, ~1011 W cm-2. In the gas phase, these molecules do not decompose. Microstructured films consisting of amorphous carbon, graphite oxide, and silicon dioxide have been obtained. The formation of carbon films was accompanied by the appearance of different hydrocarbons in the gas phase. The extensive films of graphite oxide have been obtained. The decomposition of molecules on the surface is apparently caused by non-resonant ionization and subsequent deep fragmentation. The mechanisms of ionization at relatively low intensities of the femtosecond IR radiation have been discussed.

Shock chemistry in SX358 foams

NASA Astrophysics Data System (ADS)

Maerzke, Katie; Coe, Joshua; Fredenburg, Anthony; Lang, John; Dattelbaum, Dana

2017-06-01

We have developed new equation of state models for SX358, a cross-linked PDMS polymer. Recent experiments on SX358 over a range of initial densities (0-65% porous) have yielded new data that allow for a more thorough calibration of the equations of state. SX358 chemically decomposes under shock compression, as evidenced by a cusp in the shock locus. We therefore treat this material using two equations of state, specifically a SESAME model for the unreacted material and a free energy minimization assuming full chemical and thermodynamic equilibrium for the decomposition products. The shock locus of porous SX358 is found to be ``anomalous'' in that the decomposition reaction causes a volume expansion, rather than a volume collapse. Similar behavior has been observed in other polymer foams, notably polyurethane.

Filtration of human EEG recordings from physiological artifacts with empirical mode method

NASA Astrophysics Data System (ADS)

Grubov, Vadim V.; Runnova, Anastasiya E.; Khramova, Marina V.

2017-03-01

In the paper we propose the new method for dealing with noise and physiological artifacts in experimental human EEG recordings. The method is based on analysis of EEG signals with empirical mode decomposition (Hilbert-Huang transform). We consider noises and physiological artifacts on EEG as specific oscillatory patterns that cause problems during EEG analysis and can be detected with additional signals recorded simultaneously with EEG (ECG, EMG, EOG, etc.) We introduce the algorithm of the method with following steps: empirical mode decomposition of EEG signal, choosing of empirical modes with artifacts, removing empirical modes with artifacts, reconstruction of the initial EEG signal. We test the method on filtration of experimental human EEG signals from eye-moving artifacts and show high efficiency of the method.

Response of SOM Decomposition to Anthropogenic N Deposition: Simulations From the PnET-SOM Model.

NASA Astrophysics Data System (ADS)

Tonitto, C.; Goodale, C. L.; Ollinger, S. V.; Jenkins, J. P.

2008-12-01

Anthropogenic forcing of the C and N cycles has caused rapid change in atmospheric CO2 and N deposition, with complex and uncertain effects on forest C and N balance. With some exceptions, models of forest ecosystem response to anthropogenic perturbation have historically focused more on aboveground than belowground processes; the complexity of soil organic matter (SOM) is often represented with abstract or incomplete SOM pools, and remains difficult to quantify. We developed a model of SOM dynamics in northern hardwood forests with explicit feedbacks between C and N cycles. The soil model is linked to the aboveground dynamics of the PnET model to form PnET-SOM. The SOM model includes: 1) physically measurable SOM pools, including humic and mineral-associated SOM in O, A, and B soil horizons, 2) empirical soil turnover times based on 14C data, 3) alternative SOM decomposition algorithms with and without explicit microbial processing, and 4) soluble element transport explicitly linked to the hydrologic cycle. We tested model sensitivity to changes in litter decomposition rate (k) and completeness of decomposition (limit value) by altering these parameters based on experimental observations from long-term litter decomposition experiments with N fertilization treatments. After a 100 year simulation, the Oe+Oa horizon SOC pool was reduced by 15 % and the A-horizon humified SOC was reduced by 7 % for N deposition scenarios relative to forests without N fertilization. In contrast, predictions for slower time-scale pools showed negligible variation in response to variation in the limit values tested, with A-horizon mineral SOC pools reduced by < 3 % and B-horizon mineral SOC reduced by 0.1 % for N deposition scenarios relative to forests without N fertilization. The model was also used to test the effect of varying initial litter decomposition rate to simulate response to N deposition. In contrast to the effect of varying limit values, simulations in which only k-values were varied did not drastically alter the predicted SOC pool distribution throughout the soil profile, but did significantly alter the Oi SOC pool. These results suggest that describing soil response to N deposition via alteration of the limit value alone, or as a combined alteration of limit value and the initial decomposition rate, can lead to significant variation in predicted long-term C storage.

"Self-preservation" of CO(2) gas hydrates--surface microstructure and ice perfection.

PubMed

Falenty, Andrzej; Kuhs, Werner F

2009-12-10

Gas hydrates can exhibit an anomalously slow decomposition outside their thermodynamic stability field; the phenomenon is called "self-preservation" and is mostly studied at ambient pressure and at temperatures between approximately 240 K and the melting point of ice. Here, we present a combination of in situ neutron diffraction studies, pVT work, and ex situ scanning electron microscopy (SEM) on CO(2) clathrates covering a much broader p-T field, stretching from 200 to 270 K and pressures between the hydrate stability limit and 0.6 kPa (6 mbar), a pressure far outside stability. The self-preservation regime above 240 K is confirmed over a broad pressure range and appears to be caused by the annealing of an ice cover formed in the initial hydrate decomposition. Another, previously unknown regime of the self-preservation exists below this temperature, extending however only over a rather narrow pressure range. In this case, the initial ice microstructure is dominated by a fast two-dimensional growth covering rapidly the clathrate surface. All observations lend strong support to the idea that the phenomenon of self-preservation is linked to the permeability of the ice cover governed by (1) the initial microstructure of ice and/or (2) the subsequent annealing of this ice coating. The interplay of the microstructure of newly formed ice and its annealing with the ongoing decomposition reaction leads to various decomposition paths and under certain conditions to a very pronounced preservation anomaly.

Decomposition analysis of water footprint changes in a water-limited river basin: a case study of the Haihe River basin, China

NASA Astrophysics Data System (ADS)

Zhi, Y.; Yang, Z. F.; Yin, X. A.

2014-05-01

Decomposition analysis of water footprint (WF) changes, or assessing the changes in WF and identifying the contributions of factors leading to the changes, is important to water resource management. Instead of focusing on WF from the perspective of administrative regions, we built a framework in which the input-output (IO) model, the structural decomposition analysis (SDA) model and the generating regional IO tables (GRIT) method are combined to implement decomposition analysis for WF in a river basin. This framework is illustrated in the WF in Haihe River basin (HRB) from 2002 to 2007, which is a typical water-limited river basin. It shows that the total WF in the HRB increased from 4.3 × 1010 m3 in 2002 to 5.6 × 1010 m3 in 2007, and the agriculture sector makes the dominant contribution to the increase. Both the WF of domestic products (internal) and the WF of imported products (external) increased, and the proportion of external WF rose from 29.1 to 34.4%. The technological effect was the dominant contributor to offsetting the increase of WF. However, the growth of WF caused by the economic structural effect and the scale effect was greater, so the total WF increased. This study provides insights about water challenges in the HRB and proposes possible strategies for the future, and serves as a reference for WF management and policy-making in other water-limited river basins.

Rortex—A new vortex vector definition and vorticity tensor and vector decompositions

NASA Astrophysics Data System (ADS)

Liu, Chaoqun; Gao, Yisheng; Tian, Shuling; Dong, Xiangrui

2018-03-01

A vortex is intuitively recognized as the rotational/swirling motion of the fluids. However, an unambiguous and universally accepted definition for vortex is yet to be achieved in the field of fluid mechanics, which is probably one of the major obstacles causing considerable confusions and misunderstandings in turbulence research. In our previous work, a new vector quantity that is called vortex vector was proposed to accurately describe the local fluid rotation and clearly display vortical structures. In this paper, the definition of the vortex vector, named Rortex here, is revisited from the mathematical perspective. The existence of the possible rotational axis is proved through real Schur decomposition. Based on real Schur decomposition, a fast algorithm for calculating Rortex is also presented. In addition, new vorticity tensor and vector decompositions are introduced: the vorticity tensor is decomposed to a rigidly rotational part and a non-rotationally anti-symmetric part, and the vorticity vector is decomposed to a rigidly rotational vector which is called the Rortex vector and a non-rotational vector which is called the shear vector. Several cases, including the 2D Couette flow, 2D rigid rotational flow, and 3D boundary layer transition on a flat plate, are studied to demonstrate the justification of the definition of Rortex. It can be observed that Rortex identifies both the precise swirling strength and the rotational axis, and thus it can reasonably represent the local fluid rotation and provide a new powerful tool for vortex dynamics and turbulence research.

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

DOE PAGES

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.; ...

2016-02-02

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Modular architecture of protein structures and allosteric communications: potential implications for signaling proteins and regulatory linkages

PubMed Central

del Sol, Antonio; Araúzo-Bravo, Marcos J; Amoros, Dolors; Nussinov, Ruth

2007-01-01

Background Allosteric communications are vital for cellular signaling. Here we explore a relationship between protein architectural organization and shortcuts in signaling pathways. Results We show that protein domains consist of modules interconnected by residues that mediate signaling through the shortest pathways. These mediating residues tend to be located at the inter-modular boundaries, which are more rigid and display a larger number of long-range interactions than intra-modular regions. The inter-modular boundaries contain most of the residues centrally conserved in the protein fold, which may be crucial for information transfer between amino acids. Our approach to modular decomposition relies on a representation of protein structures as residue-interacting networks, and removal of the most central residue contacts, which are assumed to be crucial for allosteric communications. The modular decomposition of 100 multi-domain protein structures indicates that modules constitute the building blocks of domains. The analysis of 13 allosteric proteins revealed that modules characterize experimentally identified functional regions. Based on the study of an additional functionally annotated dataset of 115 proteins, we propose that high-modularity modules include functional sites and are the basic functional units. We provide examples (the Gαs subunit and P450 cytochromes) to illustrate that the modular architecture of active sites is linked to their functional specialization. Conclusion Our method decomposes protein structures into modules, allowing the study of signal transmission between functional sites. A modular configuration might be advantageous: it allows signaling proteins to expand their regulatory linkages and may elicit a broader range of control mechanisms either via modular combinations or through modulation of inter-modular linkages. PMID:17531094

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

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

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li2S Film Formation on Lithium Anode Surface of Li-S batteries.

PubMed

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B; Mukherjee, Partha P

2016-02-01

The precipitation of lithium sulfide (Li2S) on the Li metal anode surface adversely impacts the performance of lithium-sulfur (Li-S) batteries. In this study, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li2S/Li metal surface interactions and the nucleation and growth of a Li2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms and Li atoms from the anode surface. Reaction pathways of the Li2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li2S (111) plane forms on a Li(110) surface and a perfect Li2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li2S film formation on the Li anode surface is thermodynamically favorable. The calculated difference charge density of the Li2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li2S formation via decomposition of Li2S8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.

Causal mediation analysis with multiple mediators.

PubMed

Daniel, R M; De Stavola, B L; Cousens, S N; Vansteelandt, S

2015-03-01

In diverse fields of empirical research-including many in the biological sciences-attempts are made to decompose the effect of an exposure on an outcome into its effects via a number of different pathways. For example, we may wish to separate the effect of heavy alcohol consumption on systolic blood pressure (SBP) into effects via body mass index (BMI), via gamma-glutamyl transpeptidase (GGT), and via other pathways. Much progress has been made, mainly due to contributions from the field of causal inference, in understanding the precise nature of statistical estimands that capture such intuitive effects, the assumptions under which they can be identified, and statistical methods for doing so. These contributions have focused almost entirely on settings with a single mediator, or a set of mediators considered en bloc; in many applications, however, researchers attempt a much more ambitious decomposition into numerous path-specific effects through many mediators. In this article, we give counterfactual definitions of such path-specific estimands in settings with multiple mediators, when earlier mediators may affect later ones, showing that there are many ways in which decomposition can be done. We discuss the strong assumptions under which the effects are identified, suggesting a sensitivity analysis approach when a particular subset of the assumptions cannot be justified. These ideas are illustrated using data on alcohol consumption, SBP, BMI, and GGT from the Izhevsk Family Study. We aim to bridge the gap from "single mediator theory" to "multiple mediator practice," highlighting the ambitious nature of this endeavor and giving practical suggestions on how to proceed. © 2014 The Authors Biometrics published by Wiley Periodicals, Inc. on behalf of International Biometric Society.

The role of bicarbonate anions in methotrexate degradation via UV/TiO2: Mechanisms, reactivity and increased toxicity.

PubMed

Lai, Webber Wei-Po; Hsu, Ming-Hao; Lin, Angela Yu-Chen

2017-04-01

Bicarbonate anion (HCO 3 - ) is a major constituent in wastewater and natural water matrices, and the aim of this study was to investigate its roles in the degradation of the antineoplastic agent methotrexate via UV/TiO 2 . A comprehensive investigation of reaction mechanisms was performed by conducting scavenger experiments and substructure reactivity and Microtox ® toxicity tests. In the presence of HCO 3 - , the methotrexate degradation rate substantially increased, indicating the involvement of CO 3 - . The estimated second-order rate constants of methotrexate with CO 3 - and OH were 1.4 × 10 7  M -1  s -1 and 8.7 × 10 9  M -1  s -1 , respectively. Both the valence hole (h vb + ) and OH resulted in the generation of CO 3 - . Initial transformation pathways of methotrexate were proposed, including the addition of atomic oxygen, hydroxylation, deamination, CC cleavage and CN cleavage. CN cleavage at the aniline moiety (the N(13) position) is the primary decomposition pathway, leading to an aminopterin yield of 43%. CO 3 - preferentially reacted with the 4-aminobenzamide (ABZ) moiety and generated toxic byproducts during the later stages of decomposition, which was not observed in the UV/TiO 2 system. The reactivity of the three methotrexate substructures decreased in the following order in the presence of HCO 3 - : ABZ ≫ DHP ≫ LG∼0; however, without HCO 3 - , the following order was observed: ABZ ∼ DHP > LG. The results of this work suggest that the increase in toxicity induced by the presence of HCO 3 - likely occurs in many other OH-based advanced oxidation processes in wastewater containing pharmaceutical cocktails with ABZ moieties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quantitation of NAD+ biosynthesis from the salvage pathway in Saccharomyces cerevisiae

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

Sporty, J; Lin, S; Kato, M

2009-02-18

Nicotinamide adenine dinucleotide (NAD{sup +}) is synthesized via two major pathways in prokaryotic and eukaryotic systems: the de novo biosynthesis pathway from tryptophan precursors, or by the salvage biosynthesis pathway from either extracellular nicotinic acid or various intracellular NAD{sup +} decomposition products. NAD{sup +} biosynthesis via the salvage pathway has been linked to an increase in yeast replicative lifespan under calorie restriction (CR). However, the relative contribution of each pathway to NAD{sup +} biosynthesis under both normal and CR conditions is not known. Here, we have performed lifespan, NAD{sup +} and NADH (the reduced form of NAD{sup +}) analyses onmore » BY4742 wild type, NAD+ salvage pathway knockout (npt1{Delta}), and NAD+ de novo pathway knockout (qpt1{Delta}) yeast strains cultured in media containing either 2% glucose (normal growth) or 0.5% glucose (CR). We have utilized {sup 14}C labeled nicotinic acid in the culture media combined with HPLC speciation and both UV and {sup 14}C detection to quantitate the total amounts of NAD{sup +} and NADH and the amounts derived from the salvage pathway. We observe that wild type and qpt1{Delta} yeast exclusively utilize extracellular nicotinic acid for NAD{sup +} and NADH biosynthesis under both the 2% and 0.5% glucose growth conditions suggesting that the de novo pathway plays little role if a functional salvage pathway is present. We also observe that NAD{sup +} concentrations decrease in all three strains under CR. However, unlike the wild type strain, NADH concentrations do not decrease and NAD{sup +}:NADH ratios do not increase under CR for either knockout strain. Lifespan analyses reveal that CR results in a lifespan increase of approximately 25% for the wild type and qpt1{Delta} strains, while no increase in lifespan is observed for the npt1{Delta} strain. In combination these data suggest that having a functional salvage pathway is more important than the absolute levels of NAD{sup +} or NADH for lifespan extension under CR.« less

Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen Storage Composite.

PubMed

Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

2017-09-20

The lightweight compound material NaNH 2 -NaBH 4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH 2 -NaBH 4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H 2 , NH 3 , B 2 H 6 , and N 2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B 6 H 12 also exists. The TG/DTA analyses show that the composite NaNH 2 -NaBH 4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na 3 (NH 2 ) 2 BH 4 hydride decomposes into Na 3 BN 2 and H 2 (200-350 °C); (2) remaining Na 3 (NH 2 ) 2 BH 4 reacts with NaBH 4 and Na 3 BN 2 , generating Na, BN, NH 3 , N 2 , and H 2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

Riparian plant litter quality increases with latitude.

PubMed

Boyero, Luz; Graça, Manuel A S; Tonin, Alan M; Pérez, Javier; J Swafford, Andrew; Ferreira, Verónica; Landeira-Dabarca, Andrea; A Alexandrou, Markos; Gessner, Mark O; McKie, Brendan G; Albariño, Ricardo J; Barmuta, Leon A; Callisto, Marcos; Chará, Julián; Chauvet, Eric; Colón-Gaud, Checo; Dudgeon, David; Encalada, Andrea C; Figueroa, Ricardo; Flecker, Alexander S; Fleituch, Tadeusz; Frainer, André; Gonçalves, José F; Helson, Julie E; Iwata, Tomoya; Mathooko, Jude; M'Erimba, Charles; Pringle, Catherine M; Ramírez, Alonso; Swan, Christopher M; Yule, Catherine M; Pearson, Richard G

2017-09-05

Plant litter represents a major basal resource in streams, where its decomposition is partly regulated by litter traits. Litter-trait variation may determine the latitudinal gradient in decomposition in streams, which is mainly microbial in the tropics and detritivore-mediated at high latitudes. However, this hypothesis remains untested, as we lack information on large-scale trait variation for riparian litter. Variation cannot easily be inferred from existing leaf-trait databases, since nutrient resorption can cause traits of litter and green leaves to diverge. Here we present the first global-scale assessment of riparian litter quality by determining latitudinal variation (spanning 107°) in litter traits (nutrient concentrations; physical and chemical defences) of 151 species from 24 regions and their relationships with environmental factors and phylogeny. We hypothesized that litter quality would increase with latitude (despite variation within regions) and traits would be correlated to produce 'syndromes' resulting from phylogeny and environmental variation. We found lower litter quality and higher nitrogen:phosphorus ratios in the tropics. Traits were linked but showed no phylogenetic signal, suggesting that syndromes were environmentally determined. Poorer litter quality and greater phosphorus limitation towards the equator may restrict detritivore-mediated decomposition, contributing to the predominance of microbial decomposers in tropical streams.

Application of Mortar Coupling in Multiscale Modelling of Coupled Flow, Transport, and Biofilm Growth in Porous Media

NASA Astrophysics Data System (ADS)

Laleian, A.; Valocchi, A. J.; Werth, C. J.

2017-12-01

Multiscale models of reactive transport in porous media are capable of capturing complex pore-scale processes while leveraging the efficiency of continuum-scale models. In particular, porosity changes caused by biofilm development yield complex feedbacks between transport and reaction that are difficult to quantify at the continuum scale. Pore-scale models, needed to accurately resolve these dynamics, are often impractical for applications due to their computational cost. To address this challenge, we are developing a multiscale model of biofilm growth in which non-overlapping regions at pore and continuum spatial scales are coupled with a mortar method providing continuity at interfaces. We explore two decompositions of coupled pore-scale and continuum-scale regions to study biofilm growth in a transverse mixing zone. In the first decomposition, all reaction is confined to a pore-scale region extending the transverse mixing zone length. Only solute transport occurs in the surrounding continuum-scale regions. Relative to a fully pore-scale result, we find the multiscale model with this decomposition has a reduced run time and consistent result in terms of biofilm growth and solute utilization. In the second decomposition, reaction occurs in both an up-gradient pore-scale region and a down-gradient continuum-scale region. To quantify clogging, the continuum-scale model implements empirical relations between porosity and continuum-scale parameters, such as permeability and the transverse dispersion coefficient. Solutes are sufficiently mixed at the end of the pore-scale region, such that the initial reaction rate is accurately computed using averaged concentrations in the continuum-scale region. Relative to a fully pore-scale result, we find accuracy of biomass growth in the multiscale model with this decomposition improves as the interface between pore-scale and continuum-scale regions moves downgradient where transverse mixing is more fully developed. Also, this decomposition poses additional challenges with respect to mortar coupling. We explore these challenges and potential solutions. While recent work has demonstrated growing interest in multiscale models, further development is needed for their application to field-scale subsurface contaminant transport and remediation.

Response of anaerobic carbon cycling to water table manipulation in an Alaskan rich fen

USGS Publications Warehouse

Kane, E.S.; Chivers, M.R.; Turetsky, M.R.; Treat, C.C.; Petersen, D.G.; Waldrop, M.; Harden, J.W.; McGuire, A.D.

2013-01-01

To test the effects of altered hydrology on organic soil decomposition, we investigated CO2 and CH4 production potential of rich-fen peat (mean surface pH = 6.3) collected from a field water table manipulation experiment including control, raised and lowered water table treatments. Mean anaerobic CO2 production potential at 10 cm depth (14.1 ± 0.9 μmol C g−1 d−1) was as high as aerobic CO2 production potential (10.6 ± 1.5 μmol C g−1 d−1), while CH4 production was low (mean of 7.8 ± 1.5 nmol C g−1 d−1). Denitrification enzyme activity indicated a very high denitrification potential (197 ± 23 μg N g−1 d−1), but net NO-3 reduction suggested this was a relatively minor pathway for anaerobic CO2 production. Abundances of denitrifier genes (nirK and nosZ) did not change across water table treatments. SO2-4 reduction also did not appear to be an important pathway for anaerobic CO2 production. The net accumulation of acetate and formate as decomposition end products in the raised water table treatment suggested that fermentation was a significant pathway for carbon mineralization, even in the presence of NO-3. Dissolved organic carbon (DOC) concentrations were the strongest predictors of potential anaerobic and aerobic CO2 production. Across all water table treatments, the CO2:CH4 ratio increased with initial DOC leachate concentrations. While the field water table treatment did not have a significant effect on mean CO2 or CH4 production potential, the CO2:CH4 ratio was highest in shallow peat incubations from the drained treatment. These data suggest that with continued drying or with a more variable water table, anaerobic CO2 production may be favored over CH4 production in this rich fen. Future research examining the potential for dissolved organic substances to facilitate anaerobic respiration, or alternative redox processes that limit the effectiveness of organic acids as substrates in anaerobic metabolism, would help explain additional uncertainty concerning carbon mineralization in this system.

ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

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

Ketusky, E.; Subramanian, K.

At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include:more » (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H area modified Purex = high Al/Fe concentration) after nearing dissolution equilibrium, and then decomposed to {le} 100 Parts per Million (ppm) oxalate. Since AOP technology largely originated on using ultraviolet (UV) light as a primary catalyst, decomposition of the spent oxalic acid, well exposed to a medium pressure mercury vapor light was considered the benchmark. However, with multi-valent metals already contained in the feed, and maintenance of the UV light a concern; testing was conducted to evaluate the impact from removing the UV light. Using current AOP terminology, the test without the UV light would likely be considered an ozone based, dark, ferrioxalate type, decomposition process. Specifically, as part of the testing, the impacts from the following were investigated: (1) Importance of the UV light on the decomposition rates when decomposing 1 wt% spent oxalic acid; (2) Impact of increasing the oxalic acid strength from 1 to 2.5 wt% on the decomposition rates; and (3) For F-area testing, the advantage of increasing the spent oxalic acid flowrate from 40 L/min (liters/minute) to 50 L/min during decomposition of the 2.5 wt% spent oxalic acid. The results showed that removal of the UV light (from 1 wt% testing) slowed the decomposition rates in both the F & H testing. Specifically, for F-Area Strike 1, the time increased from about 6 hours to 8 hours. In H-Area, the impact was not as significant, with the time required for Strike 1 to be decomposed to less than 100 ppm increasing slightly, from 5.4 to 6.4 hours. For the spent 2.5 wt% oxalic acid decomposition tests (all) without the UV light, the F-area decompositions required approx. 10 to 13 hours, while the corresponding required H-Area decompositions times ranged from 10 to 21 hours. For the 2.5 wt% F-Area sludge, the increased availability of iron likely caused the increased decomposition rates compared to the 1 wt% oxalic acid based tests. In addition, for the F-testing, increasing the recirculation flow rates from 40 liter/minute to 50 liter/minute resulted in an increased decomposition rate, suggesting a better use of ozone.« less

Non-Enzymatic Decomposition of Collagen Fibers by a Biglycan Antibody and a Plausible Mechanism for Rheumatoid Arthritis

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

Antipova, Olga; Orgel, Joseph P.R.O.

Rheumatoid arthritis (RA) is a systemic autoimmune inflammatory and destructive joint disorder that affects tens of millions of people worldwide. Normal healthy joints maintain a balance between the synthesis of extracellular matrix (ECM) molecules and the proteolytic degradation of damaged ones. In the case of RA, this balance is shifted toward matrix destruction due to increased production of cleavage enzymes and the presence of (autoimmune) immunoglobulins resulting from an inflammation induced immune response. Herein we demonstrate that a polyclonal antibody against the proteoglycan biglycan (BG) causes tissue destruction that may be analogous to that of RA affected tissues. The effectmore » of the antibody is more potent than harsh chemical and/or enzymatic treatments designed to mimic arthritis-like fibril de-polymerization. In RA cases, the immune response to inflammation causes synovial fibroblasts, monocytes and macrophages to produce cytokines and secrete matrix remodeling enzymes, whereas B cells are stimulated to produce immunoglobulins. The specific antigen that causes the RA immune response has not yet been identified, although possible candidates have been proposed, including collagen types I and II, and proteoglycans (PG's) such as biglycan. We speculate that the initiation of RA associated tissue destruction in vivo may involve a similar non-enzymatic decomposition of collagen fibrils via the immunoglobulins themselves that we observe here ex vivo.« less

Inference of Evolutionary Forces Acting on Human Biological Pathways

PubMed Central

Daub, Josephine T.; Dupanloup, Isabelle; Robinson-Rechavi, Marc; Excoffier, Laurent

2015-01-01

Because natural selection is likely to act on multiple genes underlying a given phenotypic trait, we study here the potential effect of ongoing and past selection on the genetic diversity of human biological pathways. We first show that genes included in gene sets are generally under stronger selective constraints than other genes and that their evolutionary response is correlated. We then introduce a new procedure to detect selection at the pathway level based on a decomposition of the classical McDonald–Kreitman test extended to multiple genes. This new test, called 2DNS, detects outlier gene sets and takes into account past demographic effects and evolutionary constraints specific to gene sets. Selective forces acting on gene sets can be easily identified by a mere visual inspection of the position of the gene sets relative to their two-dimensional null distribution. We thus find several outlier gene sets that show signals of positive, balancing, or purifying selection but also others showing an ancient relaxation of selective constraints. The principle of the 2DNS test can also be applied to other genomic contrasts. For instance, the comparison of patterns of polymorphisms private to African and non-African populations reveals that most pathways show a higher proportion of nonsynonymous mutations in non-Africans than in Africans, potentially due to different demographic histories and selective pressures. PMID:25971280

Decomposition of socio-economic differences in life expectancy at birth by age and cause of death among 4 million South Korean public servants and their dependents.

PubMed

Khang, Young-Ho; Yang, Seungmi; Cho, Hong-Jun; Jung-Choi, Kyunghee; Yun, Sung-Cheol

2010-12-01

Differences in life expectancy at birth across social classes can be more easily interpreted as a measure of absolute inequalities in survival. This study quantified age- and cause-specific contributions to life expectancy differences by income among 4 million public servants and their dependents in South Korea (9.1% of the total Korean population). Using 9-year mortality follow-up data (208,612 deaths) on 4,055,150 men and women aged 0-94 years, with national health insurance premiums imposed proportionally based on monthly salary as a measure of income, differences in life expectancy at birth by income were estimated by age- and cause-specific mortality differences using Arriaga's decomposition method. Life expectancy at birth gradually increased with income. Differences in life expectancy at birth between the highest and the lowest income quartile were 6.22 years in men and 1.74 years in women. Mortality differentials by income among those aged ≥50 years contributed most substantially (80.4% in men and 85.6% in women) to the socio-economic differences in life expectancy at birth. In men, cancers (stomach, liver and lung), cardiovascular diseases (stroke), digestive diseases (liver cirrhosis) and external causes (transport accidents and suicide) were important contributors to the life expectancy differences. In women, the contribution of ill-defined causes was most important. Cardiovascular diseases (stroke and hypertensive disease) and external causes (transport accidents and suicide) also contributed to the life expectancy differences in women while the contributions of cancers and digestive diseases were minimal. Reductions in socio-economic differentials in mortality from stroke and external causes (transport accidents and suicide) among middle-aged and older men and women would significantly contribute to equalizing life expectancy among income groups. Policy efforts to reduce mortality differentials in major cancers (stomach, liver and lung) and liver cirrhosis are also important for eliminating Korean men's socio-economic inequalities in life expectancy.

Mitochondrial Cardiomyopathy Caused by Elevated Reactive Oxygen Species and Impaired Cardiomyocyte Proliferation.

PubMed

Zhang, Donghui; Li, Yifei; Heims-Waldron, Danielle; Bezzerides, Vassilios; Guatimosim, Silvia; Guo, Yuxuan; Gu, Fei; Zhou, Pingzhu; Lin, Zhiqiang; Ma, Qing; Liu, Jianming; Wang, Da-Zhi; Pu, William T

2018-01-05

Although mitochondrial diseases often cause abnormal myocardial development, the mechanisms by which mitochondria influence heart growth and function are poorly understood. To investigate these disease mechanisms, we studied a genetic model of mitochondrial dysfunction caused by inactivation of Tfam (transcription factor A, mitochondrial), a nuclear-encoded gene that is essential for mitochondrial gene transcription and mitochondrial DNA replication. Tfam inactivation by Nkx2.5 Cre caused mitochondrial dysfunction and embryonic lethal myocardial hypoplasia. Tfam inactivation was accompanied by elevated production of reactive oxygen species (ROS) and reduced cardiomyocyte proliferation. Mosaic embryonic Tfam inactivation confirmed that the block to cardiomyocyte proliferation was cell autonomous. Transcriptional profiling by RNA-seq demonstrated the activation of the DNA damage pathway. Pharmacological inhibition of ROS or the DNA damage response pathway restored cardiomyocyte proliferation in cultured fetal cardiomyocytes. Neonatal Tfam inactivation by AAV9-cTnT-Cre caused progressive, lethal dilated cardiomyopathy. Remarkably, postnatal Tfam inactivation and disruption of mitochondrial function did not impair cardiomyocyte maturation. Rather, it elevated ROS production, activated the DNA damage response pathway, and decreased cardiomyocyte proliferation. We identified a transient window during the first postnatal week when inhibition of ROS or the DNA damage response pathway ameliorated the detrimental effect of Tfam inactivation. Mitochondrial dysfunction caused by Tfam inactivation induced ROS production, activated the DNA damage response, and caused cardiomyocyte cell cycle arrest, ultimately resulting in lethal cardiomyopathy. Normal mitochondrial function was not required for cardiomyocyte maturation. Pharmacological inhibition of ROS or DNA damage response pathways is a potential strategy to prevent cardiac dysfunction caused by some forms of mitochondrial dysfunction. © 2017 American Heart Association, Inc.

Simultaneous removal of formaldehyde and benzene in indoor air with a combination of sorption- and decomposition-type air filters.

PubMed

Sekine, Yoshika; Fukuda, Mitsuru; Takao, Yosuke; Ozano, Takahiro; Sakuramoto, Hikaru; Wang, Kuan Wei

2011-12-01

Urgent measures for indoor air pollution caused by volatile organic compounds are required in urban areas of China. Considering indoor air concentration levels and hazardous properties, formaldehyde and benzene should be given priority for pollution control in China. The authors proposed the use of air-cleaning devices, including stand-alone room air cleaners and in-duct devices. This study aimed to find the best combination of sorption and decomposition filters for the simultaneous removal of formaldehyde and benzene, employing four types of air filter units: an activated charcoal filter (ACF), an ACF impregnated with a trapping agent for acidic gases (ACID), a MnO2 filter (MDF) for oxidative decomposition of formaldehyde at room temperature and a photocatalyst filter (PHOTO) coupled with a parallel beam ultraviolet (UV) irradiation device. The performance of the combined systems under air flow rates of 35-165 m3 h(-1) was evaluated in a test chamber (2 m3) with a constant gas generation system. The experimental results and data analysis using a kinetic approach showed the combined system of ACF, PHOTO and MDF significantly reduced both concentrations of formaldehyde and benzene in air without any unpleasant odours caused by the UV-induced photocatalytic reaction. The system was then evaluated in a full-size laboratory (22 m3). This test proved the practical performance of the system even at full scale, and also suggested that the filters should be arranged in the order of PHOTO/ACF/MDF from upstream to downstream. The proposed system has the potential of being used for improving indoor air quality of houses and buildings in China.

The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

NASA Technical Reports Server (NTRS)

Yabuta, H.; Williams, L.; Cody, G.; Pizzarello, S.

2005-01-01

The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract.

CH 3NO 2 decomposition/isomerization mechanism and product branching ratios: An ab initio chemical kinetic study

NASA Astrophysics Data System (ADS)

Zhu, R. S.; Lin, M. C.

2009-08-01

The low-lying energy pathways for the decomposition/isomerization of nitromethane (NM) have been investigated using different molecular orbital methods. Our results show that in addition to the commonly known CH 3 + NO 2 products formed by direct C-N bond breaking and the trans-CH 3ONO formed by nitro-nitrite isomerization, NM can also isomerize to cis-CH 3ONO via a very loose transition state (TS) lying 59.2 kcal/mol above CH 3NO 2 or 0.6 kcal/mol below the CH 3 + NO 2 asymptote predicted at the UCCSD(T)/CBS level of theory. Kinetic results indicate that in the energy range of 59 ± 1 kcal/mol, production of CH 3O + NO is dominant, whereas above the C-N bond breaking threshold, the formation of CH 3 + NO 2 sharply increases and becomes dominant. The k( E) values predicted at different energies clearly indicate that CH 3O + NO could be detected in an infrared multi-photon dissociation study, whereas in UV dissociation experiments with energies high above the C-N bond breaking threshold the CH 3 + NO 2 products are generated predominantly.

Simulating coupled carbon and nitrogen dynamics following bark beetle outbreaks in the western United States

Treesearch

Steven L. Edburg; Jeffrey A. Hicke; David M. Lawrence; Peter E. Thornton

2011-01-01

Insect outbreaks are major ecosystem disturbances, affecting a similar area as forest fires annually across North America. Tree mortality caused by bark beetle outbreaks alters carbon cycling in the first several years following the disturbance by reducing stand-level primary production and by increasing the amount of dead organic matter available for decomposition....

Competitive Argumentation in Computational Theories of Cognition.

DTIC Science & Technology

1982-12-01

elements of number competence are present much earlier than strict Piagetian theory would predict (Gelman & Gallistel , 1978). A successful style of...caused considerable attention to be focused on counting. Observations by Gelman and Gallistell (1978), and others. provided evidence that significant...certain principles of counting. These premises formalized and extended a particular decomposition of counting competence proposed by Gelman and Gallistel

Retrieval of Enterobacteriaceae drug targets using singular value decomposition.

PubMed

Silvério-Machado, Rita; Couto, Bráulio R G M; Dos Santos, Marcos A

2015-04-15

The identification of potential drug target proteins in bacteria is important in pharmaceutical research for the development of new antibiotics to combat bacterial agents that cause diseases. A new model that combines the singular value decomposition (SVD) technique with biological filters composed of a set of protein properties associated with bacterial drug targets and similarity to protein-coding essential genes of Escherichia coli (strain K12) has been created to predict potential antibiotic drug targets in the Enterobacteriaceae family. This model identified 99 potential drug target proteins in the studied family, which exhibit eight different functions and are protein-coding essential genes or similar to protein-coding essential genes of E.coli (strain K12), indicating that the disruption of the activities of these proteins is critical for cells. Proteins from bacteria with described drug resistance were found among the retrieved candidates. These candidates have no similarity to the human proteome, therefore exhibiting the advantage of causing no adverse effects or at least no known adverse effects on humans. rita_silverio@hotmail.com. Supplementary data are available at Bioinformatics online. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Failure Analysis of Short-Circuited Lithium-Ion Battery with Nickel-Manganese-Cobalt/Graphite Electrode.

PubMed

Lee, Seung-Mi; Kim, Jea-Yeon; Byeon, Jai-Won

2018-09-01

Accidental failures and explosions of lithium-ion batteries have been reported in recent years. To determine the root causes and mechanisms of these failures from the perspective of material degradation, failure analysis was conducted for an intentionally shorted lithium-ion battery. The battery was subjected to electrical overcharging and mechanical pressing to simulate internal short-circuiting. After in situ measurement of the temperature increase during the short-circuiting of the electrodes, the disassembled battery components (i.e., the anode, cathode, and separator) were analyzed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Regardless of the simulated short-circuit method (mechanical or electrical), damage was observed in the shorted batteries. Numerous small cracks and chemical reaction products were observed on the electrode surface, along with pore shielding on the separator. The event of short-circuiting increased the surface temperature of the battery to approximately 90 °C, which prompted the deterioration and decomposition of the electrolyte, thus affecting the overall battery performance; this was attributed to the decomposition of the lithium salt at 60 °C. The gas generation due to the breakdown of the electrolyte causes pressure accumulation inside the cell; therefore, the electrolyte leaks.

Validation of Heat Transfer Thermal Decomposition and Container Pressurization of Polyurethane Foam.

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

Scott, Sarah Nicole; Dodd, Amanda B.; Larsen, Marvin E.

Polymer foam encapsulants provide mechanical, electrical, and thermal isolation in engineered systems. In fire environments, gas pressure from thermal decomposition of polymers can cause mechanical failure of sealed systems. In this work, a detailed uncertainty quantification study of PMDI-based polyurethane foam is presented to assess the validity of the computational model. Both experimental measurement uncertainty and model prediction uncertainty are examined and compared. Both the mean value method and Latin hypercube sampling approach are used to propagate the uncertainty through the model. In addition to comparing computational and experimental results, the importance of each input parameter on the simulation resultmore » is also investigated. These results show that further development in the physics model of the foam and appropriate associated material testing are necessary to improve model accuracy.« less

Proteases Revisited: Roles and Therapeutic Implications in Fibrosis

PubMed Central

Kryczka, Jakub

2017-01-01

Proteases target many substrates, triggering changes in distinct biological processes correlated with cell migration, EMT/EndMT and fibrosis. Extracellular protease activity, demonstrated by secreted and membrane-bound protease forms, leads to ECM degradation, activation of other proteases (i.e., proteolysis of nonactive zymogens), decomposition of cell-cell junctions, release of sequestered growth factors (TGF-β and VEGF), activation of signal proteins and receptors, degradation of inflammatory inhibitors or inflammation-related proteins, and changes in cell mechanosensing and motility. Intracellular proteases, mainly caspases and cathepsins, modulate lysosome activity and signal transduction pathways. Herein, we discuss the current knowledge on the multidimensional impact of proteases on the development of fibrosis. PMID:28642633

Combinatorial evaluation of systems including decomposition of a system representation into fundamental cycles

DOEpatents

Oliveira, Joseph S [Richland, WA; Jones-Oliveira, Janet B [Richland, WA; Bailey, Colin G [Wellington, NZ; Gull, Dean W [Seattle, WA

2008-07-01

One embodiment of the present invention includes a computer operable to represent a physical system with a graphical data structure corresponding to a matroid. The graphical data structure corresponds to a number of vertices and a number of edges that each correspond to two of the vertices. The computer is further operable to define a closed pathway arrangement with the graphical data structure and identify each different one of a number of fundamental cycles by evaluating a different respective one of the edges with a spanning tree representation. The fundamental cycles each include three or more of the vertices.

Signaling Pathway in Early Brain Injury after Subarachnoid Hemorrhage: News Update.

PubMed

Ji, Chengyuan; Chen, Gang

2016-01-01

The annual incidence of subarachnoid hemorrhage (SAH) caused by intracranial aneurysm rupture is approximately 10.5/10 million people in China, making SAH the third most frequently occurring hemorrhage of the intracranial type after cerebral embolism and hypertensive intracerebral hemorrhage. SAH caused by ruptured aneurysm leads to a mortality rate as high as 67 %, and, because of the sudden onset of this disease, approximately 12-15 % of patients die before they can receive effective treatment. Early brain injury (EBI) is the brain damage occurring within the first 72 h after SAH. Two-thirds of mortality caused by SAH occurs within 48 h, mainly as a result of EBI. With the development of molecular biology and medicine microscopy techniques, various signaling pathways involved in EBI after SAH have been revealed. Understanding these signaling pathways may help clinicians treat EBI after SAH and improve long-term prognosis of SAH patients. This chapter summarizes several important signaling pathways implicated in EBI caused by SAH.

ATOM-ECONOMICAL PATHWAYS TO METHANOL FUEL CELL FROM BIOMASS

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

MAHAJAN,D.; WEGRZYN,J.E.

1999-03-01

An economical production of alcohol fuels from biomass, a feedstock low in carbon and high in water content, is of interest. At Brookhaven National Laboratory (BNL), a Liquid Phase Low Temperature (LPLT) concept is under development to improve the economics by maximizing the conversion of energy carrier atoms (C,H) into energy liquids (fuel). So far, the LPLT concept has been successfully applied to obtain highly efficient methanol synthesis. This synthesis was achieved with specifically designed soluble catalysts, at temperatures < 150 C. A subsequent study at BNL yielded a water-gas-shift (WGS) catalyst for the production of hydrogen from a feedstockmore » of carbon monoxide and H{sub 2}O at temperatures < 120 C. With these LPLT technologies as a background, this paper extends the discussion of the LPLT concept to include methanol decomposition into 3 moles of H{sub 2} per mole of methanol. The implication of these technologies for the atom-economical pathways to methanol fuel cell from biomass is discussed.« less

Reaction trajectory revealed by a joint analysis of protein data bank.

PubMed

Ren, Zhong

2013-01-01

Structural motions along a reaction pathway hold the secret about how a biological macromolecule functions. If each static structure were considered as a snapshot of the protein molecule in action, a large collection of structures would constitute a multidimensional conformational space of an enormous size. Here I present a joint analysis of hundreds of known structures of human hemoglobin in the Protein Data Bank. By applying singular value decomposition to distance matrices of these structures, I demonstrate that this large collection of structural snapshots, derived under a wide range of experimental conditions, arrange orderly along a reaction pathway. The structural motions along this extensive trajectory, including several helical transformations, arrive at a reverse engineered mechanism of the cooperative machinery (Ren, companion article), and shed light on pathological properties of the abnormal homotetrameric hemoglobins from α-thalassemia. This method of meta-analysis provides a general approach to structural dynamics based on static protein structures in this post genomics era.

Reaction Trajectory Revealed by a Joint Analysis of Protein Data Bank

PubMed Central

Ren, Zhong

2013-01-01

Structural motions along a reaction pathway hold the secret about how a biological macromolecule functions. If each static structure were considered as a snapshot of the protein molecule in action, a large collection of structures would constitute a multidimensional conformational space of an enormous size. Here I present a joint analysis of hundreds of known structures of human hemoglobin in the Protein Data Bank. By applying singular value decomposition to distance matrices of these structures, I demonstrate that this large collection of structural snapshots, derived under a wide range of experimental conditions, arrange orderly along a reaction pathway. The structural motions along this extensive trajectory, including several helical transformations, arrive at a reverse engineered mechanism of the cooperative machinery (Ren, companion article), and shed light on pathological properties of the abnormal homotetrameric hemoglobins from α-thalassemia. This method of meta-analysis provides a general approach to structural dynamics based on static protein structures in this post genomics era. PMID:24244274

A theoretical study on the mechanistic highlights behind the Brønsted-acid dependent mer-fac isomerization of homoleptic carbenic iridium complexes for PhOLEDs.

PubMed

Setzer, Tobias; Lennartz, Christian; Dreuw, Andreas

2017-06-06

Recently, a successful Brønsted-acid mediated geometric isomerization of the meridional homoleptic carbenic iridium(iii) complexes tris-(N-phenyl,N-methyl-benzimidazol-2-yl)iridium(iii) (1) and tris-(N-phenyl,N-benzyl-benzimidazol-2-yl)iridium(iii) (2) into their facial form has been reported. In the present work the pronounced acid-dependency of this particular isomerization procedure is revisited and additional mechanistic pathways are taken into account. Moreover, the acid-induced material decomposition is addressed. All calculations are carried out using density functional theory (DFT) while the environmental effects in solution are accounted for by the COSMO-RS model. The simulated results clearly reveal the outstanding importance of the complex interplay between acid strength, coordinating power of the corresponding base and the steric influence of the ligand system in contrast to the plain calculation of minimum energy pathways for selected complexes. Eventually, general rules to enhance the material-specific reaction yields are provided.

Using metabolic flux data to further constrain the metabolic solution space and predict internal flux patterns: the Escherichia coli spectrum.

PubMed

Wiback, Sharon J; Mahadevan, Radhakrishnan; Palsson, Bernhard Ø

2004-05-05

Constraint-based metabolic modeling has been used to capture the genome-scale, systems properties of an organism's metabolism. The first generation of these models has been built on annotated gene sequence. To further this field, we now need to develop methods to incorporate additional "omic" data types including transcriptomics, metabolomics, and fluxomics to further facilitate the construction, validation, and predictive capabilities of these models. The work herein combines metabolic flux data with an in silico model of central metabolism of Escherichia coli for model centric integration of the flux data. The extreme pathways for this network, which define the allowable solution space for all possible flux distributions, are analyzed using the alpha-spectrum. The alpha-spectrum determines which extreme pathways can and cannot contribute to the metabolic flux distribution for a given condition and gives the allowable range of weightings on each extreme pathway that can contribute. Since many extreme pathways cannot be used under certain conditions, the result is a "condition-specific" solution space that is a subset of the original solution space. The alpha-spectrum results are used to create a "condition-specific" extreme pathway matrix that can be analyzed using singular value decomposition (SVD). The first mode of the SVD analysis characterizes the solution space for a given condition. We show that SVD analysis of the alpha-spectrum extreme pathway matrix that incorporates measured uptake and byproduct secretion rates, can predict internal flux trends for different experimental conditions. These predicted internal flux trends are, in general, consistent with the flux trends measured using experimental metabolic flux analysis techniques. Copyright 2004 Wiley Periodicals, Inc.