Sample records for intermediates decomposition studies

  1. HCOOH decomposition on Pt(111): A DFT study

    DOE PAGES

    Scaranto, Jessica; Mavrikakis, Manos

    2015-10-13

    Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO 2 and H 2 or dehydration leading to CO and H 2O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We alsomore » considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO 2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.« less

  2. HCOOH decomposition on Pt(111): A DFT study

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

    Scaranto, Jessica; Mavrikakis, Manos

    Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO 2 and H 2 or dehydration leading to CO and H 2O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We alsomore » considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO 2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.« less

  3. 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.

  4. Mössbauer study of the thermal decomposition of alkali tris(oxalato)ferrates(III)

    NASA Astrophysics Data System (ADS)

    Brar, A. S.; Randhawa, B. S.

    1985-07-01

    The thermal decomposition of alkali (Li,Na,K,Cs,NH 4) tris(oxalato)ferrates(III) has been studied at different temperatures up to 700°C using Mössbauer, infrared spectroscopy, and thermogravimetric techniques. The formation of different intermediates has been observed during thermal decomposition. The decomposition in these complexes starts at different temperatures, i.e., at 200°C in the case of lithium, cesium, and ammonium ferrate(III), 250°C in the case of sodium, and 270°C in the case of potassium tris(oxalato)ferrate(III). The intermediates, i.e., Fe 11C 2O 4, K 6Fe 112(ox) 5. and Cs 2Fe 11 (ox) 2(H 2O) 2, are formed during thermal decomposition of lithium, potassium, and cesium tris(oxalato)ferrates(III), respectively. In the case of sodium and ammonium tris(oxalato)ferrates(III), the decomposition occurs without reduction to the iron(II) state and leads directly to α-Fe 2O 3.

  5. 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

  6. Study on US/O3 mechanism in p-chlorophenol decomposition

    PubMed Central

    Xu, Xian-wen; Xu, Xin-hua; Shi, Hui-xiang; Wang, Da-hui

    2005-01-01

    Study on the effects of sonolysis, ozonolysis and US/O3 system on the decomposition of p-chlorophenol in aqueous solutions indicated that in the cases of US/O3 system, individual ozonolysis and sonolysis, the decomposition rate of p-chlorophenol reached 78.78%, 56.20%, 2.79% after a 16-min reaction while its CODcr (chemical oxygen demand) removal rate was 97.02%, 62.17%, 3.67% after a 120-min reaction. The decomposition reaction of p-chlorophenol follows pseudo-first-order kinetics. The enhancement factors of p-chlorophenol and its CODcr under US/O3 system reached 63% and 237% respectively. The main intermediates during the decomposition include catechol, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid, oxalic acid and formic acid. The decomposition mechanism of p-chlorophenol was also discussed. PMID:15909343

  7. Thermal decomposition of ammonium hexachloroosmate.

    PubMed

    Asanova, T I; Kantor, I; Asanov, I P; Korenev, S V; Yusenko, K V

    2016-12-07

    Structural changes of (NH 4 ) 2 [OsCl 6 ] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH 4 ) 2 [OsCl 6 ] transforms directly to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl 4 } x with a possible polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before.

  8. Density functional theory studies of HCOOH decomposition on Pd(111)

    DOE PAGES

    Scaranto, Jessica; Mavrikakis, Manos

    2015-12-02

    Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

  9. Density functional theory studies of HCOOH decomposition on Pd(111)

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

    Scaranto, Jessica; Mavrikakis, Manos

    Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

  10. Tautomerism and thermal decomposition of tetrazole: high-level ab initio study.

    PubMed

    Kiselev, Vitaly G; Cheblakov, Pavel B; Gritsan, Nina P

    2011-03-10

    The mutual interconversion and decomposition reactions of four tetrazole isomers (1H-TZ, 2H-TZ, 5H-TZ, and an N-heterocyclic carbene 14H) have been studied theoretically using the W1 high-level procedure. Computations allowed resolution of the existing discrepancies in the mechanism and key intermediates of TZ thermolysis. The tautomeric equilibria between 1H-TZ, 2H-TZ, and 14H turned out to play a very important role in the mechanism of thermal decomposition. Although the barriers of monomolecular tautomeric transformations were found to be high (∼50-70 kcal/mol), the concerted double H atom transfer reactions in the H-bonded complexes of TZ tautomers have profoundly lower barriers (∼18-28 kcal/mol). These reactions lead to fast interconversion between 1H-TZ, 2H-TZ, and 14H. The carbene 14H has never been considered before; however, it was predicted to be a key intermediate in the mechanism of thermal decomposition of TZ. For all species considered, the unimolecular reactions of N(2) elimination were predicted to dominate over the elimination of hydrazoic acid. In agreement with existing experimental data, the effective activation energy of thermolysis was calculated to be 36.2 kcal/mol.

  11. In situ spectroscopic studies on vapor phase catalytic decomposition of dimethyl oxalate.

    PubMed

    Hegde, Shweta; Tharpa, Kalsang; Akuri, Satyanarayana Reddy; K, Rakesh; Kumar, Ajay; Deshpande, Raj; Nair, Sreejit A

    2017-03-15

    Dimethyl Oxalate (DMO) has recently gained prominence as a valuable intermediate for the production of compounds of commercial importance. The stability of DMO is poor and hence this can result in the decomposition of DMO under reaction conditions. The mechanism of DMO decomposition is however not reported and more so on catalytic surfaces. Insights into the mechanism of decomposition would help in designing catalysts for its effective molecular transformation. It is well known that DMO is sensitive to moisture, which can also be a factor contributing to its decomposition. The present work reports the results of decomposition of DMO on various catalytic materials. The materials studied consist of acidic (γ-Al 2 O 3 ), basic (MgO), weakly acidic (ZnAl 2 O 4 ) and neutral surfaces such as α-Al 2 O 3 and mesoporous precipitated SiO 2 . Infrared spectroscopy is used to identify the nature of adsorption of the molecule on the various surfaces. The spectroscopy study is done at a temperature of 200 °C, which is the onset of gas phase decomposition of DMO. The results indicate that the stability of DMO is lower than the corresponding acid, i.e. oxalic acid. It is also one of the products of decomposition. Spectroscopic data suggest that DMO decomposition is related to surface acidity and the extent of decomposition depends on the number of surface hydroxyl groups. Decomposition was also observed on α-Al 2 O 3 , which was attributed to the residual surface hydroxyl groups. DMO decomposition to oxalic acid was not observed on the basic surface (MgO).

  12. 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.

  13. The Composition of Intermediate Products of the Thermal Decomposition of (NH4)2ZrF6 to ZrO2 from Vibrational-Spectroscopy Data

    NASA Astrophysics Data System (ADS)

    Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.

    2018-03-01

    Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.

  14. Ozone decomposition

    PubMed Central

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

    2014-01-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  15. Decomposition of sulfamethoxazole and trimethoprim by continuous UVA/LED/TiO2 photocatalysis: Decomposition pathways, residual antibacterial activity and toxicity.

    PubMed

    Cai, Qinqing; Hu, Jiangyong

    2017-02-05

    In this study, continuous LED/UVA/TiO 2 photocatalytic decomposition of sulfamethoxazole (SMX) and trimethoprim (TMP) was investigated. More than 90% of SMX and TMP were removed within 20min by the continuous photoreactor (with the initial concentration of 400ppb for each). The removal rates of SMX and TMP decreased with higher initial antibiotics loadings. SMX was much easier decomposed in acidic condition, while pH affected little on TMP's decomposition. 0.003% was found to be the optimum H 2 O 2 dosage to enhance SMX photocatalytic decomposition. Decomposition pathways of SMX and TMP were proposed based on the intermediates identified by using LC-MS-MS and GC-MS. Aniline was identified as a new intermediate generated during SMX photocatalytic decomposition. Antibacterial activity study with a reference Escherichia coli strain was also conducted during the photocatalytic process. Results indicated that with every portion of TMP removed, the residual antibacterial activity decreased by one portion. However, the synergistic effect between SMX and TMP tended to slow down the antibacterial activity removal of SMX and TMP mixture. Chronic toxicity studies conducted with Vibrio fischeri exhibited 13-20% bioluminescence inhibition during the decomposition of 1ppm SMX and 1ppm TMP, no acute toxicity to V. fischeri was observed during the photocatalytic process. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Optimized color decomposition of localized whole slide images and convolutional neural network for intermediate prostate cancer classification

    NASA Astrophysics Data System (ADS)

    Zhou, Naiyun; Gao, Yi

    2017-03-01

    This paper presents a fully automatic approach to grade intermediate prostate malignancy with hematoxylin and eosin-stained whole slide images. Deep learning architectures such as convolutional neural networks have been utilized in the domain of histopathology for automated carcinoma detection and classification. However, few work show its power in discriminating intermediate Gleason patterns, due to sporadic distribution of prostate glands on stained surgical section samples. We propose optimized hematoxylin decomposition on localized images, followed by convolutional neural network to classify Gleason patterns 3+4 and 4+3 without handcrafted features or gland segmentation. Crucial glands morphology and structural relationship of nuclei are extracted twice in different color space by the multi-scale strategy to mimic pathologists' visual examination. Our novel classification scheme evaluated on 169 whole slide images yielded a 70.41% accuracy and corresponding area under the receiver operating characteristic curve of 0.7247.

  17. Theoretical study of the decomposition pathways and products of C5- perfluorinated ketone (C5 PFK)

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

    Fu, Yuwei; Wang, Xiaohua, E-mail: xhw@mail.xjtu.edu.cn, E-mail: mzrong@mail.xjtu.edu.cn; Li, Xi

    Due to the high global warming potential (GWP) and increasing environmental concerns, efforts on searching the alternative gases to SF{sub 6}, which is predominantly used as insulating and interrupting medium in high-voltage equipment, have become a hot topic in recent decades. Overcoming the drawbacks of the existing candidate gases, C5- perfluorinated ketone (C5 PFK) was reported as a promising gas with remarkable insulation capacity and the low GWP of approximately 1. Experimental measurements of the dielectric strength of this novel gas and its mixtures have been carried out, but the chemical decomposition pathways and products of C5 PFK during breakdownmore » are still unknown, which are the essential factors in evaluating the electric strength of this gas in high-voltage equipment. Therefore, this paper is devoted to exploring all the possible decomposition pathways and species of C5 PFK by density functional theory (DFT). The structural optimizations, vibrational frequency calculations and energy calculations of the species involved in a considered pathway were carried out with DFT-(U)B3LYP/6-311G(d,p) method. Detailed potential energy surface was then investigated thoroughly by the same method. Lastly, six decomposition pathways of C5 PFK decomposition involving fission reactions and the reactions with a transition states were obtained. Important intermediate products were also determined. Among all the pathways studied, the favorable decomposition reactions of C5 PFK were found, involving C-C bond ruptures producing Ia and Ib in pathway I, followed by subsequent C-C bond ruptures and internal F atom transfers in the decomposition of Ia and Ib presented in pathways II + III and IV + V, respectively. Possible routes were pointed out in pathway III and lead to the decomposition of IIa, which is the main intermediate product found in pathway II of Ia decomposition. We also investigated the decomposition of Ib, which can undergo unimolecular reactions to give

  18. Study on Thermal Decomposition Characteristics of Ammonium Nitrate Emulsion Explosive in Different Scales

    NASA Astrophysics Data System (ADS)

    Wu, Qiujie; Tan, Liu; Xu, Sen; Liu, Dabin; Min, Li

    2018-04-01

    Numerous accidents of emulsion explosive (EE) are attributed to uncontrolled thermal decomposition of ammonium nitrate emulsion (ANE, the intermediate of EE) and EE in large scale. In order to study the thermal decomposition characteristics of ANE and EE in different scales, a large-scale test of modified vented pipe test (MVPT), and two laboratory-scale tests of differential scanning calorimeter (DSC) and accelerating rate calorimeter (ARC) were applied in the present study. The scale effect and water effect both play an important role in the thermal stability of ANE and EE. The measured decomposition temperatures of ANE and EE in MVPT are 146°C and 144°C, respectively, much lower than those in DSC and ARC. As the size of the same sample in DSC, ARC, and MVPT successively increases, the onset temperatures decrease. In the same test, the measured onset temperature value of ANE is higher than that of EE. The water composition of the sample stabilizes the sample. The large-scale test of MVPT can provide information for the real-life operations. The large-scale operations have more risks, and continuous overheating should be avoided.

  19. 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

  20. A quantum chemical study of the decomposition of Keggin-structured heteropolyacids.

    PubMed

    Janik, Michael J; Bardin, Billy B; Davis, Robert J; Neurock, Matthew

    2006-03-09

    Heterpolyacids (HPAs) demonstrate catalytic activity for oxidative and acid-catalyzed hydrocarbon conversion processes. Deactivation and thermal instability, however, have prevented their widespread use. Herein, ab initio density functional theory is used to study the thermal decomposition of the Keggin molecular HPA structure through the desorption of constitutional water molecules. The overall reaction energy and activation barrier are computed for the overall reaction HnXM12O40-->Hn-2XM12O39+H2O. and subsequently used to predict the effect of HPA composition on thermal stability. For example, the desorption of a constitutional water molecule is found to be increasingly endothermic in the order silicomolybdic acid (H4SiMo12O40)decomposition into a bulk mixed oxide. The equilibrium concentration of defective Keggin units is determined as a function of temperature and water partial pressure. It is concluded that the loss of constitutional water molecules is a plausible deactivation mechanism of the acid catalyst. The intermediate structures along the decomposition path are proposed as possible active sites for oxidation catalysis. The results presented herein provide molecular level insight into the dynamic nature of the heteropolyacid catalyst structure.

  1. 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.

  2. Mechanism of thermal decomposition of K2FeO4 and BaFeO4: A review

    NASA Astrophysics Data System (ADS)

    Sharma, Virender K.; Machala, Libor

    2016-12-01

    This paper presents thermal decomposition of potassium ferrate(VI) (K2FeO4) and barium ferrate(VI) (BaFeO4) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe V and Fe IV as intermediate iron species using the applied techniques are given. Thermal decomposition of K2FeO4 involved Fe V, Fe IV, and K3FeO3 as intermediate species while BaFeO3 (i.e. Fe IV) was the only intermediate species during the decomposition of BaFeO4. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K2FeO4 and BaFeO4 under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

  3. Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

    NASA Astrophysics Data System (ADS)

    Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

    2017-06-01

    The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

  4. Thermochemistry, Tautomerism, and Thermal Decomposition of 1,5-Diaminotetrazole: A High-Level ab Initio Study.

    PubMed

    Shakhova, Margarita V; Muravyev, Nikita V; Gritsan, Nina P; Kiselev, Vitaly G

    2018-04-19

    Thermochemistry, kinetics, and mechanism of thermal decomposition of 1,5-diaminotetrazole (DAT), a widely used "building block" of nitrogen-rich energetic compounds, were studied theoretically at a high and reliable level of theory (viz., using the explicitly correlated CCSD(T)-F12/aug-cc-pVTZ procedure). Quantum chemical calculations provided detailed insight into the thermolysis mechanism of DAT missing in the existing literature. Moreover, several contradictory assumptions on the mechanism and key intermediates of thermolysis were resolved. The unimolecular primary decomposition reactions of the seven isomers of DAT were studied in the gas phase and in the melt using a simplified model of the latter. The two-step reaction of N 2 elimination from the diamino tautomer was found to be the primary decomposition process of DAT in the gas phase and melt. The effective Arrhenius parameters of this process were calculated to be E a = 43.4 kcal mol -1 and log( A/s -1 ) = 15.2 in a good agreement with the experimental values. Contrary to the existing literature data, all other decomposition channels of DAT isomers turned out to be kinetically unimportant. Apart from this, a new primary decomposition channel yielding N 2 , cyanamide, and 1,1-diazene was found for some H-bonded dimers of DAT. We also determined a reliable and mutually consistent set of thermochemical values for DAT (Δ f H solid 0 = 74.5 ± 1.5 kcal·mol -1 ) by combining theoretically calculated (W1 multilevel procedure along with an isodesmic reaction) gas phase enthalpy of formation (Δ f H gas 0 = 100.7 ± 1.0 kcal·mol -1 ) and experimentally measured sublimation enthalpy (Δ sub H 0 = 26.2 ± 0.5 kcal·mol -1 ).

  5. 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

  6. 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

  7. Studies on thermal decomposition behaviors of polypropylene using molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Huang, Jinbao; He, Chao; Tong, Hong; Pan, Guiying

    2017-11-01

    Polypropylene (PP) is one of the main components of waste plastics. In order to understand the mechanism of PP thermal decomposition, the pyrolysis behaviour of PP has been simulated from 300 to 1000 K in periodic boundary conditions by molecular dynamic method, based on AMBER force field. The simulation results show that the pyrolysis process of PP can mostly be divided into three stages: low temperature pyrolysis stage, intermediate temperature stage and high temperature pyrolysis stage. PP pyrolysis is typical of random main-chain scission, and the possible formation mechanism of major pyrolysis products was analyzed.

  8. Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

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

    Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.

    2015-07-16

    The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature micro-tubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation re-analysismore » of the CH3CHO potential energy surface (PES). The lowest energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a re-isomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory based conclusions that the dominant decomposition process in CH3CHO at high temperatures is C-C bond fission with a minor contribution (~10-20%) from the roaming mechanism to form CH4 and CO. The present modeling efforts also incorporate a master-equation analysis of the H + CH2CHOH potential energy surface. This bimolecular reaction is the primary mechanism for removal of CH2CHOH, which can accumulate to minor amounts at high temperatures, T > 1000 K, in most lab-scale experiments that use large initial concentrations of CH3CHO. Our modeling efforts indicate that the observation of ketene, water and acetylene in the recent micro-tubular experiments are primarily due to bimolecular reactions of CH3CHO and CH2CHOH with H-atoms, and have no

  9. 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.

  10. Testing the Use of Pigs as Human Proxies in Decomposition Studies.

    PubMed

    Connor, Melissa; Baigent, Christiane; Hansen, Eriek S

    2017-12-28

    Pigs are a common human analogue in taphonomic study, yet data comparing the trajectory of decomposition between the two groups are lacking. This study compared decomposition rate and gross tissue change in 17 pigs and 22 human remains placed in the Forensic Investigation Research Station in western Colorado between 2012 and 2015. Accumulated degree days (ADD) were used to assess the number of thermal units required to reach a given total body score (TBS) (1) which was used as the measure of decomposition. A comparison of slopes in linear mixed effects model indicated that decomposition rates significantly differed between human donors and pig remains χ 2 (1) = 5.662, p = 0.017. Neither the pig nor the human trajectory compared well to the TBS model. Thus, (i) pigs are not an adequate proxy for human decomposition studies, and (ii) in the semiarid environment of western Colorado, there is a need to develop a regional decomposition model. © 2017 American Academy of Forensic Sciences.

  11. The Decomposition of Carbonates and Organics on Mars

    NASA Technical Reports Server (NTRS)

    Quinn, Richard C.; Zent, Aaron; McKay, Chris; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.

  12. Seasonal necrophagous insect community assembly during vertebrate carrion decomposition.

    PubMed

    Benbow, M E; Lewis, A J; Tomberlin, J K; Pechal, J L

    2013-03-01

    Necrophagous invertebrates have been documented to be a predominant driver of vertebrate carrion decomposition; however, very little is understood about the assembly of these communities both within and among seasons. The objective of this study was to evaluate the seasonal differences in insect taxa composition, richness, and diversity on carrion over decomposition with the intention that such data will be useful for refining error estimates in forensic entomology. Sus scrofa (L.) carcasses (n = 3-6, depending on season) were placed in a forested habitat near Xenia, OH, during spring, summer, autumn, and winter. Taxon richness varied substantially among seasons but was generally lower (1-2 taxa) during early decomposition and increased (3-8 taxa) through intermediate stages of decomposition. Autumn and winter showed the highest richness during late decomposition. Overall, taxon richness was higher during active decay for all seasons. While invertebrate community composition was generally consistent among seasons, the relative abundance of five taxa significantly differed across seasons, demonstrating different source communities for colonization depending on the time of year. There were significantly distinct necrophagous insect communities for each stage of decomposition, and between summer and autumn and summer and winter, but the communities were similar between autumn and winter. Calliphoridae represented significant indicator taxa for summer and autumn but replaced by Coleoptera during winter. Here we demonstrated substantial variability in necrophagous communities and assembly on carrion over decomposition and among seasons. Recognizing this variation has important consequences for forensic entomology and future efforts to provide error rates for estimates of the postmortem interval using arthropod succession data as evidence during criminal investigations.

  13. Reaction behaviors of decomposition of monocrotophos in aqueous solution by UV and UV/O processes.

    PubMed

    Ku, Y; Wang, W; Shen, Y S

    2000-02-01

    The decomposition of monocrotophos (cis-3-dimethoxyphosphinyloxy-N-methyl-crotonamide) in aqueous solution by UV and UV/O(3) processes was studied. The experiments were carried out under various solution pH values to investigate the decomposition efficiencies of the reactant and organic intermediates in order to determine the completeness of decomposition. The photolytic decomposition rate of monocrotophos was increased with increasing solution pH because the solution pH affects the distribution and light absorbance of monocrotophos species. The combination of O(3) with UV light apparently promoted the decomposition and mineralization of monocrotophos in aqueous solution. For the UV/O(3) process, the breakage of the >C=C< bond of monocrotophos by ozone molecules was found to occur first, followed by mineralization by hydroxyl radicals to generate CO(3)(2-), PO4(3-), and NO(3)(-) anions in sequence. The quasi-global kinetics based on a simplified consecutive-parallel reaction scheme was developed to describe the temporal behavior of monocrotophos decomposition in aqueous solution by the UV/O(3) process.

  14. 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

  15. A characterization of the two-step reaction mechanism of phenol decomposition by a Fenton reaction

    NASA Astrophysics Data System (ADS)

    Valdés, Cristian; Alzate-Morales, Jans; Osorio, Edison; Villaseñor, Jorge; Navarro-Retamal, Carlos

    2015-11-01

    Phenol is one of the worst contaminants at date, and its degradation has been a crucial task over years. Here, the decomposition process of phenol, in a Fenton reaction, is described. Using scavengers, it was observed that decomposition of phenol was mainly influenced by production of hydroxyl radicals. Experimental and theoretical activation energies (Ea) for phenol oxidation intermediates were calculated. According to these Ea, phenol decomposition is a two-step reaction mechanism mediated predominantly by hydroxyl radicals, producing a decomposition yield order given as hydroquinone > catechol > resorcinol. Furthermore, traces of reaction derived acids were detected by HPLC and GS-MS.

  16. Decomposition

    USGS Publications Warehouse

    Middleton, Beth A.

    2014-01-01

    A cornerstone of ecosystem ecology, decomposition was recognized as a fundamental process driving the exchange of energy in ecosystems by early ecologists such as Lindeman 1942 and Odum 1960). In the history of ecology, studies of decomposition were incorporated into the International Biological Program in the 1960s to compare the nature of organic matter breakdown in various ecosystem types. Such studies still have an important role in ecological studies of today. More recent refinements have brought debates on the relative role microbes, invertebrates and environment in the breakdown and release of carbon into the atmosphere, as well as how nutrient cycling, production and other ecosystem processes regulated by decomposition may shift with climate change. Therefore, this bibliography examines the primary literature related to organic matter breakdown, but it also explores topics in which decomposition plays a key supporting role including vegetation composition, latitudinal gradients, altered ecosystems, anthropogenic impacts, carbon storage, and climate change models. Knowledge of these topics is relevant to both the study of ecosystem ecology as well projections of future conditions for human societies.

  17. Thermogravimetric Control of Intermediate Products in the Metallurgy of Uranium; CONTROL TERMOGRAVIMETRICO DE PRODUCTOS INTERMEDIOS DE LA METALURGIA DEL URANIO

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

    Sanchez, L.G.; Cellini, R.F.

    1959-01-01

    The thermal decomposition of some intermediate compounds in the metallurgy of uranium such as uranium peroxide, ammonium uranate, ammonium uranium pentafluoride, uranium tetrafluoride, and UO/sub 2/, were studied using Chevenard's thermobalance. Some data on the pyrolysis of synthetic mixtures of intermediate compounds which may appear during the industrial processing are given. Thermogravimetric methods of control are suggested for use in uranium metallurgy. (tr-auth)

  18. A density functional theory study of the decomposition mechanism of nitroglycerin.

    PubMed

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

    2017-08-21

    The detailed decomposition mechanism of nitroglycerin (NG) in the gas phase was studied by examining reaction pathways using density functional theory (DFT) and canonical variational transition state theory combined with a small-curvature tunneling correction (CVT/SCT). The mechanism of NG autocatalytic decomposition was investigated at the B3LYP/6-31G(d,p) level of theory. Five possible decomposition pathways involving NG were identified and the rate constants for the pathways at temperatures ranging from 200 to 1000 K were calculated using CVT/SCT. There was found to be a lower energy barrier to the β-H abstraction reaction than to the α-H abstraction reaction during the initial step in the autocatalytic decomposition of NG. The decomposition pathways for CHOCOCHONO 2 (a product obtained following the abstraction of three H atoms from NG by NO 2 ) include O-NO 2 cleavage or isomer production, meaning that the autocatalytic decomposition of NG has two reaction pathways, both of which are exothermic. The rate constants for these two reaction pathways are greater than the rate constants for the three pathways corresponding to unimolecular NG decomposition. The overall process of NG decomposition can be divided into two stages based on the NO 2 concentration, which affects the decomposition products and reactions. In the first stage, the reaction pathway corresponding to O-NO 2 cleavage is the main pathway, but the rates of the two autocatalytic decomposition pathways increase with increasing NO 2 concentration. However, when a threshold NO 2 concentration is reached, the NG decomposition process enters its second stage, with the two pathways for NG autocatalytic decomposition becoming the main and secondary reaction pathways.

  19. Reactivity of Criegee Intermediates toward Carbon Dioxide.

    PubMed

    Lin, Yen-Hsiu; Takahashi, Kaito; Lin, Jim Jr-Min

    2018-01-04

    Recent theoretical work by Kumar and Francisco suggested that the high reactivity of Criegee intermediates (CIs) could be utilized for designing efficient carbon capture technologies. Because the anti-CH 3 CHOO + CO 2 reaction has the lowest barrier in their study, we chose to investigate it experimentally. We probed anti-CH 3 CHOO with its strong UV absorption at 365 nm and measured the rate coefficient to be ≤2 × 10 -17 cm 3 molecule -1 s -1 at 298 K, which is consistent with our theoretical value of 2.1 × 10 -17 cm 3  molecule -1 s -1 at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level but inconsistent with their results obtained at the M06-2X/aug-cc-pVTZ level, which tends to underestimate the barrier heights. The experimental result indicates that the reaction of a Criegee intermediate with atmospheric CO 2 (400 ppmv) would be inefficient (k eff < 0.2 s -1 ) and cannot compete with other decay processes of Criegee intermediates like reactions with water vapor (∼10 3 s -1 ) or thermal decomposition (∼10 2 s -1 ).

  20. A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

    NASA Astrophysics Data System (ADS)

    Orr, R. M.; Sims, H. E.; Taylor, R. J.

    2015-10-01

    Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or 'finishing' processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles.

  1. Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

    2003-07-01

    The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

  2. Experimental and modeling study of the thermal decomposition of methyl decanoate

    PubMed Central

    Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

    2013-01-01

    The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

  3. Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions.

    PubMed

    Newland, Mike J; Rickard, Andrew R; Alam, Mohammed S; Vereecken, Luc; Muñoz, Amalia; Ródenas, Milagros; Bloss, William J

    2015-02-14

    The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10(-5) for CH2OO, 26 (±10) × 10(-5) for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10(-5) for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10(-5) for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 10(11) cm(-3) for CH2OO, 13 (±43) × 10(11) cm(-3) for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 10(11) cm(-3) for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 10(11) cm(-3) for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10(-4) for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 10(13) for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10(-2). The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.

  4. Simulated drought regimes reveal community resilience and hydrological thresholds for altered decomposition.

    PubMed

    Rodríguez Pérez, Héctor; Borrel, Guillaume; Leroy, Céline; Carrias, Jean-François; Corbara, Bruno; Srivastava, Diane S; Céréghino, Régis

    2018-05-01

    Future climate scenarios forecast a 10-50% decline in rainfall in Eastern Amazonia. Altered precipitation patterns may change important ecosystem functions like decomposition through either changes in physical and chemical processes or shifts in the activity and/or composition of species. We experimentally manipulated hydroperiods (length of wet:dry cycles) in a tank bromeliad ecosystem to examine impacts on leaf litter decomposition. Gross loss of litter mass over 112 days was greatest in continuously submersed litter, lowest in continuously dry litter, and intermediate over a range of hydroperiods ranging from eight cycles of 7 wet:7 dry days to one cycle of 56 wet:56 dry days. The resilience of litter mass loss to hydroperiod length is due to a shift from biologically assisted decomposition (mostly microbial) at short wet:dry hydroperiods to physicochemical release of dissolved organic matter at longer wet:dry hydroperiods. Biologically assisted decomposition was maximized at wet:dry hydroperiods falling within the range of ambient conditions (12-22 consecutive dry days) but then declined under prolonged wet:dry hydroperiods (28 and 56 dry days. Fungal:bacterial ratios showed a similar pattern as biologically assisted decomposition to hydroperiod length. Our results suggest that microbial communities confer functional resilience to altered hydroperiod in tank bromeliad ecosystems. We predict a substantial decrease in biological activity relevant to decomposition under climate scenarios that increase consecutive dry days by 1.6- to 3.2-fold in our study area, whereas decreased frequency of dry periods will tend to increase the physicochemical component of decomposition.

  5. 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.

  6. In situ characterization of the decomposition behavior of Mg(BH4)2 by X-ray Raman scattering spectroscopy.

    PubMed

    Sahle, Christoph J; Kujawski, Simon; Remhof, Arndt; Yan, Yigang; Stadie, Nicholas P; Al-Zein, Ali; Tolan, Metin; Huotari, Simo; Krisch, Michael; Sternemann, Christian

    2016-02-21

    We present an in situ study of the thermal decomposition of Mg(BH4)2 in a hydrogen atmosphere of up to 4 bar and up to 500 °C using X-ray Raman scattering spectroscopy at the boron K-edge and the magnesium L2,3-edges. The combination of the fingerprinting analysis of both edges yields detailed quantitative information on the reaction products during decomposition, an issue of crucial importance in determining whether Mg(BH4)2 can be used as a next-generation hydrogen storage material. This work reveals the formation of reaction intermediate(s) at 300 °C, accompanied by a significant hydrogen release without the occurrence of stable boron compounds such as amorphous boron or MgB12H12. At temperatures between 300 °C and 400 °C, further hydrogen release proceeds via the formation of higher boranes and crystalline MgH2. Above 400 °C, decomposition into the constituting elements takes place. Therefore, at moderate temperatures, Mg(BH4)2 is shown to be a promising high-density hydrogen storage material with great potential for reversible energy storage applications.

  7. The partitioning of litter carbon during litter decomposition under different rainfall patterns: a laboratory study

    NASA Astrophysics Data System (ADS)

    Yang, X.; Szlavecz, K. A.; Langley, J. A.; Pitz, S.; Chang, C. H.

    2017-12-01

    Quantifying litter C into different C fluxes during litter decomposition is necessary to understand carbon cycling under changing climatic conditions. Rainfall patterns are predicted to change in the future, and their effects on the fate of litter carbon are poorly understood. Soils from deciduous forests in Smithsonian Environmental Research Center (SERC) in Maryland, USA were collected to reconstruct soil columns in the lab. 13C labeled tulip poplar leaf litter was used to trace carbon during litter decomposition. Top 1% and the mean of 15-minute historical precipitation data from nearby weather stations were considered as extreme and control rainfall intensity, respectively. Both intensity and frequency of rainfall were manipulated, while the total amount was kept constant. A pulse of CO2 efflux was detected right after each rainfall event in the soil columns with leaf litter. After the first event, CO2 efflux of the control rainfall treatment soils increased to threefold of the CO2 efflux before rain event and that of the extreme treatment soils increased to fivefold. However, in soils without leaf litter, CO2 efflux was suppressed right after rainfall events. After each rainfall event, the leaf litter contribution to CO2 efflux first showed an increase, decreased sharply in the following two days, and then stayed relatively constant. In soil columns with leaf litter, the order of cumulative CO2 efflux was control > extreme > intermediate. The order of cumulative CO2 efflux in the bare soil treatment was extreme > intermediate > control. The order of volume of leachate from different treatments was extreme > intermediate > control. Our initial results suggest that more intense rainfall events result in larger pulses of CO2, which is rarely measured in the field. Additionally, soils with and without leaf litter respond differently to precipitation events. This is important to consider in temperate regions where leaf litter cover changes throughout the year

  8. Sulfur species behavior in soil organic matter during decomposition

    USGS Publications Warehouse

    Schroth, A.W.; Bostick, B.C.; Graham, M.; Kaste, J.M.; Mitchell, M.J.; Friedland, A.J.

    2007-01-01

    Soil organic matter (SOM) is a primary re??servoir of terrestrial sulfur (S), but its role in the global S cycle remains poorly understood. We examine S speciation by X-ray absorption near-edge structure (XANES) spectroscopy to describe S species behavior during SOM decomposition. Sulfur species in SOM were best represented by organic sulfide, sulfoxide, sulfonate, and sulfate. The highest fraction of S in litter was organic sulfide, but as decomposition progressed, relative fractions of sulfonate and sulfate generally increased. Over 6-month laboratory incubations, organic sulfide was most reactive, suggesting that a fraction of this species was associated with a highly labile pool of SOM. During humification, relative concentrations of sulfoxide consistently decreased, demonstrating the importance of sulfoxide as a reactive S phase in soil. Sulfonate fractional abundance increased during humification irrespective of litter type, illustrating its relative stability in soils. The proportion of S species did not differ systematically by litter type, but organic sulfide became less abundant in conifer SOM during decomposition, while sulfate fractional abundance increased. Conversely, deciduous SOM exhibited lesser or nonexistent shifts in organic sulfide and sulfate fractions during decomposition, possibly suggesting that S reactivity in deciduous litter is coupled to rapid C mineralization and independent of S speciation. All trends were consistent in soils across study sites. We conclude that S reactivity is related to spqciation in SOM, particularly in conifer forests, and S species fractions in SOM change, during decomposition. Our data highlight the importance of intermediate valence species (sulfoxide and sulfonate) in the pedochemical cycling of organic bound S. Copyright 2007 by the American Geophysical Union.

  9. Decomposition Studies of Tetraphenylborate Slurries

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

    Crawford, C.L.

    1997-05-06

    This report details the decomposition of aqueous (K,Na) slurries in concentrated salt solutions using a more complete candidate catalyst recipe, extended testing temperatures (40-70 degrees C) and test durations of approximately 1500 hours (9 weeks). This study uses recently developed High-Pressure Liquid Chromatography (HPLC) methods for analysis of tetraphenylborate (TPB-), triphenylborane (3PB) and diphenylborinic acid (2PB). All of the present tests involve non-radioactive simulants and do not include investigations of radiolysis effects.

  10. NMR study of methane + ethane structure I hydrate decomposition.

    PubMed

    Dec, Steven F; Bowler, Kristen E; Stadterman, Laura L; Koh, Carolyn A; Sloan, E Dendy

    2007-05-24

    The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

  11. Experimental study of trimethyl aluminum decomposition

    NASA Astrophysics Data System (ADS)

    Zhang, Zhi; Pan, Yang; Yang, Jiuzhong; Jiang, Zhiming; Fang, Haisheng

    2017-09-01

    Trimethyl aluminum (TMA) is an important precursor used for metal-organic chemical vapor deposition (MOCVD) of most Al-containing structures, in particular of nitride structures. The reaction mechanism of TMA with ammonia is neither clear nor certain due to its complexity. Pyrolysis of trimethyl metal is the start of series of reactions, thus significantly affecting the growth. Experimental study of TMA pyrolysis, however, has not yet been conducted in detail. In this paper, a reflectron time-of-flight mass spectrometer is adopted to measure the TMA decomposition from room temperature to 800 °C in a special pyrolysis furnace, activated by soft X-ray from the synchrotron radiation. The results show that generation of methyl, ethane and monomethyl aluminum (MMA) indicates the start of the pyrolysis process. In the low temperature range from 25 °C to 700 °C, the main product is dimethyl aluminum (DMA) from decomposition of TMA. For temperatures larger than 700 °C, the main products are MMA, DMA, methyl and ethane.

  12. Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

    PubMed

    Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

    2018-04-26

    Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

  13. 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.

  14. 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.

  15. Comment on “A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states” [J. Chem. Phys. 142, 124312 (2015)

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

    Harding, Lawrence B.; Klippenstein, Stephen J.

    2015-10-28

    We discuss the recent report of a roaming type mechanism for the decomposition of the Criegee intermediate. We show that the predicted barrier height for this new pathway is too low by ∼30 kcal/mol owing to an inconsistent use of spin-restricted and spin-unrestricted calculations. As a result, this new pathway is not expected to compete significantly with the well-known dioxirane pathways for the decomposition of the Criegee intermediate.

  16. 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.

  17. Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2017-09-07

    High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

  18. 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

  19. 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

  20. Factors influencing leaf litter decomposition: An intersite decomposition experiment across China

    USGS Publications Warehouse

    Zhou, G.; Guan, L.; Wei, X.; Tang, X.; Liu, S.; Liu, J.; Zhang, Dongxiao; Yan, J.

    2008-01-01

    The Long-Term Intersite Decomposition Experiment in China (hereafter referred to as LTIDE-China) was established in 2002 to study how substrate quality and macroclimate factors affect leaf litter decomposition. The LTIDE-China includes a wide variety of natural and managed ecosystems, consisting of 12 forest types (eight regional broadleaf forests, three needle-leaf plantations and one broadleaf plantation) at eight locations across China. Samples of mixed leaf litter from the south subtropical evergreen broadleaf forest in Dinghushan (referred to as the DHS sample) were translocated to all 12 forest types. The leaf litter from each of other 11 forest types was placed in its original forest to enable comparison of decomposition rates of DHS and local litters. The experiment lasted for 30 months, involving collection of litterbags from each site every 3 months. Our results show that annual decomposition rate-constants, as represented by regression fitted k-values, ranged from 0.169 to 1.454/year. Climatic factors control the decomposition rate, in which mean annual temperature and annual actual evapotranspiration are dominant and mean annual precipitation is subordinate. Initial C/N and N/P ratios were demonstrated to be important factors of regulating litter decomposition rate. Decomposition process may apparently be divided into two phases controlled by different factors. In our study, 0.75 years is believed to be the dividing line of the two phases. The fact that decomposition rates of DHS litters were slower than those of local litters may have been resulted from the acclimation of local decomposer communities to extraneous substrate. ?? 2008 Springer Science+Business Media B.V.

  1. Decomposition of heterogeneous organic matterand its long-term stabilization in soils

    USGS Publications Warehouse

    Sierra, Carlos A.; Harmon, Mark E.; Perakis, Steven S.

    2011-01-01

    Soil organic matter is a complex mixture of material with heterogeneous biological, physical, and chemical properties. Decomposition models represent this heterogeneity either as a set of discrete pools with different residence times or as a continuum of qualities. It is unclear though, whether these two different approaches yield comparable predictions of organic matter dynamics. Here, we compare predictions from these two different approaches and propose an intermediate approach to study organic matter decomposition based on concepts from continuous models implemented numerically. We found that the disagreement between discrete and continuous approaches can be considerable depending on the degree of nonlinearity of the model and simulation time. The two approaches can diverge substantially for predicting long-term processes in soils. Based on our alternative approach, which is a modification of the continuous quality theory, we explored the temporal patterns that emerge by treating substrate heterogeneity explicitly. The analysis suggests that the pattern of carbon mineralization over time is highly dependent on the degree and form of nonlinearity in the model, mostly expressed as differences in microbial growth and efficiency for different substrates. Moreover, short-term stabilization and destabilization mechanisms operating simultaneously result in long-term accumulation of carbon characterized by low decomposition rates, independent of the characteristics of the incoming litter. We show that representation of heterogeneity in the decomposition process can lead to substantial improvements in our understanding of carbon mineralization and its long-term stability in soils.

  2. 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.

  3. Experimental and modeling study on decomposition kinetics of methane hydrates in different media.

    PubMed

    Liang, Minyan; Chen, Guangjin; Sun, Changyu; Yan, Lijun; Liu, Jiang; Ma, Qinglan

    2005-10-13

    The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.

  4. Mechanism of action of (2-haloethyl)nitrosoureas on DNA. Isolation and reactions of postulated 2-(alkylimino)-3-nitrosooxazolidine intermediates in the decomposition of 1,3-bis(2-chloroethyl)-, 1-(2-chloroethyl)-3-cyclohexyl-, and 1-(2-chloroethyl)-3-(4'-trans-methylcyclohexyl)-1-nitrosourea.

    PubMed

    Lown, J W; Chauhan, S M

    1981-03-01

    Three examples of the postulated but hitherto unisolated 2-(alkylimino)-3-nitrosooxazolidines (2) have been prepared containing cyclohexyl, trans-4-methylcyclohexyl, and 2-chloroethyl groups at the 2 position, respectively. These compounds correspond to intermediates previously postulated to be formed in the aqueous decomposition of the antitumor agents 1-(2-chloroethyl)-3-cyclohexyl- (CCNU), 1-(2-chloroethyl)-3-(4'-trans-methylcyclohexyl)- (MeCCNU), and 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU), respectively, Compounds 2 decompose under physiological conditions to give a range of products similar to those formed from the corresponding (2-chloroethyl)nitrosoureas, including the hitherto unrecognized 2-hydroxyethl N-alkylcarbamates (9). Compounds 2a and 2b are converted with hydrochloric acid into CCNU and MeCCNU, respectively, suggesting that 2a and 2b may be reaction intermediates of decomposition. The corresponding 3-alkyl-1-nitroso-1-(2-hydroxyethyl)ureas (4) were characterized and, since they also decompose to give the same products as 2, may arise from the ring opening of 2. The intermediacy of compounds 4 can explain the formation of hydroxyethylated nucleosides isolated by other workers from the reaction of (2-chloroethyl)nitrosoureas on polynucleotides.

  5. Can the biomass-ratio hypothesis predict mixed-species litter decomposition along a climatic gradient?

    PubMed Central

    Tardif, Antoine; Shipley, Bill; Bloor, Juliette M. G.; Soussana, Jean-François

    2014-01-01

    Background and Aims The biomass-ratio hypothesis states that ecosystem properties are driven by the characteristics of dominant species in the community. In this study, the hypothesis was operationalized as community-weighted means (CWMs) of monoculture values and tested for predicting the decomposition of multispecies litter mixtures along an abiotic gradient in the field. Methods Decomposition rates (mg g−1 d−1) of litter from four herb species were measured using litter-bed experiments with the same soil at three sites in central France along a correlated climatic gradient of temperature and precipitation. All possible combinations from one to four species mixtures were tested over 28 weeks of incubation. Observed mixture decomposition rates were compared with those predicted by the biomass-ratio hypothesis. Variability of the prediction errors was compared with the species richness of the mixtures, across sites, and within sites over time. Key Results Both positive and negative prediction errors occurred. Despite this, the biomass-ratio hypothesis was true as an average claim for all sites (r = 0·91) and for each site separately, except for the climatically intermediate site, which showed mainly synergistic deviations. Variability decreased with increasing species richness and in less favourable climatic conditions for decomposition. Conclusions Community-weighted mean values provided good predictions of mixed-species litter decomposition, converging to the predicted values with increasing species richness and in climates less favourable to decomposition. Under a context of climate change, abiotic variability would be important to take into account when predicting ecosystem processes. PMID:24482152

  6. Biological decomposition efficiency in different woodland soils.

    PubMed

    Herlitzius, H

    1983-03-01

    The decomposition (meaning disappearance) of different leaf types and artificial leaves made from cellulose hydrate foil was studied in three forests - an alluvial forest (Ulmetum), a beech forest on limestone soil (Melico-Fagetum), and a spruce forest in soil overlying limestone bedrock.Fine, medium, and coarse mesh litter bags of special design were used to investigate the roles of abiotic factors, microorganisms, and meso- and macrofauna in effecting decomposition in the three habitats. Additionally, the experimental design was carefully arranged so as to provide information about the effects on decomposition processes of the duration of exposure and the date or moment of exposure. 1. Exposure of litter samples oor 12 months showed: a) Litter enclosed in fine mesh bags decomposed to some 40-44% of the initial amount placed in each of the three forests. Most of this decomposition can be attributed to abiotic factors and microoganisms. b) Litter placed in medium mesh litter bags reduced by ca. 60% in alluvial forest, ca. 50% in beech forest and ca. 44% in spruce forest. c) Litter enclosed in coarse mesh litter bags was reduced by 71% of the initial weights exposed in alluvial and beech forests; in the spruce forest decomposition was no greater than observed with fine and medium mesh litter bags. Clearly, in spruce forest the macrofauna has little or no part to play in effecting decomposition. 2. Sequential month by month exposure of hazel leaves and cellulose hydrate foil in coarse mesh litter bags in all three forests showed that one month of exposure led to only slight material losses, they did occur smallest between March and May, and largest between June and October/November. 3. Coarse mesh litter bags containing either hazel or artificial leaves of cellulose hydrate foil were exposed to natural decomposition processes in December 1977 and subsampled monthly over a period of one year, this series constituted the From-sequence of experiments. Each of the From

  7. Molecular mechanism of metal-independent decomposition of lipid hydroperoxide 13-HPODE by halogenated quinoid carcinogens.

    PubMed

    Qin, Hao; Huang, Chun-Hua; Mao, Li; Xia, Hai-Ying; Kalyanaraman, Balaraman; Shao, Jie; Shan, Guo-Qiang; Zhu, Ben-Zhan

    2013-10-01

    Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection by-products in drinking water. 13-Hydroperoxy-9,11-octadecadienoic acid (13-HPODE) is the most extensively studied endogenous lipid hydroperoxide. Although it is well known that the decomposition of 13-HPODE can be catalyzed by transition metal ions, it is not clear whether halogenated quinones could enhance its decomposition independent of metal ions and, if so, what the unique characteristics and similarities are. Here we show that 2,5-dichloro-1,4-benzoquinone (DCBQ) could markedly enhance the decomposition of 13-HPODE and formation of reactive lipid alkyl radicals such as pentyl and 7-carboxyheptyl radicals, and the genotoxic 4-hydroxy-2-nonenal (HNE), through the complementary application of ESR spin trapping, HPLC-MS, and GC-MS methods. Interestingly, two chloroquinone-lipid alkoxyl conjugates were also detected and identified from the reaction between DCBQ and 13-HPODE. Analogous results were observed with other halogenated quinones. This represents the first report that halogenated quinoid carcinogens can enhance the decomposition of the endogenous lipid hydroperoxide 13-HPODE and formation of reactive lipid alkyl radicals and genotoxic HNE via a novel metal-independent nucleophilic substitution coupled with homolytic decomposition mechanism, which may partly explain their potential genotoxicity and carcinogenicity. Copyright © 2013 Elsevier Inc. All rights reserved.

  8. Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals

    NASA Astrophysics Data System (ADS)

    Ge, Qinghui; Mao, Yuezhi; Head-Gordon, Martin

    2018-02-01

    An energy decomposition analysis (EDA) scheme is developed for understanding the intermolecular interaction involving molecules in their excited states. The EDA utilizes absolutely localized molecular orbitals to define intermediate states and is compatible with excited state methods based on linear response theory such as configuration interaction singles and time-dependent density functional theory. The shift in excitation energy when an excited molecule interacts with the environment is decomposed into frozen, polarization, and charge transfer contributions, and the frozen term can be further separated into Pauli repulsion and electrostatics. These terms can be added to their counterparts obtained from the ground state EDA to form a decomposition of the total interaction energy. The EDA scheme is applied to study a variety of systems, including some model systems to demonstrate the correct behavior of all the proposed energy components as well as more realistic systems such as hydrogen-bonding complexes (e.g., formamide-water, pyridine/pyrimidine-water) and halide (F-, Cl-)-water clusters that involve charge-transfer-to-solvent excitations.

  9. Scoring of Decomposition: A Proposed Amendment to the Method When Using a Pig Model for Human Studies.

    PubMed

    Keough, Natalie; Myburgh, Jolandie; Steyn, Maryna

    2017-07-01

    Decomposition studies often use pigs as proxies for human cadavers. However, differences in decomposition sequences/rates relative to humans have not been scientifically examined. Descriptions of five main decomposition stages (humans) were developed and refined by Galloway and later by Megyesi. However, whether these changes/processes are alike in pigs is unclear. Any differences can have significant effects when pig models are used for human PMI estimation. This study compared human decomposition models to the changes observed in pigs. Twenty pigs (50-90 kg) were decomposed over five months and decompositional features recorded. Total body scores (TBS) were calculated. Significant differences were observed during early decomposition between pigs and humans. An amended scoring system to be used in future studies was developed. Standards for PMI estimation derived from porcine models may not directly apply to humans and may need adjustment. Porcine models, however, remain valuable to study variables influencing decomposition. © 2016 American Academy of Forensic Sciences.

  10. Fungal community structure of fallen pine and oak wood at different stages of decomposition in the Qinling Mountains, China.

    PubMed

    Yuan, Jie; Zheng, Xiaofeng; Cheng, Fei; Zhu, Xian; Hou, Lin; Li, Jingxia; Zhang, Shuoxin

    2017-10-24

    Historically, intense forest hazards have resulted in an increase in the quantity of fallen wood in the Qinling Mountains. Fallen wood has a decisive influence on the nutrient cycling, carbon budget and ecosystem biodiversity of forests, and fungi are essential for the decomposition of fallen wood. Moreover, decaying dead wood alters fungal communities. The development of high-throughput sequencing methods has facilitated the ongoing investigation of relevant molecular forest ecosystems with a focus on fungal communities. In this study, fallen wood and its associated fungal communities were compared at different stages of decomposition to evaluate relative species abundance and species diversity. The physical and chemical factors that alter fungal communities were also compared by performing correspondence analysis according to host tree species across all stages of decomposition. Tree species were the major source of differences in fungal community diversity at all decomposition stages, and fungal communities achieved the highest levels of diversity at the intermediate and late decomposition stages. Interactions between various physical and chemical factors and fungal communities shared the same regulatory mechanisms, and there was no tree species-specific influence. Improving our knowledge of wood-inhabiting fungal communities is crucial for forest ecosystem conservation.

  11. Synthesis of In2O3nanoparticles by thermal decomposition of a citrate gel precursor

    NASA Astrophysics Data System (ADS)

    Rey, J. F. Q.; Plivelic, T. S.; Rocha, R. A.; Tadokoro, S. K.; Torriani, I.; Muccillo, E. N. S.

    2005-06-01

    This paper describes the synthesis of indium oxide by a modified sol-gel method, and the study of thermal decomposition of the metal complex in air. The characterization of the intermediate as well as the final compounds was carried out by thermogravimetry, differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and small angle X-ray scattering. The results show that the indium complex decomposes to In2O3 with the formation of an intermediate compound. Nanoparticles of cubic In2O3 with crystallite sizes in the nanosize range were formed after calcination at temperatures up to 900°C. Calcined materials are characterized by a polydisperse distribution of spherical particles with sharp and smooth surfaces.

  12. Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

    NASA Astrophysics Data System (ADS)

    Cen, Peng; Wu, Wenyuan; Bian, Xue

    2018-06-01

    The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

  13. Three-pattern decomposition of global atmospheric circulation: part I—decomposition model and theorems

    NASA Astrophysics Data System (ADS)

    Hu, Shujuan; Chou, Jifan; Cheng, Jianbo

    2018-04-01

    In order to study the interactions between the atmospheric circulations at the middle-high and low latitudes from the global perspective, the authors proposed the mathematical definition of three-pattern circulations, i.e., horizontal, meridional and zonal circulations with which the actual atmospheric circulation is expanded. This novel decomposition method is proved to accurately describe the actual atmospheric circulation dynamics. The authors used the NCEP/NCAR reanalysis data to calculate the climate characteristics of those three-pattern circulations, and found that the decomposition model agreed with the observed results. Further dynamical analysis indicates that the decomposition model is more accurate to capture the major features of global three dimensional atmospheric motions, compared to the traditional definitions of Rossby wave, Hadley circulation and Walker circulation. The decomposition model for the first time realized the decomposition of global atmospheric circulation using three orthogonal circulations within the horizontal, meridional and zonal planes, offering new opportunities to study the large-scale interactions between the middle-high latitudes and low latitudes circulations.

  14. Photodegradation at day, microbial decomposition at night - decomposition in arid lands

    NASA Astrophysics Data System (ADS)

    Gliksman, Daniel; Gruenzweig, Jose

    2014-05-01

    Our current knowledge of decomposition in dry seasons and its role in carbon turnover is fragmentary. So far, decomposition during dry seasons was mostly attributed to abiotic mechanisms, mainly photochemical and thermal degradation, while the contribution of microorganisms to the decay process was excluded. We asked whether microbial decomposition occurs during the dry season and explored its interaction with photochemical degradation under Mediterranean climate. We conducted a litter bag experiment with local plant litter and manipulated litter exposure to radiation using radiation filters. We found notable rates of CO2 fluxes from litter which were related to microbial activity mainly during night-time throughout the dry season. This activity was correlated with litter moisture content and high levels of air humidity and dew. Day-time CO2 fluxes were related to solar radiation, and radiation manipulation suggested photodegradation as the underlying mechanism. In addition, a decline in microbial activity was followed by a reduction in photodegradation-related CO2 fluxes. The levels of microbial decomposition and photodegradation in the dry season were likely the factors influencing carbon mineralization during the subsequent wet season. This study showed that microbial decomposition can be a dominant contributor to CO2 emissions and mass loss in the dry season and it suggests a regulating effect of microbial activity on photodegradation. Microbial decomposition is an important contributor to the dry season decomposition and impacts the annual litter turn-over rates in dry regions. Global warming may lead to reduced moisture availability and dew deposition, which may greatly influence not only microbial decomposition of plant litter, but also photodegradation.

  15. Decomposition of P(CH 3) 3 on Ru(0001): comparison with PH 3 and PCl 3

    NASA Astrophysics Data System (ADS)

    Tao, H.-S.; Diebold, U.; Shinn, N. D.; Madey, T. E.

    1997-04-01

    The decomposition of P(CH 3) 3 adsorbed on Ru(0001) at 80 K is studied by soft X-ray photoelectron spectroscopy using synchrotron radiation. Using the chemical shifts in the P 2p core levels, we are able to identify various phosphorus-containing surface reaction products and follow their reactions on Ru(0001). It is found that P(CH 3) 3 undergoes a step-wise demethylation on Ru(0001), P(CH 3) 3 → P(CH 3) 2 → P(CH 3) → P, which is complete around ˜450 K. These results are compared with the decomposition of isostructural PH 3 and PCl 3 on Ru(0001). The decomposition of PH 3 involves a stable intermediate, labeled as PH x, and follows a reaction of: PH 3 → PH x → P, which is complete around ˜190 K. The conversion of chemisorbed phosphorus to ruthenium phosphide is observed and is complete around ˜700 K on Ru(0001). PCl 3 also follows a step-wise decomposition reaction, PCl 3 → PCl 2 → PCl → P, which is complete around ˜300 K. The energetics of the adsorption and the step-wise decomposition reactions of PH 3, PCl 3 and P(CH 3) 3 are estimated using the bond order conservation Morse potential (BOCMP) method. The energetics calculated using the BOCMP method agree qualitatively with the experimental data.

  16. 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(-).

  17. Thermal decomposition of pyrazole to vinylcarbene + N 2: A first principles/RRKM study

    NASA Astrophysics Data System (ADS)

    da Silva, Gabriel

    2009-05-01

    Thermal decomposition of pyrazole, a five-membered nitrogen-containing heterocycle, has been studied using ab initio G3X theory and RRKM rate theory. The decomposition mechanism involves an intramolecular hydrogen shift to 3 H-pyrazole, followed by ring opening to 3-diazo-1-propene and dissociation to vinylcarbene (CH 2CHCH) + N 2. At 1 atm the calculated rate equation k [s -1] = 1.26 × 10 50T-10.699e -41200/T is obtained, which agrees with the results of flash vacuum pyrolysis experiments. The pyrazole decomposition product vinylcarbene is expected to rearrange to propyne, making pyrazole decomposition essentially thermoneutral. It is hypothesized that at high concentrations vinylcarbene could undergo a self-reaction to 1,3- and 1,4-cyclohexadiene.

  18. A statistical approach based on accumulated degree-days to predict decomposition-related processes in forensic studies.

    PubMed

    Michaud, Jean-Philippe; Moreau, Gaétan

    2011-01-01

    Using pig carcasses exposed over 3 years in rural fields during spring, summer, and fall, we studied the relationship between decomposition stages and degree-day accumulation (i) to verify the predictability of the decomposition stages used in forensic entomology to document carcass decomposition and (ii) to build a degree-day accumulation model applicable to various decomposition-related processes. Results indicate that the decomposition stages can be predicted with accuracy from temperature records and that a reliable degree-day index can be developed to study decomposition-related processes. The development of degree-day indices opens new doors for researchers and allows for the application of inferential tools unaffected by climatic variability, as well as for the inclusion of statistics in a science that is primarily descriptive and in need of validation methods in courtroom proceedings. © 2010 American Academy of Forensic Sciences.

  19. Factors controlling bark decomposition and its role in wood decomposition in five tropical tree species

    PubMed Central

    Dossa, Gbadamassi G. O.; Paudel, Ekananda; Cao, Kunfang; Schaefer, Douglas; Harrison, Rhett D.

    2016-01-01

    Organic matter decomposition represents a vital ecosystem process by which nutrients are made available for plant uptake and is a major flux in the global carbon cycle. Previous studies have investigated decomposition of different plant parts, but few considered bark decomposition or its role in decomposition of wood. However, bark can comprise a large fraction of tree biomass. We used a common litter-bed approach to investigate factors affecting bark decomposition and its role in wood decomposition for five tree species in a secondary seasonal tropical rain forest in SW China. For bark, we implemented a litter bag experiment over 12 mo, using different mesh sizes to investigate effects of litter meso- and macro-fauna. For wood, we compared the decomposition of branches with and without bark over 24 mo. Bark in coarse mesh bags decomposed 1.11–1.76 times faster than bark in fine mesh bags. For wood decomposition, responses to bark removal were species dependent. Three species with slow wood decomposition rates showed significant negative effects of bark-removal, but there was no significant effect in the other two species. Future research should also separately examine bark and wood decomposition, and consider bark-removal experiments to better understand roles of bark in wood decomposition. PMID:27698461

  20. Factors controlling bark decomposition and its role in wood decomposition in five tropical tree species.

    PubMed

    Dossa, Gbadamassi G O; Paudel, Ekananda; Cao, Kunfang; Schaefer, Douglas; Harrison, Rhett D

    2016-10-04

    Organic matter decomposition represents a vital ecosystem process by which nutrients are made available for plant uptake and is a major flux in the global carbon cycle. Previous studies have investigated decomposition of different plant parts, but few considered bark decomposition or its role in decomposition of wood. However, bark can comprise a large fraction of tree biomass. We used a common litter-bed approach to investigate factors affecting bark decomposition and its role in wood decomposition for five tree species in a secondary seasonal tropical rain forest in SW China. For bark, we implemented a litter bag experiment over 12 mo, using different mesh sizes to investigate effects of litter meso- and macro-fauna. For wood, we compared the decomposition of branches with and without bark over 24 mo. Bark in coarse mesh bags decomposed 1.11-1.76 times faster than bark in fine mesh bags. For wood decomposition, responses to bark removal were species dependent. Three species with slow wood decomposition rates showed significant negative effects of bark-removal, but there was no significant effect in the other two species. Future research should also separately examine bark and wood decomposition, and consider bark-removal experiments to better understand roles of bark in wood decomposition.

  1. Removal behaviors of sulfamonomethoxine and its degradation intermediates in fresh aquaculture wastewater using zeolite/TiO2 composites.

    PubMed

    Nomura, Youhei; Fukahori, Shuji; Fukada, Haruhisa; Fujiwara, Taku

    2017-10-15

    Removal efficiencies of sulfamonomethoxine (SMM) and its degradation intermediates formed by treatment with zeolite/TiO 2 composites through adsorption and photocatalysis were investigated in fresh aquaculture wastewater (FAWW). Coexistent substances in the FAWW showed no inhibitory effects against SMM adsorption. Although coexistent substances in the FAWW inhibited the photocatalytic decomposition of SMM, the composites mitigated the inhibition, possibly because of concentration of SMM on their surface by adsorption. LC/MS/MS analyses revealed that hydroxylation of amino phenyl and pyrimidinyl portions, transformation of the amino group in the amino phenyl portion into a nitroso group, and substitution of the methoxy group with a hydroxyl group occurring in the initial reaction resulted in the formation of various intermediates during the photocatalysis of SMM. All detected intermediates had a ring structure, and almost all intermediates disappeared at the same time SMM was completely decomposed. Ph-OH formed by hydroxylation of the phenyl portion was detected upon decomposition of SMM during photocatalysis. The removal of Ph-OH by the composites proceeded more rapidly than that by TiO 2 alone under ultraviolet irradiation. The SMM and Ph-OH were completely degraded by the composites within 30min, showing that the zeolite/TiO 2 composites were effective in removing SMM and its intermediates from FAWW. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. 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.

  3. 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.

  4. Density-based Energy Decomposition Analysis for Intermolecular Interactions with Variationally Determined Intermediate State Energies

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

    Wu, Q.; Ayers, P.W.; Zhang, Y.

    2009-10-28

    The first purely density-based energy decomposition analysis (EDA) for intermolecular binding is developed within the density functional theory. The most important feature of this scheme is to variationally determine the frozen density energy, based on a constrained search formalism and implemented with the Wu-Yang algorithm [Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003) ]. This variational process dispenses with the Heitler-London antisymmetrization of wave functions used in most previous methods and calculates the electrostatic and Pauli repulsion energies together without any distortion of the frozen density, an important fact that enables a clean separation of these twomore » terms from the relaxation (i.e., polarization and charge transfer) terms. The new EDA also employs the constrained density functional theory approach [Q. Wu and T. Van Voorhis, Phys. Rev. A 72, 24502 (2005)] to separate out charge transfer effects. Because the charge transfer energy is based on the density flow in real space, it has a small basis set dependence. Applications of this decomposition to hydrogen bonding in the water dimer and the formamide dimer show that the frozen density energy dominates the binding in these systems, consistent with the noncovalent nature of the interactions. A more detailed examination reveals how the interplay of electrostatics and the Pauli repulsion determines the distance and angular dependence of these hydrogen bonds.« less

  5. Theoretical study of gas hydrate decomposition kinetics: model predictions.

    PubMed

    Windmeier, Christoph; Oellrich, Lothar R

    2013-11-27

    In order to provide an estimate of intrinsic gas hydrate dissolution and dissociation kinetics, the Consecutive Desorption and Melting Model (CDM) was developed in a previous publication (Windmeier, C.; Oellrich, L. R. J. Phys. Chem. A 2013, 117, 10151-10161). In this work, an extensive summary of required model data is given. Obtained model predictions are discussed with respect to their temperature dependence as well as their significance for technically relevant areas of gas hydrate decomposition. As a result, an expression for determination of the intrinsic gas hydrate decomposition kinetics for various hydrate formers is given together with an estimate for the maximum possible rates of gas hydrate decomposition.

  6. Effect of intermediate soil cover on municipal solid waste decomposition.

    PubMed

    Márquez-Benavides, L; Watson-Craik, I

    2003-01-01

    A complex series of chemical and microbiological reactions is initiated with the burial of refuse in a sanitary landfill. At the end of each labour day, the municipal solid wastes (MSW) are covered with native soil (or an alternative material). To investigate interaction between the intermediate cover and the MSW, five sets of columns were set up, one packed with refuse only, and four with a soil-refuse mixture (a clay loam, an organic-rich peaty soil, a well limed sandy soil and a chalky soil). The anaerobic degradation over 6 months was followed in terms of leachate volatile fatty acids, chemical oxygen demand, pH and ammoniacal-N performance. Results suggest that the organic-rich peaty soil may accelerate the end of the acidogenic phase. Clay appeared not to have a significant effect on the anaerobic degradation process.

  7. 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

  8. Dominant modal decomposition method

    NASA Astrophysics Data System (ADS)

    Dombovari, Zoltan

    2017-03-01

    The paper deals with the automatic decomposition of experimental frequency response functions (FRF's) of mechanical structures. The decomposition of FRF's is based on the Green function representation of free vibratory systems. After the determination of the impulse dynamic subspace, the system matrix is formulated and the poles are calculated directly. By means of the corresponding eigenvectors, the contribution of each element of the impulse dynamic subspace is determined and the sufficient decomposition of the corresponding FRF is carried out. With the presented dominant modal decomposition (DMD) method, the mode shapes, the modal participation vectors and the modal scaling factors are identified using the decomposed FRF's. Analytical example is presented along with experimental case studies taken from machine tool industry.

  9. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    PubMed

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  10. Parametric studies of diethyl phosphoramidate photocatalytic decomposition over TiO2.

    PubMed

    Sun, Bo; Vorontsov, Alexander V; Smirniotis, Panagiotis G

    2011-02-28

    The present study is focused on influences of parameters including pH, temperature, TiO(2) catalyst concentration, and reactant concentration on the rate of photocatalytic diethyl phosphoramidate (DEPA) decomposition with Hombikat UV 100 (HK) and Degussa P25 (P25) TiO(2). Total mineralization of DEPA is observed. Two regimes of pH, namely in acid and near-neutral environments were found where maximum total carbon (TC) decomposition was observed. The electrostatic effects on adsorption over the TiO(2) surface explain the above phenomena. The maximum rate is observed for P25 at DEPA concentration 1.3 mM whereas the rate grows continuously with DEPA concentration rise for HK. The temperature dependence of TC decomposition rate in the range of 15-63°C with both HK and P25 follows the Arrhenius equation. The activation energy for total carbon decomposition with HK and P25 are 29.5±1.0 and 24.3±3.1 kJ/mol, respectively. The decomposition rate of DEPA is larger over P25 than over HK. The rate over P25 increases faster than that with HK for each unit of the titania added when the TiO(2) concentration is less than 375 mg/l. The higher light absorption and particles aggregation of P25 are responsible for the decrease of reaction rate we observed at catalyst concentration above a certain level. In contrast, the rate over HK increases monotonically with the concentration of the photocatalyst used. Copyright © 2010 Elsevier B.V. All rights reserved.

  11. 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.

  12. Decomposition of 1,4-dioxane by advanced oxidation and biochemical process.

    PubMed

    Kim, Chang-Gyun; Seo, Hyung-Joon; Lee, Byung-Ryul

    2006-01-01

    This study was undertaken to determine the optimal decomposition conditions when 1,4-dioxane was degraded using either the AOPs (Advanced Oxidation Processes) or the BAC-TERRA microbial complex. The advanced oxidation was operated with H2O2, in the range 4.7 to 51 mM, under 254 nm (25 W lamp) illumination, while varying the reaction parameters, such as the air flow rate and reaction time. The greatest oxidation rate (96%) of 1,4-dioxane was achieved with H2O2 concentration of 17 mM after a 2-hr reaction. As a result of this reaction, organic acid intermediates were formed, such as acetic, propionic and butyric acids. Furthermore, the study revealed that suspended particles, i.e., bio-flocs, kaolin and pozzolan, in the reaction were able to have an impact on the extent of 1,4-dioxane decomposition. The decomposition of 1,4-dioxane in the presence of bio-flocs was significantly declined due to hindered UV penetration through the solution as a result of the consistent dispersion of bio-particles. In contrast, dosing with pozzolan decomposed up to 98.8% of the 1,4-dioxane after 2 hr of reaction. Two actual wastewaters, from polyester manufacturing, containing 1,4-dioxane in the range 370 to 450 mg/L were able to be oxidized by as high as 100% within 15 min with the introduction of 100:200 (mg/L) Fe(II):H202 under UV illumination. Aerobic biological decomposition, employing BAC-TERRA, was able to remove up to 90% of 1,4-dioxane after 15 days of incubation. In the meantime, the by-products (i.e., acetic, propionic and valeric acid) generated were similar to those formed during the AOPs investigation. According to kinetic studies, both photo-decomposition and biodegradation of 1,4-dioxane followed pseudo first-order reaction kinetics, with k = 5 x 10(-4) s(-1) and 2.38 x 10(-6) s(-1), respectively. It was concluded that 1,4-dioxane could be readily degraded by both AOPs and BAC-TERRA, and that the actual polyester wastewater containing 1,4-dioxane could be successfully

  13. Repeated decompositions reveal the stability of infomax decomposition of fMRI data

    PubMed Central

    Duann, Jeng-Ren; Jung, Tzyy-Ping; Sejnowski, Terrence J.; Makeig, Scott

    2010-01-01

    In this study, we decomposed 12 fMRI data sets from six subjects each 101 times using the infomax algorithm. The first decomposition was taken as a reference decomposition; the others were used to form a component matrix of 100 by 100 components. Equivalence relations between components in this matrix, defined as maximum spatial correlations to the components of the reference decomposition, were found by the Hungarian sorting method and used to form 100 equivalence classes for each data set. We then tested the reproducibility of the matched components in the equivalence classes using uncertainty measures based on component distributions, time courses, and ROC curves. Infomax ICA rarely failed to derive nearly the same components in different decompositions. Very few components per data set were poorly reproduced, even using vector angle uncertainty measures stricter than correlation and detection theory measures. PMID:17281453

  14. 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.

  15. 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.

  16. Oxidative decomposition of propylene carbonate in lithium ion batteries: a DFT study.

    PubMed

    Leggesse, Ermias Girma; Lin, Rao Tung; Teng, Tsung-Fan; Chen, Chi-Liang; Jiang, Jyh-Chiang

    2013-08-22

    This paper reports an in-depth mechanistic study on the oxidative decomposition of propylene carbonate in the presence of lithium salts (LiClO4, LiBF4, LiPF6, and LiAsF6) with the aid of density functional theory calculations at the B3LYP/6-311++G(d,p) level of theory. The solvent effect is accounted for by using the implicit solvation model with density method. Moreover, the rate constants for the decompositions of propylene carbonate have been investigated by using transition-state theory. The shortening of the original carbonyl C-O bond and a lengthening of the adjacent ethereal C-O bonds of propylene carbonate, which occurs as a result of oxidation, leads to the formation of acetone radical and CO2 as a primary oxidative decomposition product. The termination of the primary radical generates polycarbonate, acetone, diketone, 2-(ethan-1-ylium-1-yl)-4-methyl-1,3-dioxolan-4-ylium, and CO2. The thermodynamic and kinetic data show that the major oxidative decomposition products of propylene carbonate are independent of the type of lithium salt. However, the decomposition rate constants of propylene carbonate are highly affected by the lithium salt type. On the basis of the rate constant calculations using transition-state theory, the order of gas volume generation is: [PC-ClO4](-) > [PC-BF4](-) > [PC-AsF6](-) > [PC-PF6](-).

  17. 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

  18. A two-stage linear discriminant analysis via QR-decomposition.

    PubMed

    Ye, Jieping; Li, Qi

    2005-06-01

    Linear Discriminant Analysis (LDA) is a well-known method for feature extraction and dimension reduction. It has been used widely in many applications involving high-dimensional data, such as image and text classification. An intrinsic limitation of classical LDA is the so-called singularity problems; that is, it fails when all scatter matrices are singular. Many LDA extensions were proposed in the past to overcome the singularity problems. Among these extensions, PCA+LDA, a two-stage method, received relatively more attention. In PCA+LDA, the LDA stage is preceded by an intermediate dimension reduction stage using Principal Component Analysis (PCA). Most previous LDA extensions are computationally expensive, and not scalable, due to the use of Singular Value Decomposition or Generalized Singular Value Decomposition. In this paper, we propose a two-stage LDA method, namely LDA/QR, which aims to overcome the singularity problems of classical LDA, while achieving efficiency and scalability simultaneously. The key difference between LDA/QR and PCA+LDA lies in the first stage, where LDA/QR applies QR decomposition to a small matrix involving the class centroids, while PCA+LDA applies PCA to the total scatter matrix involving all training data points. We further justify the proposed algorithm by showing the relationship among LDA/QR and previous LDA methods. Extensive experiments on face images and text documents are presented to show the effectiveness of the proposed algorithm.

  19. Decomposition techniques

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1992-01-01

    Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed. ?? 1992.

  20. Regular Decompositions for H(div) Spaces

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

    Kolev, Tzanio; Vassilevski, Panayot

    We study regular decompositions for H(div) spaces. In particular, we show that such regular decompositions are closely related to a previously studied “inf-sup” condition for parameter-dependent Stokes problems, for which we provide an alternative, more direct, proof.

  1. Live Decomposition Imaging of HMX/HTPB Based Formulations During Cook-Off in the Dual Window Test Vehicle

    NASA Astrophysics Data System (ADS)

    White, Nathan; Reeves, Tom; Cheese, Phil; Stennett, Christopher; Wood, Andrew; Cook, Malcolm; Syanco Ltd Team; Cranfield University Team; DE&S, MoD Abbey Wood Team

    2017-06-01

    Thin, cylindrical samples of HMX/HTPB formulations with solids loadings from 85-95% by mass have been heated at 1oC/minute until a reaction occurred in the new dual window cook-off test vehicle. The test vehicle has captured the response of these formulations, and shown the influence of variables such as confinement, heating rate and sample size. Live imaging of the heated samples revealed that as with pure nitramine samples, three distinct stages of change take place during heating; phase changes, melting and slow, flameless decomposition with production of gaseous intermediates and finally burning with a luminous flame of the gaseous intermediates. In addition, the binder appears to undergo decomposition before the HMX, darkening along the edge closest to the thermal input before the HMX melts. Prior to violent reaction, flame speeds were measured at approximately 30m/s for high confinement, which reduces by 2-3 orders of magnitude when confinement is lowered. The melting point of HMX has been observed below the widely reported value at 220oC, and requires further investigation.

  2. Thermal Decomposition of 1,5-Dinitrobiuret (DNB): Direct Dynamics Trajectory Simulations and Statistical Modeling

    DTIC Science & Technology

    2011-05-03

    18 . NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON Dr. Tommy W. Hawkins a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE...branching using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, 18 and finally to the analysis of inter-conversions of primary decomposition products...theory, 18 was employed to examine the properties of the reactant, intermediate complex and transition states as a function of the total internal energy

  3. DFT study of hydrogen production from formic acid decomposition on Pd-Au alloy nanoclusters

    NASA Astrophysics Data System (ADS)

    Liu, D.; Gao, Z. Y.; Wang, X. C.; Zeng, J.; Li, Y. M.

    2017-12-01

    Recently, it has been reported that the hydrogen production rate of formic acid decomposition can be significantly increased using Pd-Au binary alloy nano-catalysts [Wang et al. J. Mater. Chem. A 1 (2013) 12721-12725]. To explain the reaction mechanism of this alloy catalysis method, formic acid decomposition reactions on pure Pd and Pd-Au alloy nanoclusters are studied via density functional theory simulations. The simulation results indicate that the addition of inert element Au would not influence formic acid decomposition on Pd surface sites of Pd-Au alloy nanoclusters. On the other hand, the existence of Au surface sites brings relative weak hydrogen atom adsorption. On Pd-Au alloy nanoclusters, the dissociated hydrogen atoms from formic acid are easier to combine as hydrogen molecules than that on pure Pd clusters. Via the synergetic effect between Pd and Au, both formic acid decomposition and hydrogen production are events with large probability, which eventually results in high hydrogen production rate.

  4. Optimal domain decomposition strategies

    NASA Technical Reports Server (NTRS)

    Yoon, Yonghyun; Soni, Bharat K.

    1995-01-01

    The primary interest of the authors is in the area of grid generation, in particular, optimal domain decomposition about realistic configurations. A grid generation procedure with optimal blocking strategies has been developed to generate multi-block grids for a circular-to-rectangular transition duct. The focus of this study is the domain decomposition which optimizes solution algorithm/block compatibility based on geometrical complexities as well as the physical characteristics of flow field. The progress realized in this study is summarized in this paper.

  5. GC × GC-TOFMS and supervised multivariate approaches to study human cadaveric decomposition olfactive signatures.

    PubMed

    Stefanuto, Pierre-Hugues; Perrault, Katelynn A; Stadler, Sonja; Pesesse, Romain; LeBlanc, Helene N; Forbes, Shari L; Focant, Jean-François

    2015-06-01

    In forensic thanato-chemistry, the understanding of the process of soft tissue decomposition is still limited. A better understanding of the decomposition process and the characterization of the associated volatile organic compounds (VOC) can help to improve the training of victim recovery (VR) canines, which are used to search for trapped victims in natural disasters or to locate corpses during criminal investigations. The complexity of matrices and the dynamic nature of this process require the use of comprehensive analytical methods for investigation. Moreover, the variability of the environment and between individuals creates additional difficulties in terms of normalization. The resolution of the complex mixture of VOCs emitted by a decaying corpse can be improved using comprehensive two-dimensional gas chromatography (GC × GC), compared to classical single-dimensional gas chromatography (1DGC). This study combines the analytical advantages of GC × GC coupled to time-of-flight mass spectrometry (TOFMS) with the data handling robustness of supervised multivariate statistics to investigate the VOC profile of human remains during early stages of decomposition. Various supervised multivariate approaches are compared to interpret the large data set. Moreover, early decomposition stages of pig carcasses (typically used as human surrogates in field studies) are also monitored to obtain a direct comparison of the two VOC profiles and estimate the robustness of this human decomposition analog model. In this research, we demonstrate that pig and human decomposition processes can be described by the same trends for the major compounds produced during the early stages of soft tissue decomposition.

  6. Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

    PubMed

    Pathak, Vinay; Prasad, Ankush; Pospíšil, Pavel

    2017-01-01

    Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

  7. Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II

    PubMed Central

    Pathak, Vinay; Prasad, Ankush

    2017-01-01

    Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. PMID:28732060

  8. Pseudospectral reverse time migration based on wavefield decomposition

    NASA Astrophysics Data System (ADS)

    Du, Zengli; Liu, Jianjun; Xu, Feng; Li, Yongzhang

    2017-05-01

    The accuracy of seismic numerical simulations and the effectiveness of imaging conditions are important in reverse time migration studies. Using the pseudospectral method, the precision of the calculated spatial derivative of the seismic wavefield can be improved, increasing the vertical resolution of images. Low-frequency background noise, generated by the zero-lag cross-correlation of mismatched forward-propagated and backward-propagated wavefields at the impedance interfaces, can be eliminated effectively by using the imaging condition based on the wavefield decomposition technique. The computation complexity can be reduced when imaging is performed in the frequency domain. Since the Fourier transformation in the z-axis may be derived directly as one of the intermediate results of the spatial derivative calculation, the computation load of the wavefield decomposition can be reduced, improving the computation efficiency of imaging. Comparison of the results for a pulse response in a constant-velocity medium indicates that, compared with the finite difference method, the peak frequency of the Ricker wavelet can be increased by 10-15 Hz for avoiding spatial numerical dispersion, when the second-order spatial derivative of the seismic wavefield is obtained using the pseudospectral method. The results for the SEG/EAGE and Sigsbee2b models show that the signal-to-noise ratio of the profile and the imaging quality of the boundaries of the salt dome migrated using the pseudospectral method are better than those obtained using the finite difference method.

  9. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    NASA Astrophysics Data System (ADS)

    Sun, Hongyan; Vaghjiani, Ghanshyam L.

    2015-05-01

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation

  10. Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

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

    Sun, Hongyan; Vaghjiani, Ghanshyam G.

    2015-05-26

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal

  11. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

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

    Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of

  12. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret.

    PubMed

    Sun, Hongyan; Vaghjiani, Ghanshyam L

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation

  13. The impact of shallow burial on differential decomposition to the body: a temperate case study.

    PubMed

    Schotsmans, Eline M J; Van de Voorde, Wim; De Winne, Joan; Wilson, Andrew S

    2011-03-20

    Extant literature contains a number of specific case studies on differential decomposition involving adipocere formation or desiccation, but few describe the co-occurrence of these features within a temperate climate. The case of a 65-year-old male, partially buried in a shallow grave for 7 months, is presented in which the soft tissues of the body were outwardly well preserved. The right leg was desiccated, some parts of the body were covered with adipocere (head, neck, right shoulder, upper torso and left leg) and other parts could be classified as in the early stages of decomposition. In this study the taphonomic variables resulting in differential decomposition with desiccation and adipocere formation are discussed. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  14. Trend extraction using empirical mode decomposition and statistical empirical mode decomposition: Case study: Kuala Lumpur stock market

    NASA Astrophysics Data System (ADS)

    Jaber, Abobaker M.

    2014-12-01

    Two nonparametric methods for prediction and modeling of financial time series signals are proposed. The proposed techniques are designed to handle non-stationary and non-linearity behave and to extract meaningful signals for reliable prediction. Due to Fourier Transform (FT), the methods select significant decomposed signals that will be employed for signal prediction. The proposed techniques developed by coupling Holt-winter method with Empirical Mode Decomposition (EMD) and it is Extending the scope of empirical mode decomposition by smoothing (SEMD). To show performance of proposed techniques, we analyze daily closed price of Kuala Lumpur stock market index.

  15. A procedure for the assessment of the toxicity of intermediates and products formed during the accidental thermal decomposition of a chemical species.

    PubMed

    Di Somma, Ilaria; Pollio, Antonino; Pinto, Gabriele; De Falco, Maria; Pizzo, Elio; Andreozzi, Roberto

    2010-04-15

    The knowledge of the substances which form when a molecule undergoes chemical reactions under unusual conditions is required by European legislation to evaluate the risks associated with an industrial chemical process. A thermal decomposition is often the result of a loss of control of the process which leads to the formation of many substances in some cases not easily predictable. The evaluation of the change of an overall toxicity passing from the parent compound to the mixture of its thermal decomposition products has been already proposed as a practical approach to this problem when preliminary indications about the temperature range in which the molecule decomposes are available. A new procedure is proposed in this work for the obtainment of the mixtures of thermal decomposition products also when there is no previous information about the thermal behaviour of investigated molecules. A scanning calorimetric run that is aimed to identify the onset temperature of the decomposition process is coupled to an isoperibolic one in order to obtain and collect the products. An algal strain is adopted for toxicological assessments of chemical compounds and mixtures. An extension of toxicological investigations to human cells is also attempted. 2009 Elsevier B.V. All rights reserved.

  16. Reactive molecular dynamics simulation of solid nitromethane impact on (010) surfaces induced and nonimpact thermal decomposition.

    PubMed

    Guo, Feng; Cheng, Xin-lu; Zhang, Hong

    2012-04-12

    Which is the first step in the decomposition process of nitromethane is a controversial issue, proton dissociation or C-N bond scission. We applied reactive force field (ReaxFF) molecular dynamics to probe the initial decomposition mechanisms of nitromethane. By comparing the impact on (010) surfaces and without impact (only heating) for nitromethane simulations, we found that proton dissociation is the first step of the pyrolysis of nitromethane, and the C-N bond decomposes in the same time scale as in impact simulations, but in the nonimpact simulation, C-N bond dissociation takes place at a later time. At the end of these simulations, a large number of clusters are formed. By analyzing the trajectories, we discussed the role of the hydrogen bond in the initial process of nitromethane decompositions, the intermediates observed in the early time of the simulations, and the formation of clusters that consisted of C-N-C-N chain/ring structures.

  17. 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.

  18. TE/TM decomposition of electromagnetic sources

    NASA Technical Reports Server (NTRS)

    Lindell, Ismo V.

    1988-01-01

    Three methods are given by which bounded EM sources can be decomposed into two parts radiating transverse electric (TE) and transverse magnetic (TM) fields with respect to a given constant direction in space. The theory applies source equivalence and nonradiating source concepts, which lead to decomposition methods based on a recursive formula or two differential equations for the determination of the TE and TM components of the original source. Decompositions for a dipole in terms of point, line, and plane sources are studied in detail. The planar decomposition is seen to match to an earlier result given by Clemmow (1963). As an application of the point decomposition method, it is demonstrated that the general exact image expression for the Sommerfeld half-space problem, previously derived through heuristic reasoning, can be more straightforwardly obtained through the present decomposition method.

  19. 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

  20. Nitrosonium-catalyzed decomposition of s-nitrosothiols in solution: a theoretical and experimental study.

    PubMed

    Zhao, Yi-Lei; McCarren, Patrick R; Houk, K N; Choi, Bo Yoon; Toone, Eric J

    2005-08-10

    The decomposition of S-nitrosothiols (RSNO) in solution under oxidative conditions is significantly faster than can be accounted for by homolysis of the S-N bond. Here we propose a cationic chain mechanism in which nitrosation of nitrosothiol produces a nitrosated cation that, in turn, reacts with a second nitrosothiol to produce nitrosated disulfide and the NO dimer. The nitrosated disulfide acts as a source of nitrosonium for nitrosothiol nitrosation, completing the catalytic cycle. The mechanism accounts for several unexplained facets of nitrosothiol chemistry in solution, including the observation that the decomposition of an RSNO is accelerated by O(2), mixtures of O(2) and NO, and other oxidants, that decomposition is inhibited by thiols and other antioxidants, that decomposition is dependent on sulfur substitution, and that decomposition often shows nonintegral kinetic orders.

  1. 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.

  2. RESOLVING THE ACTIVE GALACTIC NUCLEUS AND HOST EMISSION IN THE MID-INFRARED USING A MODEL-INDEPENDENT SPECTRAL DECOMPOSITION

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

    Hernán-Caballero, Antonio; Alonso-Herrero, Almudena; Hatziminaoglou, Evanthia

    2015-04-20

    We present results on the spectral decomposition of 118 Spitzer Infrared Spectrograph (IRS) spectra from local active galactic nuclei (AGNs) using a large set of Spitzer/IRS spectra as templates. The templates are themselves IRS spectra from extreme cases where a single physical component (stellar, interstellar, or AGN) completely dominates the integrated mid-infrared emission. We show that a linear combination of one template for each physical component reproduces the observed IRS spectra of AGN hosts with unprecedented fidelity for a template fitting method with no need to model extinction separately. We use full probability distribution functions to estimate expectation values andmore » uncertainties for observables, and find that the decomposition results are robust against degeneracies. Furthermore, we compare the AGN spectra derived from the spectral decomposition with sub-arcsecond resolution nuclear photometry and spectroscopy from ground-based observations. We find that the AGN component derived from the decomposition closely matches the nuclear spectrum with a 1σ dispersion of 0.12 dex in luminosity and typical uncertainties of ∼0.19 in the spectral index and ∼0.1 in the silicate strength. We conclude that the emission from the host galaxy can be reliably removed from the IRS spectra of AGNs. This allows for unbiased studies of the AGN emission in intermediate- and high-redshift galaxies—currently inaccesible to ground-based observations—with archival Spitzer/IRS data and in the future with the Mid-InfraRed Instrument of the James Webb Space Telescope. The decomposition code and templates are available at http://denebola.org/ahc/deblendIRS.« less

  3. HPLC and HPLC/MS/MS Studies on Stress, Accelerated and Intermediate Degradation Tests of Antivirally Active Tricyclic Analog of Acyclovir.

    PubMed

    Lesniewska, Monika A; Dereziński, Paweł; Klupczyńska, Agnieszka; Kokot, Zenon J; Ostrowski, Tomasz; Zeidler, Joanna; Muszalska, Izabela

    2015-01-01

    The degradation behavior of a tricyclic analog of acyclovir [6-(4-MeOPh)-TACV] was determined in accordance with International Conference on Harmonization guidelines for good clinical practice under different stress conditions (neutral hydrolysis, strong acid/base degradation, oxidative decomposition, photodegradation, and thermal degradation). Accelerated [40±2°C/75%±5% relative humidity (RH)] and intermediate (30±2°C/65%±5% RH) stability tests were also performed. For observation of the degradation of the tested compound the RP-HPLC was used, whereas for the analysis of its degradation products HPLC/MS/MS was used. Degradation of the tested substance allowed its classification as unstable in neutral environment, acidic/alkaline medium, and in the presence of oxidizing agent. The tested compound was also light sensitive and was classified as photolabile both in solution and in the solid phase. However, the observed photodegradation in the solid phase was at a much lower level than in the case of photodegradation in solution. The study showed that both air temperature and RH had no significant effect on the stability of the tested substance during storage for 1 month at 100°C (dry heat) as well as during accelerated and intermediate tests. Based on the HPLC/MS/MS analysis, it can be concluded that acyclovir was formed as a degradation product of 6-(4-MeOPh)-TACV.

  4. Efficient photoreductive decomposition of N-nitrosodimethylamine by UV/iodide process.

    PubMed

    Sun, Zhuyu; Zhang, Chaojie; Zhao, Xiaoyun; Chen, Jing; Zhou, Qi

    2017-05-05

    N-nitrosodimethylamine (NDMA) has aroused extensive concern as a disinfection byproduct due to its high toxicity and elevated concentration levels in water sources. This study investigates the photoreductive decomposition of NDMA by UV/iodide process. The results showed that this process is an effective strategy for the treatment of NDMA with 99.2% NDMA removed within 10min. The depletion of NDMA by UV/iodide process obeyed pseudo-first-order kinetics with a rate constant (k 1 ) of 0.60±0.03min -1 . Hydrated electrons (e aq - ) generated by the UV irradiation of iodide were proven to play a critical role. Dimethylamine (DMA) and nitrite (NO 2 - ) were formed as the main intermediate products, which completely converted to formate (HCOO - ), ammonium (NH 4 + ) and nitrogen (N 2 ). Therefore, not only the high efficiencies in NDMA destruction, but the elimination of toxic intermediates make UV/iodide process advantageous. A photoreduction mechanism was proposed: NDMA initially absorbed photons to a photoexcited state, and underwent a cleavage of NNO bond under the attack of e aq - . The solution pH had little impact on NDMA removal. However, alkaline conditions were more favorable for the elimination of DMA and NO 2 - , thus effectively reducing the secondary pollution. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Decomposition Mechanism and Decomposition Promoting Factors of Waste Hard Metal for Zinc Decomposition Process (ZDP)

    NASA Astrophysics Data System (ADS)

    Pee, J. H.; Kim, Y. J.; Kim, J. Y.; Seong, N. E.; Cho, W. S.; Kim, K. J.

    2011-10-01

    Decomposition promoting factors and decomposition mechanism in the zinc decomposition process of waste hard metals which are composed mostly of tungsten carbide and cobalt were evaluated. Zinc volatility amount was suppressed and zinc steam pressure was produced in the reaction graphite crucible inside an electric furnace for ZDP. Reaction was done for 2 hrs at 650 °C, which 100 % decomposed the waste hard metals that were over 30 mm thick. As for the separation-decomposition of waste hard metals, zinc melted alloy formed a liquid composed of a mixture of γ-β1 phase from the cobalt binder layer (reaction interface). The volume of reacted zone was expanded and the waste hard metal layer was decomposed-separated horizontally from the hard metal. Zinc used in the ZDP process was almost completely removed-collected by decantation and volatilization-collection process at 1000 °C. The small amount of zinc remaining in the tungsten carbide-cobalt powder which was completely decomposed was fully removed by using phosphate solution which had a slow cobalt dissolution speed.

  6. Perfluoropolyalkylether decomposition on catalytic aluminas

    NASA Technical Reports Server (NTRS)

    Morales, Wilfredo

    1994-01-01

    The decomposition of Fomblin Z25, a commercial perfluoropolyalkylether liquid lubricant, was studied using the Penn State Micro-oxidation Test, and a thermal gravimetric/differential scanning calorimetry unit. The micro-oxidation test was conducted using 440C stainless steel and pure iron metal catalyst specimens, whereas the thermal gravimetric/differential scanning calorimetry tests were conducted using catalytic alumina pellets. Analysis of the thermal data, high pressure liquid chromatography data, and x-ray photoelectron spectroscopy data support evidence that there are two different decomposition mechanisms for Fomblin Z25, and that reductive sites on the catalytic surfaces are responsible for the decomposition of Fomblin Z25.

  7. Social Studies Program Guide, 3-6: Intermediate Grades.

    ERIC Educational Resources Information Center

    Spokane School District 81, WA.

    This curriculum guide suggests materials, resources, and activities related to social studies knowledge and skill development for grades 4-6. Third grade activities are also included to inform intermediate teachers what has been previously taught. Part of a series of social studies program guides designed to be used in the Spokane public schools…

  8. Decomposition Rate and Pattern in Hanging Pigs.

    PubMed

    Lynch-Aird, Jeanne; Moffatt, Colin; Simmons, Tal

    2015-09-01

    Accurate prediction of the postmortem interval requires an understanding of the decomposition process and the factors acting upon it. A controlled experiment, over 60 days at an outdoor site in the northwest of England, used 20 freshly killed pigs (Sus scrofa) as human analogues to study decomposition rate and pattern. Ten pigs were hung off the ground and ten placed on the surface. Observed differences in the decomposition pattern required a new decomposition scoring scale to be produced for the hanging pigs to enable comparisons with the surface pigs. The difference in the rate of decomposition between hanging and surface pigs was statistically significant (p=0.001). Hanging pigs reached advanced decomposition stages sooner, but lagged behind during the early stages. This delay is believed to result from lower variety and quantity of insects, due to restricted beetle access to the aerial carcass, and/or writhing maggots falling from the carcass. © 2015 American Academy of Forensic Sciences.

  9. 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.

  10. Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

    PubMed

    Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

    2017-08-30

    Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular

  11. Chinese Orthographic Decomposition and Logographic Structure

    ERIC Educational Resources Information Center

    Cheng, Chao-Ming; Lin, Shan-Yuan

    2013-01-01

    "Chinese orthographic decomposition" refers to a sense of uncertainty about the writing of a well-learned Chinese character following a prolonged inspection of the character. This study investigated the decomposition phenomenon in a test situation in which Chinese characters were repeatedly presented in a word context and assessed…

  12. Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50).

    PubMed

    Muravyev, Nikita V; Monogarov, Konstantin A; Asachenko, Andrey F; Nechaev, Mikhail S; Ananyev, Ivan V; Fomenkov, Igor V; Kiselev, Vitaly G; Pivkina, Alla N

    2016-12-21

    Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5'-bistetrazole-1,1'-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

  13. Metal-porphyrin: a potential catalyst for direct decomposition of N(2)O by theoretical reaction mechanism investigation.

    PubMed

    Maitarad, Phornphimon; Namuangruk, Supawadee; Zhang, Dengsong; Shi, Liyi; Li, Hongrui; Huang, Lei; Boekfa, Bundet; Ehara, Masahiro

    2014-06-17

    The adsorption of nitrous oxide (N2O) on metal-porphyrins (metal: Ti, Cr, Fe, Co, Ni, Cu, or Zn) has been theoretically investigated using density functional theory with the M06L functional to explore their use as potential catalysts for the direct decomposition of N2O. Among these metal-porphyrins, Ti-porphyrin is the most active for N2O adsorption in the triplet ground state with the strongest adsorption energy (-13.32 kcal/mol). Ti-porphyrin was then assessed for the direct decomposition of N2O. For the overall reaction mechanism of three N2O molecules on Ti-porphyrin, two plausible catalytic cycles are proposed. Cycle 1 involves the consecutive decomposition of the first two N2O molecules, while cycle 2 is the decomposition of the third N2O molecule. For cycle 1, the activation energies of the first and second N2O decompositions are computed to be 3.77 and 49.99 kcal/mol, respectively. The activation energy for the third N2O decomposition in cycle 2 is 47.79 kcal/mol, which is slightly lower than that of the second activation energy of the first cycle. O2 molecules are released in cycles 1 and 2 as the products of the reaction, which requires endothermic energies of 102.96 and 3.63 kcal/mol, respectively. Therefore, the O2 desorption is mainly released in catalytic cycle 2 of a TiO3-porphyrin intermediate catalyst. In conclusion, regarding the O2 desorption step for the direct decomposition of N2O, the findings would be very useful to guide the search for potential N2O decomposition catalysts in new directions.

  14. Studying Reaction Intermediates Formed at Graphenic Surfaces

    NASA Astrophysics Data System (ADS)

    Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

    2014-03-01

    We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

  15. Differential Decomposition Among Pig, Rabbit, and Human Remains.

    PubMed

    Dautartas, Angela; Kenyhercz, Michael W; Vidoli, Giovanna M; Meadows Jantz, Lee; Mundorff, Amy; Steadman, Dawnie Wolfe

    2018-03-30

    While nonhuman animal remains are often utilized in forensic research to develop methods to estimate the postmortem interval, systematic studies that directly validate animals as proxies for human decomposition are lacking. The current project compared decomposition rates among pigs, rabbits, and humans at the University of Tennessee's Anthropology Research Facility across three seasonal trials that spanned nearly 2 years. The Total Body Score (TBS) method was applied to quantify decomposition changes and calculate the postmortem interval (PMI) in accumulated degree days (ADD). Decomposition trajectories were analyzed by comparing the estimated and actual ADD for each seasonal trial and by fuzzy cluster analysis. The cluster analysis demonstrated that the rabbits formed one group while pigs and humans, although more similar to each other than either to rabbits, still showed important differences in decomposition patterns. The decomposition trends show that neither nonhuman model captured the pattern, rate, and variability of human decomposition. © 2018 American Academy of Forensic Sciences.

  16. Molecular dynamics simulations of methane hydrate decomposition.

    PubMed

    Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

    2009-03-12

    Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

  17. 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.

  18. Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

    NASA Astrophysics Data System (ADS)

    Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

    2004-11-01

    The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

  19. Early stage litter decomposition across biomes

    Treesearch

    Ika Djukic; Sebastian Kepfer-Rojas; Inger Kappel Schmidt; Klaus Steenberg Larsen; Claus Beier; Björn Berg; Kris Verheyen; Adriano Caliman; Alain Paquette; Alba Gutiérrez-Girón; Alberto Humber; Alejandro Valdecantos; Alessandro Petraglia; Heather Alexander; Algirdas Augustaitis; Amélie Saillard; Ana Carolina Ruiz Fernández; Ana I. Sousa; Ana I. Lillebø; Anderson da Rocha Gripp; André-Jean Francez; Andrea Fischer; Andreas Bohner; Andrey Malyshev; Andrijana Andrić; Andy Smith; Angela Stanisci; Anikó Seres; Anja Schmidt; Anna Avila; Anne Probst; Annie Ouin; Anzar A. Khuroo; Arne Verstraeten; Arely N. Palabral-Aguilera; Artur Stefanski; Aurora Gaxiola; Bart Muys; Bernard Bosman; Bernd Ahrends; Bill Parker; Birgit Sattler; Bo Yang; Bohdan Juráni; Brigitta Erschbamer; Carmen Eugenia Rodriguez Ortiz; Casper T. Christiansen; E. Carol Adair; Céline Meredieu; Cendrine Mony; Charles A. Nock; Chi-Ling Chen; Chiao-Ping Wang; Christel Baum; Christian Rixen; Christine Delire; Christophe Piscart; Christopher Andrews; Corinna Rebmann; Cristina Branquinho; Dana Polyanskaya; David Fuentes Delgado; Dirk Wundram; Diyaa Radeideh; Eduardo Ordóñez-Regil; Edward Crawford; Elena Preda; Elena Tropina; Elli Groner; Eric Lucot; Erzsébet Hornung; Esperança Gacia; Esther Lévesque; Evanilde Benedito; Evgeny A. Davydov; Evy Ampoorter; Fabio Padilha Bolzan; Felipe Varela; Ferdinand Kristöfel; Fernando T. Maestre; Florence Maunoury-Danger; Florian Hofhansl; Florian Kitz; Flurin Sutter; Francisco Cuesta; Francisco de Almeida Lobo; Franco Leandro de Souza; Frank Berninger; Franz Zehetner; Georg Wohlfahrt; George Vourlitis; Geovana Carreño-Rocabado; Gina Arena; Gisele Daiane Pinha; Grizelle González; Guylaine Canut; Hanna Lee; Hans Verbeeck; Harald Auge; Harald Pauli; Hassan Bismarck Nacro; Héctor A. Bahamonde; Heike Feldhaar; Heinke Jäger; Helena C. Serrano; Hélène Verheyden; Helge Bruelheide; Henning Meesenburg; Hermann Jungkunst; Hervé Jactel; Hideaki Shibata; Hiroko Kurokawa; Hugo López Rosas; Hugo L. Rojas Villalobos; Ian Yesilonis; Inara Melece; Inge Van Halder; Inmaculada García Quirós; Isaac Makelele; Issaka Senou; István Fekete; Ivan Mihal; Ivika Ostonen; Jana Borovská; Javier Roales; Jawad Shoqeir; Jean-Christophe Lata; Jean-Paul Theurillat; Jean-Luc Probst; Jess Zimmerman; Jeyanny Vijayanathan; Jianwu Tang; Jill Thompson; Jiří Doležal; Joan-Albert Sanchez-Cabeza; Joël Merlet; Joh Henschel; Johan Neirynck; Johannes Knops; John Loehr; Jonathan von Oppen; Jónína Sigríður Þorláksdóttir; Jörg Löffler; José-Gilberto Cardoso-Mohedano; José-Luis Benito-Alonso; Jose Marcelo Torezan; Joseph C. Morina; Juan J. Jiménez; Juan Dario Quinde; Juha Alatalo; Julia Seeber; Jutta Stadler; Kaie Kriiska; Kalifa Coulibaly; Karibu Fukuzawa; Katalin Szlavecz; Katarína Gerhátová; Kate Lajtha; Kathrin Käppeler; Katie A. Jennings; Katja Tielbörger; Kazuhiko Hoshizaki; Ken Green; Lambiénou Yé; Laryssa Helena Ribeiro Pazianoto; Laura Dienstbach; Laura Williams; Laura Yahdjian; Laurel M. Brigham; Liesbeth van den Brink; Lindsey Rustad; al. et

    2018-01-01

    Through litter decomposition enormous amounts of carbon is emitted to the atmosphere. Numerous large-scale decomposition experiments have been conducted focusing on this fundamental soil process in order to understand the controls on the terrestrial carbon transfer to the atmosphere. However, previous studies were mostly based on site-specific litter and methodologies...

  20. Criegee intermediates and their impacts on the troposphere

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

    Khan, M. A. H.; Percival, C. J.; Caravan, R. L.

    We report Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 10 4 cm -3 to 1 × 10 5 cm -3, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found tomore » be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO 2 to form SO 3, which can go on to form a significant amount of H 2SO 4 which is a key atmospheric nucleation species and therefore vital to the formation of clouds. Lastly, the sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.« less

  1. Criegee intermediates and their impacts on the troposphere

    DOE PAGES

    Khan, M. A. H.; Percival, C. J.; Caravan, R. L.; ...

    2018-02-15

    We report Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 10 4 cm -3 to 1 × 10 5 cm -3, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found tomore » be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO 2 to form SO 3, which can go on to form a significant amount of H 2SO 4 which is a key atmospheric nucleation species and therefore vital to the formation of clouds. Lastly, the sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.« less

  2. Comparison of decomposition rates between autopsied and non-autopsied human remains.

    PubMed

    Bates, Lennon N; Wescott, Daniel J

    2016-04-01

    Penetrating trauma has been cited as a significant factor in the rate of decomposition. Therefore, penetrating trauma may have an effect on estimations of time-since-death in medicolegal investigations and on research examining decomposition rates and processes when autopsied human bodies are used. The goal of this study was to determine if there are differences in the rate of decomposition between autopsied and non-autopsied human remains in the same environment. The purpose is to shed light on how large incisions, such as those from a thorocoabdominal autopsy, effect time-since-death estimations and research on the rate of decomposition that use both autopsied and non-autopsied human remains. In this study, 59 non-autopsied and 24 autopsied bodies were studied. The number of accumulated degree days required to reach each decomposition stage was then compared between autopsied and non-autopsied remains. Additionally, both types of bodies were examined for seasonal differences in decomposition rates. As temperature affects the rate of decomposition, this study also compared the internal body temperatures of autopsied and non-autopsied remains to see if differences between the two may be leading to differential decomposition. For this portion of this study, eight non-autopsied and five autopsied bodies were investigated. Internal temperature was collected once a day for two weeks. The results showed that differences in the decomposition rate between autopsied and non-autopsied remains was not statistically significant, though the average ADD needed to reach each stage of decomposition was slightly lower for autopsied bodies than non-autopsied bodies. There was also no significant difference between autopsied and non-autopsied bodies in the rate of decomposition by season or in internal temperature. Therefore, this study suggests that it is unnecessary to separate autopsied and non-autopsied remains when studying gross stages of human decomposition in Central Texas

  3. Decomposition rates and termite assemblage composition in semiarid Africa

    USGS Publications Warehouse

    Schuurman, G.

    2005-01-01

    Outside of the humid tropics, abiotic factors are generally considered the dominant regulators of decomposition, and biotic influences are frequently not considered in predicting decomposition rates. In this study, I examined the effect of termite assemblage composition and abundance on decomposition of wood litter of an indigenous species (Croton megalobotrys) in five terrestrial habitats of the highly seasonal semiarid Okavango Delta region of northern Botswana, to determine whether natural variation in decomposer community composition and abundance influences decomposition rates. 1 conducted the study in two areas, Xudum and Santawani, with the Xudum study preceding the Santawani study. I assessed termite assemblage composition and abundance using a grid of survey baits (rolls of toilet paper) placed on the soil surface and checked 2-4 times/month. I placed a billet (a section of wood litter) next to each survey bait and measured decomposition in a plot by averaging the mass loss of its billets. Decomposition rates varied up to sixfold among plots within the same habitat and locality, despite the fact that these plots experienced the same climate. In addition, billets decomposed significantly faster during the cooler and drier Santawani study, contradicting climate-based predictions. Because termite incidence was generally higher in Santawani plots, termite abundance initially seemed a likely determinant of decomposition in this system. However, no significant effect of termite incidence on billet mass loss rates was observed among the Xudum plots, where decomposition rates remained low even though termite incidence varied considerably. Considering the incidences of fungus-growing termites and non-fungus-growing termites separately resolves this apparent contradiction: in both Santawani and Xudum, only fungus-growing termites play a significant role in decomposition. This result is mirrored in an analysis of the full data set of combined Xudum and Santawani data

  4. Let's Break it Down: A Study of Organic Decomposition Rates in Clay Soil

    NASA Astrophysics Data System (ADS)

    Weiss, E.

    2016-12-01

    In this experiment I will be testing if temperature affects the organic decomposition rates in clay soil. I will need to be able to clean and weigh each filter paper without disrupting my data damaging or brushing off additional paper material. From there I need to be able to analyze and interpret my data to factor anything else that may affect the decomposition rates in the soil. Soil decomposers include bacteria and fungi. They obtain energy from plant and animal detritus through aerobic decomposition, which is similar to how humans break down sugar. The formula is: C6H12O6 + O2 → CO2 + H2O + energy. Besides oxygen and sugar the organisms need nutrients such as water and sustainable temperatures. Decomposition is important to us because it helps regulate soil structure, moisture, temperature, and provides nutrients to soil organisms. This matters on a global scale since decomposers release a large amount of carbon when breaking down matter, which contributes to greenhouse gasses such as carbon dioxide and methane. These greenhouse gasses affect the earth's climate. People who care about decomposition are farmers and those in agriculture, as well as environmental scientists. Even national parks might care because decomposition may affect park safety, how the park looks, and the amount of plants and wildlife. Things that can affect decomposition are the decomposers in the soil, temperature, and water or moisture. My secondary research also showed that PH and chemical composition of the soil affect the rate of decomposition.Cold or freezing temperatures can help preserve organic material in soil because it freezes the soil and moisture, making it too dense for the organic decomposers to break down the organic matter. Soil also can be preserved by drying out and being stored at 4º Celsius (or 39º Fahrenheit) for 28 days. However, soil can degrade slowly in these conditions because it is not frozen and can be oxidized.

  5. Direct observation of nanowire growth and decomposition.

    PubMed

    Rackauskas, Simas; Shandakov, Sergey D; Jiang, Hua; Wagner, Jakob B; Nasibulin, Albert G

    2017-09-26

    Fundamental concepts of the crystal formation suggest that the growth and decomposition are determined by simultaneous embedding and removal of the atoms. Apparently, by changing the crystal formation conditions one can switch the regimes from the growth to decomposition. To the best of our knowledge, so far this has been only postulated, but never observed at the atomic level. By means of in situ environmental transmission electron microscopy we monitored and examined the atomic layer transformation at the conditions of the crystal growth and its decomposition using CuO nanowires selected as a model object. The atomic layer growth/decomposition was studied by varying an O 2 partial pressure. Three distinct regimes of the atomic layer evolution were experimentally observed: growth, transition and decomposition. The transition regime, at which atomic layer growth/decomposition switch takes place, is characterised by random nucleation of the atomic layers on the growing {111} surface. The decomposition starts on the side of the nanowire by removing the atomic layers without altering the overall crystal structure, which besides the fundamental importance offers new possibilities for the nanowire manipulation. Understanding of the crystal growth kinetics and nucleation at the atomic level is essential for the precise control of 1D crystal formation.

  6. Spectroscopic study of shock-induced decomposition in ammonium perchlorate single crystals.

    PubMed

    Gruzdkov, Y A; Winey, J M; Gupta, Y M

    2008-05-01

    Time-resolved Raman scattering measurements were performed on ammonium perchlorate (AP) single crystals under stepwise shock loading. For particular temperature and pressure conditions, the intensity of the Raman spectra in shocked AP decayed exponentially with time. This decay is attributed to shock-induced chemical decomposition in AP. A series of shock experiments, reaching peak stresses from 10-18 GPa, demonstrated that higher stresses inhibit decomposition while higher temperatures promote it. No orientation dependence was found when AP crystals were shocked normal to the (210) and (001) crystallographic planes. VISAR (velocity interferometer system for any reflector) particle velocity measurements and time-resolved optical extinction measurements carried out to verify these observations are consistent with the Raman data. The combined kinetic and spectroscopic results are consistent with a proton-transfer reaction as the first decomposition step in shocked AP.

  7. Online kinetic studies on intermediates of laccase-catalyzed reaction in reversed micelle.

    PubMed

    Liu, Zhi-Hong; Shao, Mei; Cai, Ru-Xiu; Shen, Ping

    2006-02-01

    Using water/AOT/n-octane reversed micelle as the medium, the optical signal of the reactive intermediate of laccase-catalyzed oxidation of o-phenylenediamine, which was indetectable in aqueous solutions, was successfully captured. Thus online kinetic studies of the intermediate were accomplished. Two-way kinetic spectral data were acquired with stopped-flow technique. By resolving the data with global analysis software, both the kinetic curves and the absorption spectra of the components involved in the reaction process were simultaneously obtained. The whole reaction in the reversed micelle was proved to be composed of two successive steps, an enzymatic generation of the intermediate and a following nonenzymatic decay of the intermediate. A consecutive first-order kinetic model of the whole reaction was confirmed. The influences of microenvironmental factors of the medium (such as the pH value of the water pool and the water/AOT ratio) on the detection of the intermediate were also investigated.

  8. An ab initio molecular dynamics study of thermal decomposition of 3,6-di(azido)-1,2,4,5-tetrazine.

    PubMed

    Wu, Qiong; Zhu, Weihua; Xiao, Heming

    2014-10-21

    Ab initio molecular dynamics simulations were performed to study the thermal decomposition of isolated and crystal 3,6-di(azido)-1,2,4,5-tetrazine (DiAT). During unimolecular decomposition, the three different initiation mechanisms were observed to be N-N2 cleavage, ring opening, and isomerization, respectively. The preferential initial decomposition step is the homolysis of the N-N2 bond in the azido group. The release mechanisms of nitrogen gas are found to be very different in the early and later decomposition stages of crystal DiAT. In the early decomposition, DiAT decomposes very fast and drastically without forming any stable long-chains or heterocyclic clusters, and most of the nitrogen gases are released through rapid rupture of nitrogen-nitrogen and carbon-nitrogen bonds. But in the later decomposition stage, the release of nitrogen gas is inhibited due to low mobility, long distance from each other, and strong carbon-nitrogen bonds. To overcome the obstacles, the nitrogen gases are released through slow formation and disintegration of polycyclic networks. Our simulations suggest a new decomposition mechanism for the organic polyazido initial explosive at the atomistic level.

  9. Effect of bait decomposition on the attractiveness to species of Diptera of veterinary and forensic importance in a rainforest fragment in Brazil.

    PubMed

    Oliveira, Diego L; Soares, Thiago F; Vasconcelos, Simão D

    2016-01-01

    Insects associated with carrion can have parasitological importance as vectors of several pathogens and causal agents of myiasis to men and to domestic and wild animals. We tested the attractiveness of animal baits (chicken liver) at different stages of decomposition to necrophagous species of Diptera (Calliphoridae, Fanniidae, Muscidae, Phoridae and Sarcophagidae) in a rainforest fragment in Brazil. Five types of bait were used: fresh and decomposed at room temperature (26 °C) for 24, 48, 72 and 96 h. A positive correlation was detected between the time of decomposition and the abundance of Calliphoridae and Muscidae, whilst the abundance of adults of Phoridae decreased with the time of decomposition. Ten species of calliphorids were registered, of which Chrysomya albiceps, Chrysomya megacephala and Chloroprocta idioidea showed a positive significant correlation between abundance and decomposition. Specimens of Sarcophagidae and Fanniidae did not discriminate between fresh and highly decomposed baits. A strong female bias was registered for all species of Calliphoridae irrespective of the type of bait. The results reinforce the feasibility of using animal tissues as attractants to a wide diversity of dipterans of medical, parasitological and forensic importance in short-term surveys, especially using baits at intermediate stages of decomposition.

  10. Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

    NASA Astrophysics Data System (ADS)

    Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

    2016-04-01

    The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

  11. Three-Component Decomposition of Polarimetric SAR Data Integrating Eigen-Decomposition Results

    NASA Astrophysics Data System (ADS)

    Lu, Da; He, Zhihua; Zhang, Huan

    2018-01-01

    This paper presents a novel three-component scattering power decomposition of polarimetric SAR data. There are two problems in three-component decomposition method: volume scattering component overestimation in urban areas and artificially set parameter to be a fixed value. Though volume scattering component overestimation can be partly solved by deorientation process, volume scattering still dominants some oriented urban areas. The speckle-like decomposition results introduced by artificially setting value are not conducive to further image interpretation. This paper integrates the results of eigen-decomposition to solve the aforementioned problems. Two principal eigenvectors are used to substitute the surface scattering model and the double bounce scattering model. The decomposed scattering powers are obtained using a constrained linear least-squares method. The proposed method has been verified using an ESAR PolSAR image, and the results show that the proposed method has better performance in urban area.

  12. Warming accelerates decomposition of decades-old carbon in forest soils

    DOE PAGES

    Hopkins, F. M.; Torn, M. S.; Trumbore, S. E.

    2012-06-11

    Global climate carbon-cycle models predict acceleration of soil organic carbon losses to the atmosphere with warming, but the size of this feedback is poorly known. The temperature sensitivity of soil carbon decomposition is commonly determined by measuring changes in the rate of carbon dioxide (CO 2) production under controlled laboratory conditions. We added measurements of carbon isotopes in respired CO 2 to constrain the age of carbon substrates contributing to the temperature response of decomposition for surface soils from two temperate forest sites with very different overall rates of carbon cycling. Roughly one-third of the carbon respired at any temperaturemore » was fixed from the atmosphere more than 10 y ago, and the mean age of respired carbon reflected a mixture of substrates of varying ages. Consistent with global ecosystem model predictions, the temperature sensitivity of the carbon fixed more than a decade ago was the same as the temperature sensitivity for carbon fixed less than 10 y ago. However, we also observed an overall increase in the mean age of carbon respired at higher temperatures, even correcting for potential substrate limitation effects. The combination of several age constraints from carbon isotopes showed that warming had a similar effect on respiration of decades-old and younger (<10 y) carbon but a greater effect on decomposition of substrates of intermediate (between 7 and 13 y) age. Our results highlight the vulnerability of soil carbon to warming that is years-to-decades old, which makes up a large fraction of total soil carbon in forest soils globally.« less

  13. Warming accelerates decomposition of decades-old carbon in forest soils.

    PubMed

    Hopkins, Francesca M; Torn, Margaret S; Trumbore, Susan E

    2012-06-26

    Global climate carbon-cycle models predict acceleration of soil organic carbon losses to the atmosphere with warming, but the size of this feedback is poorly known. The temperature sensitivity of soil carbon decomposition is commonly determined by measuring changes in the rate of carbon dioxide (CO(2)) production under controlled laboratory conditions. We added measurements of carbon isotopes in respired CO(2) to constrain the age of carbon substrates contributing to the temperature response of decomposition for surface soils from two temperate forest sites with very different overall rates of carbon cycling. Roughly one-third of the carbon respired at any temperature was fixed from the atmosphere more than 10 y ago, and the mean age of respired carbon reflected a mixture of substrates of varying ages. Consistent with global ecosystem model predictions, the temperature sensitivity of the carbon fixed more than a decade ago was the same as the temperature sensitivity for carbon fixed less than 10 y ago. However, we also observed an overall increase in the mean age of carbon respired at higher temperatures, even correcting for potential substrate limitation effects. The combination of several age constraints from carbon isotopes showed that warming had a similar effect on respiration of decades-old and younger (<10 y) carbon but a greater effect on decomposition of substrates of intermediate (between 7 and 13 y) age. Our results highlight the vulnerability of soil carbon to warming that is years-to-decades old, which makes up a large fraction of total soil carbon in forest soils globally.

  14. Decomposition of forest products buried in landfills

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

    Wang, Xiaoming, E-mail: xwang25@ncsu.edu; Padgett, Jennifer M.; Powell, John S.

    Highlights: • This study tracked chemical changes of wood and paper in landfills. • A decomposition index was developed to quantify carbohydrate biodegradation. • Newsprint biodegradation as measured here is greater than previous reports. • The field results correlate well with previous laboratory measurements. - Abstract: The objective of this study was to investigate the decomposition of selected wood and paper products in landfills. The decomposition of these products under anaerobic landfill conditions results in the generation of biogenic carbon dioxide and methane, while the un-decomposed portion represents a biogenic carbon sink. Information on the decomposition of these municipal wastemore » components is used to estimate national methane emissions inventories, for attribution of carbon storage credits, and to assess the life-cycle greenhouse gas impacts of wood and paper products. Hardwood (HW), softwood (SW), plywood (PW), oriented strand board (OSB), particleboard (PB), medium-density fiberboard (MDF), newsprint (NP), corrugated container (CC) and copy paper (CP) were buried in landfills operated with leachate recirculation, and were excavated after approximately 1.5 and 2.5 yr. Samples were analyzed for cellulose (C), hemicellulose (H), lignin (L), volatile solids (VS), and organic carbon (OC). A holocellulose decomposition index (HOD) and carbon storage factor (CSF) were calculated to evaluate the extent of solids decomposition and carbon storage. Samples of OSB made from HW exhibited cellulose plus hemicellulose (C + H) loss of up to 38%, while loss for the other wood types was 0–10% in most samples. The C + H loss was up to 81%, 95% and 96% for NP, CP and CC, respectively. The CSFs for wood and paper samples ranged from 0.34 to 0.47 and 0.02 to 0.27 g OC g{sup −1} dry material, respectively. These results, in general, correlated well with an earlier laboratory-scale study, though NP and CC decomposition measured in this study were

  15. Decomposition Characteristics of Acetone in a DC Corona Discharge at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Sakamoto, Takahiro; Satoh, Kohki; Itoh, Hidenori

    Decomposition characteristics of acetone in a DC corona discharge generated between a multi-needle and a plane electrodes in nitrogen-oxygen mixtures at atmospheric pressure are investigated mainly by infrared absorption spectroscopy in this work. It is found that CO2, CO, CH4, HCHO, HCOOH and HCN are the by-products of acetone in the corona discharge, and that CO, CH4, HCHO, HCOOH and HCN are intermediate products, which tend to be decomposed in the corona discharge. CO2 is found to be the major and end-product. It is also found that acetone is chiefly inverted to CO2 via CO at high oxygen concentration (20%) and via CO and CH4 at relatively low oxygen concentration (0.2%), in addition to the direct conversion from acetone to CO2. As the oxygen concentration increases, the percentages of carbon atoms contained in deposit on the plane electrode and the wall of the discharge chamber increases. Further, the decomposition process of acetone is deduced from the examination of rate constants for the reactions in the gaseous phase.

  16. English and Turkish Pupils' Understanding of Decomposition

    ERIC Educational Resources Information Center

    Cetin, Gulcan

    2007-01-01

    This study aimed to describe seventh grade English and Turkish students' levels of understanding of decomposition. Data were analyzed descriptively from the students' written responses to four diagnostic questions about decomposition. Results revealed that the English students had considerably higher sound understanding and lower no understanding…

  17. Rank-based decompositions of morphological templates.

    PubMed

    Sussner, P; Ritter, G X

    2000-01-01

    Methods for matrix decomposition have found numerous applications in image processing, in particular for the problem of template decomposition. Since existing matrix decomposition techniques are mainly concerned with the linear domain, we consider it timely to investigate matrix decomposition techniques in the nonlinear domain with applications in image processing. The mathematical basis for these investigations is the new theory of rank within minimax algebra. Thus far, only minimax decompositions of rank 1 and rank 2 matrices into outer product expansions are known to the image processing community. We derive a heuristic algorithm for the decomposition of matrices having arbitrary rank.

  18. Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

    DOE PAGES

    Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

    2017-04-25

    A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

  19. Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

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

    Schimmenti, Roberto; Cortese, Remedios; Duca, Dario

    A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

  20. 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.

  1. 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

  2. Study on the decomposition of trace benzene over V2O5-WO3 ...

    EPA Pesticide Factsheets

    Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene (ClBz) in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employed to measure real-time, trace concentrations of ClBz contained in the flue gas before and after the catalyst. The effects of various parameters, including vanadium content of the catalyst, the catalyst support, as well as the reaction temperature on decomposition of ClBz were investigated. The results showed that the ClBz decomposition efficiency was significantly enhanced when nano-TiO2 instead of conventional TiO2 was used as the catalyst support. No promotion effects were found in the ClBz decomposition process when the catalysts were wet-impregnated with CuO and CeO2. Tests with different concentrations (1,000, 500, and 100 ppb) of ClBz showed that ClBz-decomposition efficiency decreased with increasing concentration, unless active sites were plentiful. A comparison between ClBz and benzene decomposition on the V2O5–WO3/TiO2-based catalyst and the relative kinetics analysis showed that two different active sites were likely involved in the decomposition mechanism and the V=O and V-O-Ti groups may only work for the degradation of the phenyl group and the benzene ring rather than the C-Cl bond. V2O5-WO3/TiO2 based catalysts, that have been used for destruction of a wide variet

  3. Decomposition of forest products buried in landfills.

    PubMed

    Wang, Xiaoming; Padgett, Jennifer M; Powell, John S; Barlaz, Morton A

    2013-11-01

    The objective of this study was to investigate the decomposition of selected wood and paper products in landfills. The decomposition of these products under anaerobic landfill conditions results in the generation of biogenic carbon dioxide and methane, while the un-decomposed portion represents a biogenic carbon sink. Information on the decomposition of these municipal waste components is used to estimate national methane emissions inventories, for attribution of carbon storage credits, and to assess the life-cycle greenhouse gas impacts of wood and paper products. Hardwood (HW), softwood (SW), plywood (PW), oriented strand board (OSB), particleboard (PB), medium-density fiberboard (MDF), newsprint (NP), corrugated container (CC) and copy paper (CP) were buried in landfills operated with leachate recirculation, and were excavated after approximately 1.5 and 2.5yr. Samples were analyzed for cellulose (C), hemicellulose (H), lignin (L), volatile solids (VS), and organic carbon (OC). A holocellulose decomposition index (HOD) and carbon storage factor (CSF) were calculated to evaluate the extent of solids decomposition and carbon storage. Samples of OSB made from HW exhibited cellulose plus hemicellulose (C+H) loss of up to 38%, while loss for the other wood types was 0-10% in most samples. The C+H loss was up to 81%, 95% and 96% for NP, CP and CC, respectively. The CSFs for wood and paper samples ranged from 0.34 to 0.47 and 0.02 to 0.27gOCg(-1) dry material, respectively. These results, in general, correlated well with an earlier laboratory-scale study, though NP and CC decomposition measured in this study were higher than previously reported. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Simulation of toluene decomposition in a pulse-periodic discharge operating in a mixture of molecular nitrogen and oxygen

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

    Trushkin, A. N.; Kochetov, I. V.

    The kinetic model of toluene decomposition in nonequilibrium low-temperature plasma generated by a pulse-periodic discharge operating in a mixture of nitrogen and oxygen is developed. The results of numerical simulation of plasma-chemical conversion of toluene are presented; the main processes responsible for C{sub 6}H{sub 5}CH{sub 3} decomposition are identified; the contribution of each process to total removal of toluene is determined; and the intermediate and final products of C{sub 6}H{sub 5}CH{sub 3} decomposition are identified. It was shown that toluene in pure nitrogen is mostly decomposed in its reactions with metastable N{sub 2}(A{sub 3}{Sigma}{sub u}{sup +}) and N{sub 2}(a Primemore » {sup 1}{Sigma}{sub u}{sup -}) molecules. In the presence of oxygen, in the N{sub 2} : O{sub 2} gas mixture, the largest contribution to C{sub 6}H{sub 5}CH{sub 3} removal is made by the hydroxyl radical OH which is generated in this mixture exclusively due to plasma-chemical reactions between toluene and oxygen decomposition products. Numerical simulation showed the existence of an optimum oxygen concentration in the mixture, at which toluene removal is maximum at a fixed energy deposition.« less

  5. Wood decomposition as influenced by invertebrates.

    PubMed

    Ulyshen, Michael D

    2016-02-01

    The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial ecosystems. Three broad conclusions can be reached from the available literature. First, wood decomposition is largely driven by microbial activity but invertebrates also play a significant role in both temperate and tropical environments. Primary mechanisms include enzymatic digestion (involving both endogenous enzymes and those produced by endo- and ectosymbionts), substrate alteration (tunnelling and fragmentation), biotic interactions and nitrogen fertilization (i.e. promoting nitrogen fixation by endosymbiotic and free-living bacteria). Second, the effects of individual invertebrate taxa or functional groups can be accelerative or inhibitory but the cumulative effect of the entire community is generally to accelerate wood decomposition, at least during the early stages of the process (most studies are limited to the first 2-3 years). Although methodological differences and design limitations preclude meta-analysis, studies aimed at quantifying the contributions of invertebrates to wood decomposition commonly attribute 10-20% of wood loss to these organisms. Finally, some taxa appear to be particularly influential with respect to promoting wood decomposition. These include large wood-boring beetles (Coleoptera) and termites (Termitoidae), especially fungus-farming macrotermitines. The presence or absence of these species may be more consequential than species richness and the influence of invertebrates is likely to vary biogeographically. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

  6. Aging-driven decomposition in zolpidem hemitartrate hemihydrate and the single-crystal structure of its decomposition products.

    PubMed

    Vega, Daniel R; Baggio, Ricardo; Roca, Mariana; Tombari, Dora

    2011-04-01

    The "aging-driven" decomposition of zolpidem hemitartrate hemihydrate (form A) has been followed by X-ray powder diffraction (XRPD), and the crystal and molecular structures of the decomposition products studied by single-crystal methods. The process is very similar to the "thermally driven" one, recently described in the literature for form E (Halasz and Dinnebier. 2010. J Pharm Sci 99(2): 871-874), resulting in a two-phase system: the neutral free base (common to both decomposition processes) and, in the present case, a novel zolpidem tartrate monohydrate, unique to the "aging-driven" decomposition. Our room-temperature single-crystal analysis gives for the free base comparable results as the high-temperature XRPD ones already reported by Halasz and Dinnebier: orthorhombic, Pcba, a = 9.6360(10) Å, b = 18.2690(5) Å, c = 18.4980(11) Å, and V = 3256.4(4) Å(3) . The unreported zolpidem tartrate monohydrate instead crystallizes in monoclinic P21 , which, for comparison purposes, we treated in the nonstandard setting P1121 with a = 20.7582(9) Å, b = 15.2331(5) Å, c = 7.2420(2) Å, γ = 90.826(2)°, and V = 2289.73(14) Å(3) . The structure presents two complete moieties in the asymmetric unit (z = 4, z' = 2). The different phases obtained in both decompositions are readily explained, considering the diverse genesis of both processes. Copyright © 2010 Wiley-Liss, Inc.

  7. Sparse Solution of Fiber Orientation Distribution Function by Diffusion Decomposition

    PubMed Central

    Yeh, Fang-Cheng; Tseng, Wen-Yih Isaac

    2013-01-01

    Fiber orientation is the key information in diffusion tractography. Several deconvolution methods have been proposed to obtain fiber orientations by estimating a fiber orientation distribution function (ODF). However, the L 2 regularization used in deconvolution often leads to false fibers that compromise the specificity of the results. To address this problem, we propose a method called diffusion decomposition, which obtains a sparse solution of fiber ODF by decomposing the diffusion ODF obtained from q-ball imaging (QBI), diffusion spectrum imaging (DSI), or generalized q-sampling imaging (GQI). A simulation study, a phantom study, and an in-vivo study were conducted to examine the performance of diffusion decomposition. The simulation study showed that diffusion decomposition was more accurate than both constrained spherical deconvolution and ball-and-sticks model. The phantom study showed that the angular error of diffusion decomposition was significantly lower than those of constrained spherical deconvolution at 30° crossing and ball-and-sticks model at 60° crossing. The in-vivo study showed that diffusion decomposition can be applied to QBI, DSI, or GQI, and the resolved fiber orientations were consistent regardless of the diffusion sampling schemes and diffusion reconstruction methods. The performance of diffusion decomposition was further demonstrated by resolving crossing fibers on a 30-direction QBI dataset and a 40-direction DSI dataset. In conclusion, diffusion decomposition can improve angular resolution and resolve crossing fibers in datasets with low SNR and substantially reduced number of diffusion encoding directions. These advantages may be valuable for human connectome studies and clinical research. PMID:24146772

  8. Dictionary-Based Tensor Canonical Polyadic Decomposition

    NASA Astrophysics Data System (ADS)

    Cohen, Jeremy Emile; Gillis, Nicolas

    2018-04-01

    To ensure interpretability of extracted sources in tensor decomposition, we introduce in this paper a dictionary-based tensor canonical polyadic decomposition which enforces one factor to belong exactly to a known dictionary. A new formulation of sparse coding is proposed which enables high dimensional tensors dictionary-based canonical polyadic decomposition. The benefits of using a dictionary in tensor decomposition models are explored both in terms of parameter identifiability and estimation accuracy. Performances of the proposed algorithms are evaluated on the decomposition of simulated data and the unmixing of hyperspectral images.

  9. Error reduction in EMG signal decomposition

    PubMed Central

    Kline, Joshua C.

    2014-01-01

    Decomposition of the electromyographic (EMG) signal into constituent action potentials and the identification of individual firing instances of each motor unit in the presence of ambient noise are inherently probabilistic processes, whether performed manually or with automated algorithms. Consequently, they are subject to errors. We set out to classify and reduce these errors by analyzing 1,061 motor-unit action-potential trains (MUAPTs), obtained by decomposing surface EMG (sEMG) signals recorded during human voluntary contractions. Decomposition errors were classified into two general categories: location errors representing variability in the temporal localization of each motor-unit firing instance and identification errors consisting of falsely detected or missed firing instances. To mitigate these errors, we developed an error-reduction algorithm that combines multiple decomposition estimates to determine a more probable estimate of motor-unit firing instances with fewer errors. The performance of the algorithm is governed by a trade-off between the yield of MUAPTs obtained above a given accuracy level and the time required to perform the decomposition. When applied to a set of sEMG signals synthesized from real MUAPTs, the identification error was reduced by an average of 1.78%, improving the accuracy to 97.0%, and the location error was reduced by an average of 1.66 ms. The error-reduction algorithm in this study is not limited to any specific decomposition strategy. Rather, we propose it be used for other decomposition methods, especially when analyzing precise motor-unit firing instances, as occurs when measuring synchronization. PMID:25210159

  10. Experimental and DFT simulation study of a novel felodipine cocrystal: Characterization, dissolving properties and thermal decomposition kinetics.

    PubMed

    Yang, Caiqin; Guo, Wei; Lin, Yulong; Lin, Qianqian; Wang, Jiaojiao; Wang, Jing; Zeng, Yanli

    2018-05-30

    In this study, a new cocrystal of felodipine (Fel) and glutaric acid (Glu) with a high dissolution rate was developed using the solvent ultrasonic method. The prepared cocrystal was characterized using X-ray powder diffraction, differential scanning calorimetry, thermogravimetric (TG) analysis, and infrared (IR) spectroscopy. To provide basic information about the optimization of pharmaceutical preparations of Fel-based cocrystals, this work investigated the thermal decomposition kinetics of the Fel-Glu cocrystal through non-isothermal thermogravimetry. Density functional theory (DFT) simulations were also performed on the Fel monomer and the trimolecular cocrystal compound for exploring the mechanisms underlying hydrogen bonding formation and thermal decomposition. Combined results of IR spectroscopy and DFT simulation verified that the Fel-Glu cocrystal formed via the NH⋯OC and CO⋯HO hydrogen bonds between Fel and Glu at the ratio of 1:2. The TG/derivative TG curves indicated that the thermal decomposition of the Fel-Glu cocrystal underwent a two-step process. The apparent activation energy (E a ) and pre-exponential factor (A) of the thermal decomposition for the first stage were 84.90 kJ mol -1 and 7.03 × 10 7  min -1 , respectively. The mechanism underlying thermal decomposition possibly involved nucleation and growth, with the integral mechanism function G(α) of α 3/2 . DFT calculation revealed that the hydrogen bonding between Fel and Glu weakened the terminal methoxyl, methyl, and ethyl groups in the Fel molecule. As a result, these groups were lost along with the Glu molecule in the first thermal decomposition. In conclusion, the formed cocrystal exhibited different thermal decomposition kinetics and showed different E a , A, and shelf life from the intact active pharmaceutical ingredient. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. The trait contribution to wood decomposition rates of 15 Neotropical tree species.

    PubMed

    van Geffen, Koert G; Poorter, Lourens; Sass-Klaassen, Ute; van Logtestijn, Richard S P; Cornelissen, Johannes H C

    2010-12-01

    The decomposition of dead wood is a critical uncertainty in models of the global carbon cycle. Despite this, relatively few studies have focused on dead wood decomposition, with a strong bias to higher latitudes. Especially the effect of interspecific variation in species traits on differences in wood decomposition rates remains unknown. In order to fill these gaps, we applied a novel method to study long-term wood decomposition of 15 tree species in a Bolivian semi-evergreen tropical moist forest. We hypothesized that interspecific differences in species traits are important drivers of variation in wood decomposition rates. Wood decomposition rates (fractional mass loss) varied between 0.01 and 0.31 yr(-1). We measured 10 different chemical, anatomical, and morphological traits for all species. The species' average traits were useful predictors of wood decomposition rates, particularly the average diameter (dbh) of the tree species (R2 = 0.41). Lignin concentration further increased the proportion of explained inter-specific variation in wood decomposition (both negative relations, cumulative R2 = 0.55), although it did not significantly explain variation in wood decomposition rates if considered alone. When dbh values of the actual dead trees sampled for decomposition rate determination were used as a predictor variable, the final model (including dead tree dbh and lignin concentration) explained even more variation in wood decomposition rates (R2 = 0.71), underlining the importance of dbh in wood decomposition. Other traits, including wood density, wood anatomical traits, macronutrient concentrations, and the amount of phenolic extractives could not significantly explain the variation in wood decomposition rates. The surprising results of this multi-species study, in which for the first time a large set of traits is explicitly linked to wood decomposition rates, merits further testing in other forest ecosystems.

  12. A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

    PubMed

    Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

    2016-09-29

    The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

  13. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

    PubMed

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

    2013-05-02

    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  14. Structure based aggregation studies reveal the presence of helix-rich intermediate during α-Synuclein aggregation

    PubMed Central

    Ghosh, Dhiman; Singh, Pradeep K.; Sahay, Shruti; Jha, Narendra Nath; Jacob, Reeba S.; Sen, Shamik; Kumar, Ashutosh; Riek, Roland; Maji, Samir K.

    2015-01-01

    Mechanistic understanding of nucleation dependent polymerization by α-synuclein (α-Syn) into toxic oligomers and amyloids is important for the drug development against Parkinson's disease. However the structural and morphological characterization during nucleation and subsequent fibrillation process of α-Syn is not clearly understood. Using a variety of complementary biophysical techniques monitoring entire pathway of nine different synucleins, we found that transition of unstructured conformation into β-sheet rich fibril formation involves helix-rich intermediates. These intermediates are common for all aggregating synucleins, contain high solvent-exposed hydrophobic surfaces, are cytotoxic to SHSY-5Y cells and accelerate α-Syn aggregation efficiently. A multidimensional NMR study characterizing the intermediate accompanied with site-specific fluorescence study suggests that the N-terminal and central portions mainly participate in the helix-rich intermediate formation while the C-terminus remained in an extended conformation. However, significant conformational transitions occur at the middle and at the C-terminus during helix to β-sheet transition as evident from Trp fluorescence study. Since partial helix-rich intermediates were also observed for other amyloidogenic proteins such as Aβ and IAPP, we hypothesize that this class of intermediates may be one of the important intermediates for amyloid formation pathway by many natively unstructured protein/peptides and represent a potential target for drug development against amyloid diseases. PMID:25784353

  15. FTIR study of methanol decomposition on gold catalyst for fuel cells

    NASA Astrophysics Data System (ADS)

    Boccuzzi, F.; Chiorino, A.; Manzoli, M.

    The interaction of methanol (m), methanol-water (mw) and methanol-water-oxygen (mwo) on Au/TiO 2 catalyst has been investigated by in situ infrared spectroscopy (FTIR) and quadrupole mass spectrometry (QMS) at different temperatures. The aim of the work is to elucidate the nature and the abundance of the surface intermediates formed in different experimental conditions and to understand the mechanisms of methanol decomposition, of steam reforming and of combined reforming reactions. FTIR spectra run at room temperature in the different reaction mixtures show that differently coordinated methoxy species, that is on top species adsorbed on oxygen vacancy sites, on top species on uncoordinated Ti 4+ sites and bridged species on two Ti 4+ ions, are produced in all the mixtures. Quite strong formaldehyde and formate species adsorbed on gold are produced already at 403 K only in the combined reforming reaction mixture. At 473 K, on top species on uncoordinated Ti 4+ sites and methoxy species adsorbed on oxygen vacancy sites reduce their intensity and, at the same time, some formate species adsorbed on the support are produced in the steam reforming and combined reforming mixtures. At 523 K, on both methanol and methanol-water reaction mixtures, no more definite surface species are evidenced by FTIR on the catalysts, while in the methanol-water-oxygen mixture some residual methoxy and formate species are still present. Moreover, methanol is no more detected by QMS in the gas phase. A role of oxygen adsorbed on gold particles near oxygen vacancies of the support in the oxidative dehydrogenation of methanol is proposed.

  16. Electrochemical and Infrared Absorption Spectroscopy Detection of SF₆ Decomposition Products.

    PubMed

    Dong, Ming; Zhang, Chongxing; Ren, Ming; Albarracín, Ricardo; Ye, Rixin

    2017-11-15

    Sulfur hexafluoride (SF₆) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF₆ decomposition and ultimately generates several types of decomposition products. These SF₆ decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF₆ decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF₆ gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF₆ decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF₆ gas decomposition and is verified to reliably and accurately detect the gas components and concentrations.

  17. Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

    PubMed Central

    Biddle, Eric; Kerfoot, Douglas G. S.; Kho, Yioe Hwa; Russell, Kenneth E.

    1976-01-01

    The decomposition of 2-chloroethylphosphonic acid in aqueous solution has been studied at pH values from 6 to 9 and at temperatures in the 30 to 55 C range. The rate of decomposition is estimated from the rate of formation of ethylene. The rate is proportional to the concentration of the phosphonate dianion and is independent of the hydroxyl ion concentration. The rate constant at 40 C is 1.9 × 10−4 sec−1 and the activation energy is 29.8 kcal mol−1. The rate of reaction is not affected significantly by the presence of potassium iodide or urea (substances which increase the rate of leaf abscission in trees sprayed by 2-chloroethylphosphonic acid). The rate decreases slightly in the presence of low concentrations of magnesium and calcium ions. PMID:16659748

  18. Fundamental Studies of Beta Phase Decomposition Modes in Titanium Alloys

    DTIC Science & Technology

    1989-01-31

    and H. I. Aaronson, "The Carbon-Carbon Interaction Energy in Alpha Fe- C Alloys", Acta Met., in press. Raju V. Ramanujan , H. I. Aaronson and P. H. Leo...ACCESSIO% %. C 20332 61102F 2306 Al 11 TITLE (Include Security Classification) FUNDAMENTAL STUDIES OF BETA PHASE DECOMPOSITION MODES IN TITANIUM ALLOYS 12...SECUR1Tv CLASSiI-CAtION M) UNCLASSIFIED/UNLIMITED C SAME AS RPT C ] YfC ’SERS UNCLASSIFIED 22a NAME OF RESPONSIBLE INOI’JIDUAL 22b TELEPwONE (Include Area

  19. OER Use in Intermediate Language Instruction: A Case Study

    ERIC Educational Resources Information Center

    Godwin-Jones, Robert

    2017-01-01

    This paper reports on a case study in the experimental use of Open Educational Resources (OERs) in intermediate level language instruction. The resources come from three sources: the instructor, the students, and open content repositories. The objective of this action research project was to provide student-centered learning materials, enhance…

  20. 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.

  1. Long-term straw decomposition in agro-ecosystems described by a unified three-exponentiation equation with thermal time.

    PubMed

    Cai, Andong; Liang, Guopeng; Zhang, Xubo; Zhang, Wenju; Li, Ling; Rui, Yichao; Xu, Minggang; Luo, Yiqi

    2018-05-01

    Understanding drivers of straw decomposition is essential for adopting appropriate management practice to improve soil fertility and promote carbon (C) sequestration in agricultural systems. However, predicting straw decomposition and characteristics is difficult because of the interactions between many factors related to straw properties, soil properties, and climate, especially under future climate change conditions. This study investigated the driving factors of straw decomposition of six types of crop straw including wheat, maize, rice, soybean, rape, and other straw by synthesizing 1642 paired data from 98 published papers at spatial and temporal scales across China. All the data derived from the field experiments using little bags over twelve years. Overall, despite large differences in climatic and soil properties, the remaining straw carbon (C, %) could be accurately represented by a three-exponent equation with thermal time (accumulative temperature). The lignin/nitrogen and lignin/phosphorus ratios of straw can be used to define the size of labile, intermediate, and recalcitrant C pool. The remaining C for an individual type of straw in the mild-temperature zone was higher than that in the warm-temperature and subtropical zone within one calendar year. The remaining straw C after one thermal year was 40.28%, 37.97%, 37.77%, 34.71%, 30.87%, and 27.99% for rice, soybean, rape, wheat, maize, and other straw, respectively. Soil available nitrogen and phosphorus influenced the remaining straw C at different decomposition stages. For one calendar year, the total amount of remaining straw C was estimated to be 29.41 Tg and future temperature increase of 2 °C could reduce the remaining straw C by 1.78 Tg. These findings confirmed the long-term straw decomposition could be mainly driven by temperature and straw quality, and quantitatively predicted by thermal time with the three-exponent equation for a wide array of straw types at spatial and temporal

  2. Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

    PubMed

    Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

    2017-07-01

    Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Domain decomposition for aerodynamic and aeroacoustic analyses, and optimization

    NASA Technical Reports Server (NTRS)

    Baysal, Oktay

    1995-01-01

    The overarching theme was the domain decomposition, which intended to improve the numerical solution technique for the partial differential equations at hand; in the present study, those that governed either the fluid flow, or the aeroacoustic wave propagation, or the sensitivity analysis for a gradient-based optimization. The role of the domain decomposition extended beyond the original impetus of discretizing geometrical complex regions or writing modular software for distributed-hardware computers. It induced function-space decompositions and operator decompositions that offered the valuable property of near independence of operator evaluation tasks. The objectives have gravitated about the extensions and implementations of either the previously developed or concurrently being developed methodologies: (1) aerodynamic sensitivity analysis with domain decomposition (SADD); (2) computational aeroacoustics of cavities; and (3) dynamic, multibody computational fluid dynamics using unstructured meshes.

  4. The Effect of Body Mass on Outdoor Adult Human Decomposition.

    PubMed

    Roberts, Lindsey G; Spencer, Jessica R; Dabbs, Gretchen R

    2017-09-01

    Forensic taphonomy explores factors impacting human decomposition. This study investigated the effect of body mass on the rate and pattern of adult human decomposition. Nine males and three females aged 49-95 years ranging in mass from 73 to 159 kg who were donated to the Complex for Forensic Anthropology Research between December 2012 and September 2015 were included in this study. Kelvin accumulated degree days (KADD) were used to assess the thermal energy required for subjects to reach several total body score (TBS) thresholds: early decomposition (TBS ≥6.0), TBS ≥12.5, advanced decomposition (TBS ≥19.0), TBS ≥23.0, and skeletonization (TBS ≥27.0). Results indicate no significant correlation between body mass and KADD at any TBS threshold. Body mass accounted for up to 24.0% of variation in decomposition rate depending on stage, and minor differences in decomposition pattern were observed. Body mass likely has a minimal impact on postmortem interval estimation. © 2017 American Academy of Forensic Sciences.

  5. Crop residue decomposition in Minnesota biochar amended plots

    NASA Astrophysics Data System (ADS)

    Weyers, S. L.; Spokas, K. A.

    2014-02-01

    Impacts of biochar application at laboratory scales are routinely studied, but impacts of biochar application on decomposition of crop residues at field scales have not been widely addressed. The priming or hindrance of crop residue decomposition could have a cascading impact on soil processes, particularly those influencing nutrient availability. Our objectives were to evaluate biochar effects on field decomposition of crop residue, using plots that were amended with biochars made from different feedstocks and pyrolysis platforms prior to the start of this study. Litterbags containing wheat straw material were buried below the soil surface in a continuous-corn cropped field in plots that had received one of seven different biochar amendments or a non-charred wood pellet amendment 2.5 yr prior to start of this study. Litterbags were collected over the course of 14 weeks. Microbial biomass was assessed in treatment plots the previous fall. Though first-order decomposition rate constants were positively correlated to microbial biomass, neither parameter was statistically affected by biochar or wood-pellet treatments. The findings indicated only a residual of potentially positive and negative initial impacts of biochars on residue decomposition, which fit in line with established feedstock and pyrolysis influences. Though no significant impacts were observed with field-weathered biochars, effective soil management may yet have to account for repeat applications of biochar.

  6. Nonlinear mode decomposition: A noise-robust, adaptive decomposition method

    NASA Astrophysics Data System (ADS)

    Iatsenko, Dmytro; McClintock, Peter V. E.; Stefanovska, Aneta

    2015-09-01

    The signals emanating from complex systems are usually composed of a mixture of different oscillations which, for a reliable analysis, should be separated from each other and from the inevitable background of noise. Here we introduce an adaptive decomposition tool—nonlinear mode decomposition (NMD)—which decomposes a given signal into a set of physically meaningful oscillations for any wave form, simultaneously removing the noise. NMD is based on the powerful combination of time-frequency analysis techniques—which, together with the adaptive choice of their parameters, make it extremely noise robust—and surrogate data tests used to identify interdependent oscillations and to distinguish deterministic from random activity. We illustrate the application of NMD to both simulated and real signals and demonstrate its qualitative and quantitative superiority over other approaches, such as (ensemble) empirical mode decomposition, Karhunen-Loève expansion, and independent component analysis. We point out that NMD is likely to be applicable and useful in many different areas of research, such as geophysics, finance, and the life sciences. The necessary matlab codes for running NMD are freely available for download.

  7. Microbial Community Functional Change during Vertebrate Carrion Decomposition

    PubMed Central

    Pechal, Jennifer L.; Crippen, Tawni L.; Tarone, Aaron M.; Lewis, Andrew J.; Tomberlin, Jeffery K.; Benbow, M. Eric

    2013-01-01

    Microorganisms play a critical role in the decomposition of organic matter, which contributes to energy and nutrient transformation in every ecosystem. Yet, little is known about the functional activity of epinecrotic microbial communities associated with carrion. The objective of this study was to provide a description of the carrion associated microbial community functional activity using differential carbon source use throughout decomposition over seasons, between years and when microbial communities were isolated from eukaryotic colonizers (e.g., necrophagous insects). Additionally, microbial communities were identified at the phyletic level using high throughput sequencing during a single study. We hypothesized that carrion microbial community functional profiles would change over the duration of decomposition, and that this change would depend on season, year and presence of necrophagous insect colonization. Biolog EcoPlates™ were used to measure the variation in epinecrotic microbial community function by the differential use of 29 carbon sources throughout vertebrate carrion decomposition. Pyrosequencing was used to describe the bacterial community composition in one experiment to identify key phyla associated with community functional changes. Overall, microbial functional activity increased throughout decomposition in spring, summer and winter while it decreased in autumn. Additionally, microbial functional activity was higher in 2011 when necrophagous arthropod colonizer effects were tested. There were inconsistent trends in the microbial function of communities isolated from remains colonized by necrophagous insects between 2010 and 2011, suggesting a greater need for a mechanistic understanding of the process. These data indicate that functional analyses can be implemented in carrion studies and will be important in understanding the influence of microbial communities on an essential ecosystem process, carrion decomposition. PMID:24265741

  8. Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

    NASA Technical Reports Server (NTRS)

    Schroeder, M. A.

    1980-01-01

    A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

  9. Microbial Signatures of Cadaver Gravesoil During Decomposition.

    PubMed

    Finley, Sheree J; Pechal, Jennifer L; Benbow, M Eric; Robertson, B K; Javan, Gulnaz T

    2016-04-01

    Genomic studies have estimated there are approximately 10(3)-10(6) bacterial species per gram of soil. The microbial species found in soil associated with decomposing human remains (gravesoil) have been investigated and recognized as potential molecular determinants for estimates of time since death. The nascent era of high-throughput amplicon sequencing of the conserved 16S ribosomal RNA (rRNA) gene region of gravesoil microbes is allowing research to expand beyond more subjective empirical methods used in forensic microbiology. The goal of the present study was to evaluate microbial communities and identify taxonomic signatures associated with the gravesoil human cadavers. Using 16S rRNA gene amplicon-based sequencing, soil microbial communities were surveyed from 18 cadavers placed on the surface or buried that were allowed to decompose over a range of decomposition time periods (3-303 days). Surface soil microbial communities showed a decreasing trend in taxon richness, diversity, and evenness over decomposition, while buried cadaver-soil microbial communities demonstrated increasing taxon richness, consistent diversity, and decreasing evenness. The results show that ubiquitous Proteobacteria was confirmed as the most abundant phylum in all gravesoil samples. Surface cadaver-soil communities demonstrated a decrease in Acidobacteria and an increase in Firmicutes relative abundance over decomposition, while buried soil communities were consistent in their community composition throughout decomposition. Better understanding of microbial community structure and its shifts over time may be important for advancing general knowledge of decomposition soil ecology and its potential use during forensic investigations.

  10. Water/cortical bone decomposition: A new approach in dual energy CT imaging for bone marrow oedema detection. A feasibility study.

    PubMed

    Biondi, M; Vanzi, E; De Otto, G; Banci Buonamici, F; Belmonte, G M; Mazzoni, L N; Guasti, A; Carbone, S F; Mazzei, M A; La Penna, A; Foderà, E; Guerreri, D; Maiolino, A; Volterrani, L

    2016-12-01

    Many studies aimed at validating the application of Dual Energy Computed Tomography (DECT) in clinical practice where conventional CT is not exhaustive. An example is given by bone marrow oedema detection, in which DECT based on water/calcium (W/Ca) decomposition was applied. In this paper a new DECT approach, based on water/cortical bone (W/CB) decomposition, was investigated. Eight patients suffering from marrow oedema were scanned with MRI and DECT. Two-materials density decomposition was performed in ROIs corresponding to normal bone marrow and oedema. These regions were drawn on DECT images using MRI informations. Both W/Ca and W/CB were considered as material basis. Scatter plots of W/Ca and W/CB concentrations were made for each ROI in order to evaluate if oedema could be distinguished from normal bone marrow. Thresholds were defined on the scatter plots in order to produce DECT images where oedema regions were highlighted through color maps. The agreement between these images and MR was scored by two expert radiologists. For all the patients, the best scores were obtained using W/CB density decomposition. In all cases, DECT color map images based on W/CB decomposition showed better agreement with MR in bone marrow oedema identification with respect to W/Ca decomposition. This result encourages further studies in order to evaluate if DECT based on W/CB decomposition could be an alternative technique to MR, which would be important when short scanning duration is relevant, as in the case of aged or traumatic patients. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  11. Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process.

    PubMed

    Tryba, Beata; Morawski, Antoni W; Inagaki, Michio; Toyoda, Masahiro

    2006-08-01

    Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.

  12. Residue decomposition of submodel of WEPS

    USDA-ARS?s Scientific Manuscript database

    The Residue Decomposition submodel of the Wind Erosion Prediction System (WEPS) simulates the decrease in crop residue biomass due to microbial activity. The decomposition process is modeled as a first-order reaction with temperature and moisture as driving variables. Decomposition is a function of ...

  13. 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.

  14. 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.

  15. 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.

  16. Characteristic of root decomposition in a tropical rainforest in Sarawak, Malaysi

    NASA Astrophysics Data System (ADS)

    Ohashi, Mizue; Makita, Naoki; Katayam, Ayumi; Kume, Tomonori; Matsumoto, Kazuho; Khoon Kho, L.

    2016-04-01

    Woody roots play a significant role in forest carbon cycling, as up to 60 percent of tree photosynthetic production can be allocated to belowground. Root decay is one of the main processes of soil C dynamics and potentially relates to soil C sequestration. However, much less attention has been paid for root litter decomposition compared to the studies of leaf litter because roots are hidden from view. Previous studies have revealed that physico-chemical quality of roots, climate, and soil organisms affect root decomposition significantly. However, patterns and mechanisms of root decomposition are still poorly understood because of the high variability of root properties, field environment and potential decomposers. For example, root size would be a factor controlling decomposition rates, but general understanding of the difference between coarse and fine root decompositions is still lacking. Also, it is known that root decomposition is performed by soil animals, fungi and bacteria, but their relative importance is poorly understood. In this study, therefore, we aimed to characterize the root decomposition in a tropical rainforest in Sarawak, Malaysia, and clarify the impact of soil living organisms and root sizes on root litter decomposition. We buried soil cores with fine and coarse root litter bags in soil in Lambir Hills National Park. Three different types of soil cores that are covered by 1.5 cm plastic mesh, root-impermeable sheet (50um) and fungi-impermeable sheet (1um) were prepared. The soil cores were buried in February 2013 and collected 4 times, 134 days, 226 days, 786 days and 1151 days after the installation. We found that nearly 80 percent of the coarse root litter was decomposed after two years, whereas only 60 percent of the fine root litter was decomposed. Our results also showed significantly different ratio of decomposition between different cores, suggesting the different contribution of soil living organisms to decomposition process.

  17. Hydrazine decomposition and other reactions

    NASA Technical Reports Server (NTRS)

    Armstrong, Warren E. (Inventor); La France, Donald S. (Inventor); Voge, Hervey H. (Inventor)

    1978-01-01

    This invention relates to the catalytic decomposition of hydrazine, catalysts useful for this decomposition and other reactions, and to reactions in hydrogen atmospheres generally using carbon-containing catalysts.

  18. Decomposition of Multi-player Games

    NASA Astrophysics Data System (ADS)

    Zhao, Dengji; Schiffel, Stephan; Thielscher, Michael

    Research in General Game Playing aims at building systems that learn to play unknown games without human intervention. We contribute to this endeavour by generalising the established technique of decomposition from AI Planning to multi-player games. To this end, we present a method for the automatic decomposition of previously unknown games into independent subgames, and we show how a general game player can exploit a successful decomposition for game tree search.

  19. Confounding, causality, and confusion: the role of intermediate variables in interpreting observational studies in obstetrics.

    PubMed

    Ananth, Cande V; Schisterman, Enrique F

    2017-08-01

    Prospective and retrospective cohorts and case-control studies are some of the most important study designs in epidemiology because, under certain assumptions, they can mimic a randomized trial when done well. These assumptions include, but are not limited to, properly accounting for 2 important sources of bias: confounding and selection bias. While not adjusting the causal association for an intermediate variable will yield an unbiased estimate of the exposure-outcome's total causal effect, it is often that obstetricians will want to adjust for an intermediate variable to assess if the intermediate is the underlying driver of the association. Such a practice must be weighed in light of the underlying research question and whether such an adjustment is necessary should be carefully considered. Gestational age is, by far, the most commonly encountered variable in obstetrics that is often mislabeled as a confounder when, in fact, it may be an intermediate. If, indeed, gestational age is an intermediate but if mistakenly labeled as a confounding variable and consequently adjusted in an analysis, the conclusions can be unexpected. The implications of this overadjustment of an intermediate as though it were a confounder can render an otherwise persuasive study downright meaningless. This commentary provides an exposition of confounding bias, collider stratification, and selection biases, with applications in obstetrics and perinatal epidemiology. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Computational study on the aminolysis of beta-hydroxy-alpha,beta-unsaturated ester via the favorable path including the formation of alpha-oxo ketene intermediate.

    PubMed

    Jin, Lu; Xue, Ying; Zhang, Hui; Kim, Chan Kyung; Xie, Dai Qian; Yan, Guo Sen

    2008-05-15

    The possible mechanisms of the aminolysis of N-methyl-3-(methoxycarbonyl)-4-hydroxy-2-pyridone (beta-hydroxy-alpha,beta-unsaturated ester) with dimethylamine are investigated at the hybrid density functional theory B3LYP/6-31G(d,p) level in the gas phase. Single-point computations at the B3LYP/6-311++G(d,p) and the Becke88-Becke95 1-parameter model BB1K/6-311++G(d,p) levels are performed for more precise energy predictions. Solvent effects are also assessed by single-point calculations at the integral equation formalism polarized continuum model IEFPCM-B3LYP/6-311++G(d,p) and IEFPCM-BB1K/6-311++G(d,p) levels on the gas-phase optimized geometries. Three possible pathways, the concerted pathway (path A), the stepwise pathway involving tetrahedral intermediates (path B), and the stepwise pathway via alpha-oxo ketene intermediate due to the participation of beta-hydroxy (path C), are taken into account for the title reaction. Moreover, path C includes two sequential processes. The first process is to generate alpha-oxo ketene intermediate via the decomposition of N-methyl-3-(methoxycarbonyl)-4-hydroxy-2-pyridone; the second process is the addition of dimethylamine to alpha-oxo ketene intermediate. Our results indicate that path C is more favorable than paths A and B both in the gas phase and in solvent (heptane). In path C, the first process is the rate-determining step, and the second process is revealed to be a [4+2] pseudopericyclic reaction without the energy barrier. Being independent of the concentration of amine, the first process obeys the first-order rate law.

  1. Tree species diversity affects decomposition through modified micro-environmental conditions across European forests.

    PubMed

    Joly, François-Xavier; Milcu, Alexandru; Scherer-Lorenzen, Michael; Jean, Loreline-Katia; Bussotti, Filippo; Dawud, Seid Muhie; Müller, Sandra; Pollastrini, Martina; Raulund-Rasmussen, Karsten; Vesterdal, Lars; Hättenschwiler, Stephan

    2017-05-01

    Different tree species influence litter decomposition directly through species-specific litter traits, and indirectly through distinct modifications of the local decomposition environment. Whether these indirect effects on decomposition are influenced by tree species diversity is presently not clear. We addressed this question by studying the decomposition of two common substrates, cellulose paper and wood sticks, in a total of 209 forest stands of varying tree species diversity across six major forest types at the scale of Europe. Tree species richness showed a weak but positive correlation with the decomposition of cellulose but not with that of wood. Surprisingly, macroclimate had only a minor effect on cellulose decomposition and no effect on wood decomposition despite the wide range in climatic conditions among sites from Mediterranean to boreal forests. Instead, forest canopy density and stand-specific litter traits affected the decomposition of both substrates, with a particularly clear negative effect of the proportion of evergreen tree litter. Our study suggests that species richness and composition of tree canopies modify decomposition indirectly through changes in microenvironmental conditions. These canopy-induced differences in the local decomposition environment control decomposition to a greater extent than continental-scale differences in macroclimatic conditions. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  2. In depth study of acrylamide formation in coffee during roasting: role of sucrose decomposition and lipid oxidation.

    PubMed

    Kocadağlı, Tolgahan; Göncüoğlu, Neslihan; Hamzalıoğlu, Aytül; Gökmen, Vural

    2012-09-01

    Coffee, as a source of acrylamide, needs to be investigated in depth to understand the contribution of different precursors. This study aimed to investigate the contributions of sucrose decomposition and lipid oxidation on acrylamide formation in coffee during roasting. Coffee beans and model systems were used to monitor the accumulation of neo-formed carbonyls during heating through sucrose decomposition and lipid oxidation. High resolution mass spectrometry analyses confirmed the formation of 5-hydroxymethylfurfural (HMF) and 3,4-dideoxyosone, which were identified as the major sugar decomposition products in both roasted coffee and model systems. Among others, 2-octenal, 2,4-decadienal, 2,4-heptadienal, 4-hydroxynonenal, and 4,5-epoxy-2-decenal were identified in relatively high quantities in roasted coffee. Formation and elimination of HMF in coffee during roasting had a kinetic pattern similar to those of acrylamide. Its concentration rapidly increased within 10 min followed by an exponential decrease afterward. The amount of lipid oxidation products tended to increase linearly during roasting. It was concluded from the results that roasting formed a pool of neo-formed carbonyls from sucrose decomposition and lipid oxidation, and they play certain role on acrylamide formation in coffee.

  3. Dynamics in the Decompositions Approach to Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Harding, John

    2017-12-01

    In Harding (Trans. Amer. Math. Soc. 348(5), 1839-1862 1996) it was shown that the direct product decompositions of any non-empty set, group, vector space, and topological space X form an orthomodular poset Fact X. This is the basis for a line of study in foundational quantum mechanics replacing Hilbert spaces with other types of structures. Here we develop dynamics and an abstract version of a time independent Schrödinger's equation in the setting of decompositions by considering representations of the group of real numbers in the automorphism group of the orthomodular poset Fact X of decompositions.

  4. Reactivity continuum modeling of leaf, root, and wood decomposition across biomes

    NASA Astrophysics Data System (ADS)

    Koehler, Birgit; Tranvik, Lars J.

    2015-07-01

    Large carbon dioxide amounts are released to the atmosphere during organic matter decomposition. Yet the large-scale and long-term regulation of this critical process in global carbon cycling by litter chemistry and climate remains poorly understood. We used reactivity continuum (RC) modeling to analyze the decadal data set of the "Long-term Intersite Decomposition Experiment," in which fine litter and wood decomposition was studied in eight biome types (224 time series). In 32 and 46% of all sites the litter content of the acid-unhydrolyzable residue (AUR, formerly referred to as lignin) and the AUR/nitrogen ratio, respectively, retarded initial decomposition rates. This initial rate-retarding effect generally disappeared within the first year of decomposition, and rate-stimulating effects of nutrients and a rate-retarding effect of the carbon/nitrogen ratio became more prevalent. For needles and leaves/grasses, the influence of climate on decomposition decreased over time. For fine roots, the climatic influence was initially smaller but increased toward later-stage decomposition. The climate decomposition index was the strongest climatic predictor of decomposition. The similar variability in initial decomposition rates across litter categories as across biome types suggested that future changes in decomposition may be dominated by warming-induced changes in plant community composition. In general, the RC model parameters successfully predicted independent decomposition data for the different litter-biome combinations (196 time series). We argue that parameterization of large-scale decomposition models with RC model parameters, as opposed to the currently common discrete multiexponential models, could significantly improve their mechanistic foundation and predictive accuracy across climate zones and litter categories.

  5. Soil fauna and plant litter decomposition in tropical and subalpine forests

    Treesearch

    G. Gonzalez; T.R. Seastedt

    2001-01-01

    The decomposition of plant residues is influenced by their chemical composition, the physical-chemical environment, and the decomposer organisms. Most studies interested in latitudinal gradients of decomposition have focused on substrate quality and climate effects on decomposition, and have excluded explicit recognition of the soil organisms involved in the process....

  6. Surface-Accelerated Decomposition of δ-HMX.

    PubMed

    Sharia, Onise; Tsyshevsky, Roman; Kuklja, Maija M

    2013-03-07

    Despite extensive efforts to study the explosive decomposition of HMX, a cyclic nitramine widely used as a solid fuel, explosive, and propellant, an understanding of the physicochemical processes, governing the sensitivity of condensed HMX to detonation initiation is not yet achieved. Experimental and theoretical explorations of the initiation of chemistry are equally challenging because of many complex parallel processes, including the β-δ phase transition and the decomposition from both phases. Among four known polymorphs, HMX is produced in the most stable β-phase, which transforms into the most reactive δ-phase under heat or pressure. In this study, the homolytic NO2 loss and HONO elimination precursor reactions of the gas-phase, ideal crystal, and the (100) surface of δ-HMX are explored by first principles modeling. Our calculations revealed that the high sensitivity of δ-HMX is attributed to interactions of surfaces and molecular dipole moments. While both decomposition reactions coexist, the exothermic HONO-isomer formation catalyzes the N-NO2 homolysis, leading to fast violent explosions.

  7. Factors Influencing Decomposition of Surface Litter from the Cerrado in Central Brazil

    EPA Science Inventory

    It is well-established that light-induced decomposition can accelerate the decomposition of the organic matter in aquatic environments. In this study, using the production of carbon monoxide as an indicator of decomposition, we investigated the wavelength dependence of the photod...

  8. Crop residue decomposition in Minnesota biochar-amended plots

    NASA Astrophysics Data System (ADS)

    Weyers, S. L.; Spokas, K. A.

    2014-06-01

    Impacts of biochar application at laboratory scales are routinely studied, but impacts of biochar application on decomposition of crop residues at field scales have not been widely addressed. The priming or hindrance of crop residue decomposition could have a cascading impact on soil processes, particularly those influencing nutrient availability. Our objectives were to evaluate biochar effects on field decomposition of crop residue, using plots that were amended with biochars made from different plant-based feedstocks and pyrolysis platforms in the fall of 2008. Litterbags containing wheat straw material were buried in July of 2011 below the soil surface in a continuous-corn cropped field in plots that had received one of seven different biochar amendments or a uncharred wood-pellet amendment 2.5 yr prior to start of this study. Litterbags were collected over the course of 14 weeks. Microbial biomass was assessed in treatment plots the previous fall. Though first-order decomposition rate constants were positively correlated to microbial biomass, neither parameter was statistically affected by biochar or wood-pellet treatments. The findings indicated only a residual of potentially positive and negative initial impacts of biochars on residue decomposition, which fit in line with established feedstock and pyrolysis influences. Overall, these findings indicate that no significant alteration in the microbial dynamics of the soil decomposer communities occurred as a consequence of the application of plant-based biochars evaluated here.

  9. Experimental study on the performance of the vapor injection refrigeration system with an economizer for intermediate pressures

    NASA Astrophysics Data System (ADS)

    Moon, Chang-Uk; Choi, Kwang-Hwan; Yoon, Jung-In; Kim, Young-Bok; Son, Chang-Hyo; Ha, Soo-Jung; Jeon, Min-Ju; An, Sang-Young; Lee, Joon-Hyuk

    2018-04-01

    In this study, to investigate the performance characteristics of vapor injection refrigeration system with an economizer at an intermediate pressure, the vapor injection refrigeration system was analyzed under various experiment conditions. As a result, the optimum design data of the vapor injection refrigeration system with an economizer were obtained. The findings from this study can be summarized as follows. The mass flow rate through the compressor increases with intermediate pressure. The compression power input showed an increasing trend under all the test conditions. The evaporation capacity increased and then decreased at the intermediate pressure, and as such, it became maximum at the given intermediate pressure. The increased mass flow rate of the by-passed refrigerant enhanced the evaporation capacity at the low medium pressure range, but the increased saturation temperature limited the subcooling degree of the liquid refrigerant after the application of the economizer when the intermediate pressure kept rising, and degenerated the evaporation capacity. The coefficient of performance (COP) increased and then decreased with respect to the intermediate pressures under all the experiment conditions. Nevertheless, there was an optimum intermediate pressure for the maximum COP under each experiment condition. Therefore, the optimum intermediate pressure in this study was found at -99.08 kPa, which is the theoretical standard medium pressure under all the test conditions.

  10. Analytical separations of mammalian decomposition products for forensic science: a review.

    PubMed

    Swann, L M; Forbes, S L; Lewis, S W

    2010-12-03

    The study of mammalian soft tissue decomposition is an emerging area in forensic science, with a major focus of the research being the use of various chemical and biological methods to study the fate of human remains in the environment. Decomposition of mammalian soft tissue is a postmortem process that, depending on environmental conditions and physiological factors, will proceed until complete disintegration of the tissue. The major stages of decomposition involve complex reactions which result in the chemical breakdown of the body's main constituents; lipids, proteins, and carbohydrates. The first step to understanding this chemistry is identifying the compounds present in decomposition fluids and determining when they are produced. This paper provides an overview of decomposition chemistry and reviews recent advances in this area utilising analytical separation science. Copyright © 2010 Elsevier B.V. All rights reserved.

  11. Delineating gas bearing reservoir by using spectral decomposition attribute: Case study of Steenkool formation, Bintuni Basin

    NASA Astrophysics Data System (ADS)

    Haris, A.; Pradana, G. S.; Riyanto, A.

    2017-07-01

    Tectonic setting of the Bird Head Papua Island becomes an important model for petroleum system in Eastern part of Indonesia. The current exploration has been started since the oil seepage finding in Bintuni and Salawati Basin. The biogenic gas in shallow layer turns out to become an interesting issue in the hydrocarbon exploration. The hydrocarbon accumulation appearance in a shallow layer with dry gas type, appeal biogenic gas for further research. This paper aims at delineating the sweet spot hydrocarbon potential in shallow layer by applying the spectral decomposition technique. The spectral decomposition is decomposing the seismic signal into an individual frequency, which has significant geological meaning. One of spectral decomposition methods is Continuous Wavelet Transform (CWT), which transforms the seismic signal into individual time and frequency simultaneously. This method is able to make easier time-frequency map analysis. When time resolution increases, the frequency resolution will be decreased, and vice versa. In this study, we perform low-frequency shadow zone analysis in which the amplitude anomaly at a low frequency of 15 Hz was observed and we then compare it to the amplitude at the mid (20 Hz) and the high-frequency (30 Hz). The appearance of the amplitude anomaly at a low frequency was disappeared at high frequency, this anomaly disappears. The spectral decomposition by using CWT algorithm has been successfully applied to delineate the sweet spot zone.

  12. Decomposition of aquatic plants in lakes

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

    Godshalk, G.L.

    1977-01-01

    This study was carried out to systematically determine the effects of temperature and oxygen concentration, two environmental parameters crucial to lake metabolism in general, on decomposition of five species of aquatic vascular plants of three growth forms in a Michigan lake. Samples of dried plant material were decomposed in flasks in the laboratory under three different oxygen regimes, aerobic-to-anaerobic, strict anaerobic, and aerated, each at 10/sup 0/C and 25/sup 0/C. In addition, in situ decomposition of the same species was monitored using the litter bag technique under four conditions.

  13. The influence of preburial insect access on the decomposition rate.

    PubMed

    Bachmann, Jutta; Simmons, Tal

    2010-07-01

    This study compared total body score (TBS) in buried remains (35 cm depth) with and without insect access prior to burial. Sixty rabbit carcasses were exhumed at 50 accumulated degree day (ADD) intervals. Weight loss, TBS, intra-abdominal decomposition, carcass/soil interface temperature, and below-carcass soil pH were recorded and analyzed. Results showed significant differences (p < 0.001) in decomposition rates between carcasses with and without insect access prior to burial. An approximately 30% enhanced decomposition rate with insects was observed. TBS was the most valid tool in postmortem interval (PMI) estimation. All other variables showed only weak relationships to decomposition stages, adding little value to PMI estimation. Although progress in estimating the PMI for surface remains has been made, no previous studies have accomplished this for buried remains. This study builds a framework to which further comparable studies can contribute, to produce predictive models for PMI estimation in buried human remains.

  14. Decomposition and arthropod succession in Whitehorse, Yukon Territory, Canada.

    PubMed

    Bygarski, Katherine; LeBlanc, Helene N

    2013-03-01

    Forensic arthropod succession patterns are known to vary between regions. However, the northern habitats of the globe have been largely left unstudied. Three pig carcasses were studied outdoors in Whitehorse, Yukon Territory. Adult and immature insects were collected for identification and comparison. The dominant Diptera and Coleoptera species at all carcasses were Protophormia terraneovae (R-D) (Fam: Calliphoridae) and Thanatophilus lapponicus (Herbst) (Fam: Silphidae), respectively. Rate of decomposition, patterns of Diptera and Coleoptera succession, and species dominance were shown to differ from previous studies in temperate regions, particularly as P. terraenovae showed complete dominance among blowfly species. Rate of decomposition through the first four stages was generally slow, and the last stage of decomposition was not observed at any carcass due to time constraints. It is concluded that biogeoclimatic range has a significant effect on insect presence and rate of decomposition, making it an important factor to consider when calculating a postmortem interval. © 2012 American Academy of Forensic Sciences.

  15. 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.

  16. Electrochemical and Infrared Absorption Spectroscopy Detection of SF6 Decomposition Products

    PubMed Central

    Dong, Ming; Ren, Ming; Ye, Rixin

    2017-01-01

    Sulfur hexafluoride (SF6) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF6 decomposition and ultimately generates several types of decomposition products. These SF6 decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF6 decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF6 gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF6 decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF6 gas decomposition and is verified to reliably and accurately detect the gas components and concentrations. PMID:29140268

  17. Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement.

    PubMed

    Thompson, Helen; Soper, Alan K; Buchanan, Piers; Aldiwan, Nawaf; Creek, Jefferson L; Koh, Carolyn A

    2006-04-28

    Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.

  18. Microbial ecological succession during municipal solid waste decomposition.

    PubMed

    Staley, Bryan F; de Los Reyes, Francis L; Wang, Ling; Barlaz, Morton A

    2018-04-28

    The decomposition of landfilled refuse proceeds through distinct phases, each defined by varying environmental factors such as volatile fatty acid concentration, pH, and substrate quality. The succession of microbial communities in response to these changing conditions was monitored in a laboratory-scale simulated landfill to minimize measurement difficulties experienced at field scale. 16S rRNA gene sequences retrieved at separate stages of decomposition showed significant succession in both Bacteria and methanogenic Archaea. A majority of Bacteria sequences in landfilled refuse belong to members of the phylum Firmicutes, while Proteobacteria levels fluctuated and Bacteroidetes levels increased as decomposition proceeded. Roughly 44% of archaeal sequences retrieved under conditions of low pH and high acetate were strictly hydrogenotrophic (Methanomicrobiales, Methanobacteriales). Methanosarcina was present at all stages of decomposition. Correspondence analysis showed bacterial population shifts were attributed to carboxylic acid concentration and solids hydrolysis, while archaeal populations were affected to a higher degree by pH. T-RFLP analysis showed specific taxonomic groups responded differently and exhibited unique responses during decomposition, suggesting that species composition and abundance within Bacteria and Archaea are highly dynamic. This study shows landfill microbial demographics are highly variable across both spatial and temporal transects.

  19. Seasonal variation of carcass decomposition and gravesoil chemistry in a cold (Dfa) climate.

    PubMed

    Meyer, Jessica; Anderson, Brianna; Carter, David O

    2013-09-01

    It is well known that temperature significantly affects corpse decomposition. Yet relatively few taphonomy studies investigate the effects of seasonality on decomposition. Here, we propose the use of the Köppen-Geiger climate classification system and describe the decomposition of swine (Sus scrofa domesticus) carcasses during the summer and winter near Lincoln, Nebraska, USA. Decomposition was scored, and gravesoil chemistry (total carbon, total nitrogen, ninhydrin-reactive nitrogen, ammonium, nitrate, and soil pH) was assessed. Gross carcass decomposition in summer was three to seven times greater than in winter. Initial significant changes in gravesoil chemistry occurred following approximately 320 accumulated degree days, regardless of season. Furthermore, significant (p < 0.05) correlations were observed between ammonium and pH (positive correlation) and between nitrate and pH (negative correlation). We hope that future decomposition studies employ the Köppen-Geiger climate classification system to understand the seasonality of corpse decomposition, to validate taphonomic methods, and to facilitate cross-climate comparisons of carcass decomposition. © 2013 American Academy of Forensic Sciences.

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

    PubMed

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

    2012-10-15

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

  1. Decomposition mechanism of chromite in sulfuric acid-dichromic acid solution

    NASA Astrophysics Data System (ADS)

    Zhao, Qing; Liu, Cheng-jun; Li, Bao-kuan; Jiang, Mao-fa

    2017-12-01

    The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg-Al, Mg-Fe, and Mg-Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid-dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg-Al spinel and Mg-Fe spinel because Mg2+, Al3+, and Fe3+ in spinels cannot be oxidized by Cr6+. However, in the case of the Mg-Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid-dichromic acid solution was illustrated on the basis of the findings of this study.

  2. Effects of anthropogenic heavy metal contamination on litter decomposition in streams - A meta-analysis.

    PubMed

    Ferreira, Verónica; Koricheva, Julia; Duarte, Sofia; Niyogi, Dev K; Guérold, François

    2016-03-01

    Many streams worldwide are affected by heavy metal contamination, mostly due to past and present mining activities. Here we present a meta-analysis of 38 studies (reporting 133 cases) published between 1978 and 2014 that reported the effects of heavy metal contamination on the decomposition of terrestrial litter in running waters. Overall, heavy metal contamination significantly inhibited litter decomposition. The effect was stronger for laboratory than for field studies, likely due to better control of confounding variables in the former, antagonistic interactions between metals and other environmental variables in the latter or differences in metal identity and concentration between studies. For laboratory studies, only copper + zinc mixtures significantly inhibited litter decomposition, while no significant effects were found for silver, aluminum, cadmium or zinc considered individually. For field studies, coal and metal mine drainage strongly inhibited litter decomposition, while drainage from motorways had no significant effects. The effect of coal mine drainage did not depend on drainage pH. Coal mine drainage negatively affected leaf litter decomposition independently of leaf litter identity; no significant effect was found for wood decomposition, but sample size was low. Considering metal mine drainage, arsenic mines had a stronger negative effect on leaf litter decomposition than gold or pyrite mines. Metal mine drainage significantly inhibited leaf litter decomposition driven by both microbes and invertebrates, independently of leaf litter identity; no significant effect was found for microbially driven decomposition, but sample size was low. Overall, mine drainage negatively affects leaf litter decomposition, likely through negative effects on invertebrates. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Long-term amelioration of acidity accelerates decomposition in headwater streams.

    PubMed

    Jenkins, Gareth B; Woodward, Guy; Hildrew, Alan G

    2013-04-01

    The secondary production of culturally acidified streams is low, with a few species of generalist detritivores dominating invertebrate assemblages, while decomposition processes are impaired. In a series of lowland headwater streams in southern England, we measured the rate of cellulolytic decomposition and compared it with values measured three decades ago, when anthropogenic acidification was at its peak. We hypothesized that, if acidity has indeed ameliorated, the rate of decomposition will have accelerated, thus potentially supporting greater secondary production and the longer food chains that have been observed in some well-studied recovering freshwater systems. We used cellulose Shirley test cloth as a standardized bioassay to measure the rate of cellulolytic decomposition, via loss in tensile strength, for 31 streams in the Ashdown Forest over 7 days in summer 2011 and 49 days in winter 2012. We compared this with data from an otherwise identical study conducted in 1978 and 1979. In a secondary study, we determined whether decomposition followed a linear or logarithmic decay and, as Shirley cloth is no longer available, we tested an alternative in the form of readily available calico. Overall mean pH had increased markedly over the 32 years between the studies (from 6.0 to 6.7). In both the previous and contemporary studies, the relationship between decomposition and pH was strongest in winter, when pH reaches a seasonal minimum. As in the late 1970s, there was no relationship in 2011/2012 between pH and decay rate in summer. As postulated, decomposition in winter was significantly faster in 2011/2012 than in 1978/1979, with an average increase in decay rate of 18.1%. Recovery from acidification, due to decreased acidifying emissions and deposition, has led to an increase in the rate of cellulolytic decomposition. This response in a critical ecosystem process offers a potential explanation of one aspect of the limited biological recovery that has been

  4. Application of the nonlinear Blinder-Oaxaca decomposition to study racial/ethnic disparities in antiobesity medication use in the United States.

    PubMed

    Mehta, Hemalkumar B; Rajan, Suja S; Aparasu, Rajender R; Johnson, Michael L

    2013-01-01

    The nonlinear Blinder-Oaxaca (BO) decomposition method is gaining popularity in health services research because of its ability to explain disparity issues. The present study demonstrates the use of this method for categorical variables by addressing antiobesity medication use disparity. To examine racial/ethnic disparity in antiobesity medication use and to quantify the observed factor contribution behind the disparity using the nonlinear BO decomposition. Medical Expenditure Panel Survey data, 2002-2007, were used in this retrospective cross-sectional study. Adults with body mass index (BMI) >30, or BMI ≥27 and comorbidities such as hypertension, cardiovascular diseases, diabetes, or hyperlipidemia were included in the cohort (N=65,886,625). Multivariable logistic regression was performed to examine racial/ethnic disparity in antiobesity medication use controlling for predisposing, enabling, and need factors. The nonlinear BO decomposition was used to identify the contribution of each predisposing, enabling, and need factors in explaining the racial/ethnic disparity and to estimate the residual unexplained disparity. Non-Hispanic Blacks were 46% (odds ratio [OR]: 0.54; 95% confidence interval [CI]: 0.35-0.83) less likely to use antiobesity drugs compared with non-Hispanic Whites, whereas no difference was observed between Hispanics and non-Hispanic Whites. A 0.22 percentage point of disparity existed between non-Hispanic Whites and Blacks. The nonlinear BO decomposition estimated a decomposition coefficient of -0.0013 indicating that the observed disparity would have been 58% higher (-0.0013/0.0022) if non-Hispanic Blacks had similar observed characteristics as non-Hispanic Whites. Age, gender, marital status, region, and BMI were significant factors in the decomposition model; only marital status explained the racial/ethnic disparity among all observed characteristics. The study revealed that differences in the predisposing, enabling, and need characteristics

  5. Neural Correlates of Morphological Decomposition in a Morphologically Rich Language: An fMRI Study

    ERIC Educational Resources Information Center

    Lehtonen, Minna; Vorobyev, Victor A.; Hugdahl, Kenneth; Tuokkola, Terhi; Laine, Matti

    2006-01-01

    By employing visual lexical decision and functional MRI, we studied the neural correlates of morphological decomposition in a highly inflected language (Finnish) where most inflected noun forms elicit a consistent processing cost during word recognition. This behavioral effect could reflect suffix stripping at the visual word form level and/or…

  6. Analysis of Self-Excited Combustion Instabilities Using Decomposition Techniques

    DTIC Science & Technology

    2016-07-05

    are evaluated for the study of self-excited longitudinal combustion instabilities in laboratory-scaled single-element gas turbine and rocket...Air Force Base, California 93524 DOI: 10.2514/1.J054557 Proper orthogonal decomposition and dynamic mode decomposition are evaluated for the study of...instabilities. In addition, we also evaluate the capabilities of the methods to deal with data sets of different spatial extents and temporal resolution

  7. Associational Patterns of Scavenger Beetles to Decomposition Stages.

    PubMed

    Zanetti, Noelia I; Visciarelli, Elena C; Centeno, Nestor D

    2015-07-01

    Beetles associated with carrion play an important role in recycling organic matter in an ecosystem. Four experiments on decomposition, one per season, were conducted in a semirural area in Bahía Blanca, Argentina. Melyridae are reported for the first time of forensic interest. Apart from adults and larvae of Scarabaeidae, thirteen species and two genera of other coleopteran families are new forensic records in Argentina. Diversity, abundance, and species composition of beetles showed differences between stages and seasons. Our results differed from other studies conducted in temperate regions. Four guilds and succession patterns were established in relation to decomposition stages and seasons. Dermestidae (necrophages) predominated in winter during the decomposition process; Staphylinidae (necrophiles) in Fresh and Bloat stages during spring, summer, and autumn; and Histeridae (necrophiles) and Cleridae (omnivores) in the following stages during those seasons. Finally, coleopteran activity, diversity and abundance, and decomposition rate change with biogeoclimatic characteristics, which is of significance in forensics. © 2015 American Academy of Forensic Sciences.

  8. An ammonia-stabilized mixed-cation borohydride: synthesis, structure and thermal decomposition behavior.

    PubMed

    Yang, Yanjing; Liu, Yongfeng; Wu, Hui; Zhou, Wei; Gao, Mingxia; Pan, Hongge

    2014-01-07

    We demonstrate the synthesis, crystal structure and thermal decomposition behavior of a novel ammonia-stabilized mixed-cation borohydride where the NH3 groups enable the coexistence of Li and Mg cations as an "assistant". Li2Mg(BH4)4·6NH3, which is comprised of orderly arranged Mg[NH3]6(2+) ammine complexes and Li2[BH4]4(2-) complex anions, was synthesized by the mechanochemical reaction between Mg(BH4)2·6NH3 and LiBH4. This novel compound crystallizes in a tetragonal P4(3)2(1)2 (No. 96) structure with lattice parameters a = b = 10.7656(8) Å and c = 13.843(1) Å with very short dihydrogen bonds, which determine a very low onset temperature of 80 °C for hydrogen release and are also responsible for the nucleation of Li2Mg(BH4)4·3NH3 as a decomposition intermediate. Mechanistic investigations on the thermal decomposition showed that the H(δ+)-H(δ-) combination in the ammonia-stabilized mixed-cation borohydride was significantly enhanced due to the strengthened Mg-N bonds. Upon heating, 11.02 moles of H2 (equivalent to 11.1 wt%) and 3.07 moles of NH3 are evolved from one mole of Li2Mg(BH4)4·6NH3 with a three-step reaction. The insights into the formation mechanism of ammonia-stabilized mixed-cation borohydride and the role played by NH3 group are very useful as a guideline for the design and synthesis of novel B-N-based materials with high hydrogen content.

  9. The Outer Loop bioreactor: a case study of settlement monitoring and solids decomposition.

    PubMed

    Abichou, Tarek; Barlaz, Morton A; Green, Roger; Hater, Gary

    2013-10-01

    The Outer Loop landfill bioreactor (OLLB) located in Louisville, KY, USA has been in operation since 2000 and represents an opportunity to evaluate long-term bioreactor monitoring data at a full-scale operational landfill. Three types of landfill units were studied including a Control cell, a new landfill area that had a piping network installed as waste was being placed to support leachate recirculation (As-Built cell), and a conventional landfill that was modified to allow for liquid recirculation (Retrofit cell). The objective of this study is to summarize the results of settlement data and assess how these data relate to solids decomposition monitoring at the OLLB. The Retrofit cells started to settle as soon as liquids were introduced. The cumulative settlement during the 8years of monitoring varied from 60 to 100cm. These results suggest that liquid recirculation in the Retrofit cells caused a 5-8% reduction in the thickness of the waste column. The average long-term settlement in the As-Built and Control Cells was about 37% and 19%, respectively. The modified compression index (Cα(')) was 0.17 for the Control cells and 0.2-0.48 for the As-Built cells. While the As-Built cells exhibited greater settlement than the Control cells, the data do not support biodegradation as the only explanation. The increased settlement in the As-Built bioreactor cell appeared to be associated with liquid movement and not with biodegradation because both chemical (biochemical methane potential) and physical (moisture content) indicators of decomposition were similar in the Control and As-Built cells. The solids data are consistent with the concept that bioreactor operations accelerate the rate of decomposition, but not necessarily the cumulative loss of anaerobically degradable solids. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. On the Possibility of Studying the Reactions of the Thermal Decomposition of Energy Substances by the Methods of High-Resolution Terahertz Spectroscopy

    NASA Astrophysics Data System (ADS)

    Vaks, V. L.; Domracheva, E. G.; Chernyaeva, M. B.; Pripolzin, S. I.; Revin, L. S.; Tretyakov, I. V.; Anfertyev, V. A.; Yablokov, A. A.; Lukyanenko, I. A.; Sheikov, Yu. V.

    2018-02-01

    We show prospects for using the method of high-resolution terahertz spectroscopy for a continuous analysis of the decomposition products of energy substances in the gas phase (including short-lived ones) in a wide temperature range. The experimental setup, which includes a terahertz spectrometer for studying the thermal decomposition reactions, is described. The results of analysis of the gaseous decomposition products of energy substances by the example of ammonium nitrate heated from room temperature to 167°C are presented.

  11. Direct and Indirect Effects of UV-B Exposure on Litter Decomposition: A Meta-Analysis

    PubMed Central

    Song, Xinzhang; Peng, Changhui; Jiang, Hong; Zhu, Qiuan; Wang, Weifeng

    2013-01-01

    Ultraviolet-B (UV-B) exposure in the course of litter decomposition may have a direct effect on decomposition rates via changing states of photodegradation or decomposer constitution in litter while UV-B exposure during growth periods may alter chemical compositions and physical properties of plants. Consequently, these changes will indirectly affect subsequent litter decomposition processes in soil. Although studies are available on both the positive and negative effects (including no observable effects) of UV-B exposure on litter decomposition, a comprehensive analysis leading to an adequate understanding remains unresolved. Using data from 93 studies across six biomes, this introductory meta-analysis found that elevated UV-B directly increased litter decomposition rates by 7% and indirectly by 12% while attenuated UV-B directly decreased litter decomposition rates by 23% and indirectly increased litter decomposition rates by 7%. However, neither positive nor negative effects were statistically significant. Woody plant litter decomposition seemed more sensitive to UV-B than herbaceous plant litter except under conditions of indirect effects of elevated UV-B. Furthermore, levels of UV-B intensity significantly affected litter decomposition response to UV-B (P<0.05). UV-B effects on litter decomposition were to a large degree compounded by climatic factors (e.g., MAP and MAT) (P<0.05) and litter chemistry (e.g., lignin content) (P<0.01). Results suggest these factors likely have a bearing on masking the important role of UV-B on litter decomposition. No significant differences in UV-B effects on litter decomposition were found between study types (field experiment vs. laboratory incubation), litter forms (leaf vs. needle), and decay duration. Indirect effects of elevated UV-B on litter decomposition significantly increased with decay duration (P<0.001). Additionally, relatively small changes in UV-B exposure intensity (30%) had significant direct effects on litter

  12. 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

  13. A comparative study of the decomposition of pig carcasses in a methyl methacrylate box and open air conditions.

    PubMed

    Li, Liangliang; Wang, Jiangfeng; Wang, Yu

    2016-08-01

    Analysis of the process of decomposition is essential in establishing the postmortem interval. However, despite the fact that insects are important players in body decomposition, their exact function within the decay process is still unclear. There is also limited knowledge as to how the decomposition process occurs in the absence of insects. In the present study, we compared the decomposition of a pig carcass in open air with that of one placed in a methyl methacrylate box to prevent insect contact. The pig carcass in the methyl methacrylate box was in the fresh stage for 1 day, the bloated stage from 2 d to 11 d, and underwent deflated decay from 12 d. In contrast, the pig carcass in open air went through the fresh, bloated, active decay and post-decay stages; and 22.3 h (0.93 d), 62.47 h (2.60 d), 123.63 h (5.15 d) and 246.5 h (10.27 d) following the start of the experiment respectively, prior to entering the skeletonization stage. A large amount of soft tissue were remained on the pig carcass in the methyl methacrylate box on 26 d, while only scattered bones remained on the pig carcass in open air. The results indicate that insects greatly accelerate the decomposition process. Copyright © 2016 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

  14. A Longitudinal Study on Human Outdoor Decomposition in Central Texas.

    PubMed

    Suckling, Joanna K; Spradley, M Katherine; Godde, Kanya

    2016-01-01

    The development of a methodology that estimates the postmortem interval (PMI) from stages of decomposition is a goal for which forensic practitioners strive. A proposed equation (Megyesi et al. 2005) that utilizes total body score (TBS) and accumulated degree days (ADD) was tested using longitudinal data collected from human remains donated to the Forensic Anthropology Research Facility (FARF) at Texas State University-San Marcos. Exact binomial tests examined the rate of the equation to successfully predict ADD. Statistically significant differences were found between ADD estimated by the equation and the observed value for decomposition stage. Differences remained significant after carnivore scavenged donations were removed from analysis. Low success rates for the equation to predict ADD from TBS and the wide standard errors demonstrate the need to re-evaluate the use of this equation and methodology for PMI estimation in different environments; rather, multivariate methods and equations should be derived that are environmentally specific. © 2015 American Academy of Forensic Sciences.

  15. A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

    NASA Astrophysics Data System (ADS)

    Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

    2015-03-01

    We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

  16. 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

  17. Spatial, temporal, and hybrid decompositions for large-scale vehicle routing with time windows

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

    Bent, Russell W

    This paper studies the use of decomposition techniques to quickly find high-quality solutions to large-scale vehicle routing problems with time windows. It considers an adaptive decomposition scheme which iteratively decouples a routing problem based on the current solution. Earlier work considered vehicle-based decompositions that partitions the vehicles across the subproblems. The subproblems can then be optimized independently and merged easily. This paper argues that vehicle-based decompositions, although very effective on various problem classes also have limitations. In particular, they do not accommodate temporal decompositions and may produce spatial decompositions that are not focused enough. This paper then proposes customer-based decompositionsmore » which generalize vehicle-based decouplings and allows for focused spatial and temporal decompositions. Experimental results on class R2 of the extended Solomon benchmarks demonstrates the benefits of the customer-based adaptive decomposition scheme and its spatial, temporal, and hybrid instantiations. In particular, they show that customer-based decompositions bring significant benefits over large neighborhood search in contrast to vehicle-based decompositions.« less

  18. Descent theory for semiorthogonal decompositions

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

    Elagin, Alexei D

    We put forward a method for constructing semiorthogonal decompositions of the derived category of G-equivariant sheaves on a variety X under the assumption that the derived category of sheaves on X admits a semiorthogonal decomposition with components preserved by the action of the group G on X. This method is used to obtain semiorthogonal decompositions of equivariant derived categories for projective bundles and blow-ups with a smooth centre as well as for varieties with a full exceptional collection preserved by the group action. Our main technical tool is descent theory for derived categories. Bibliography: 12 titles.

  19. Children's use of decomposition strategies mediates the visuospatial memory and arithmetic accuracy relation.

    PubMed

    Foley, Alana E; Vasilyeva, Marina; Laski, Elida V

    2017-06-01

    This study examined the mediating role of children's use of decomposition strategies in the relation between visuospatial memory (VSM) and arithmetic accuracy. Children (N = 78; Age M = 9.36) completed assessments of VSM, arithmetic strategies, and arithmetic accuracy. Consistent with previous findings, VSM predicted arithmetic accuracy in children. Extending previous findings, the current study showed that the relation between VSM and arithmetic performance was mediated by the frequency of children's use of decomposition strategies. Identifying the role of arithmetic strategies in this relation has implications for increasing the math performance of children with lower VSM. Statement of contribution What is already known on this subject? The link between children's visuospatial working memory and arithmetic accuracy is well documented. Frequency of decomposition strategy use is positively related to children's arithmetic accuracy. Children's spatial skill positively predicts the frequency with which they use decomposition. What does this study add? Short-term visuospatial memory (VSM) positively relates to the frequency of children's decomposition use. Decomposition use mediates the relation between short-term VSM and arithmetic accuracy. Children with limited short-term VSM may struggle to use decomposition, decreasing accuracy. © 2016 The British Psychological Society.

  20. Calibration methods influence quantitative material decomposition in photon-counting spectral CT

    NASA Astrophysics Data System (ADS)

    Curtis, Tyler E.; Roeder, Ryan K.

    2017-03-01

    Photon-counting detectors and nanoparticle contrast agents can potentially enable molecular imaging and material decomposition in computed tomography (CT). Material decomposition has been investigated using both simulated and acquired data sets. However, the effect of calibration methods on material decomposition has not been systematically investigated. Therefore, the objective of this study was to investigate the influence of the range and number of contrast agent concentrations within a modular calibration phantom on quantitative material decomposition. A commerciallyavailable photon-counting spectral micro-CT (MARS Bioimaging) was used to acquire images with five energy bins selected to normalize photon counts and leverage the contrast agent k-edge. Material basis matrix values were determined using multiple linear regression models and material decomposition was performed using a maximum a posteriori estimator. The accuracy of quantitative material decomposition was evaluated by the root mean squared error (RMSE), specificity, sensitivity, and area under the curve (AUC). An increased maximum concentration (range) in the calibration significantly improved RMSE, specificity and AUC. The effects of an increased number of concentrations in the calibration were not statistically significant for the conditions in this study. The overall results demonstrated that the accuracy of quantitative material decomposition in spectral CT is significantly influenced by calibration methods, which must therefore be carefully considered for the intended diagnostic imaging application.

  1. Root traits predict decomposition across a landscape-scale grazing experiment

    PubMed Central

    Smith, Stuart W; Woodin, Sarah J; Pakeman, Robin J; Johnson, David; van der Wal, René

    2014-01-01

    Root litter is the dominant soil carbon and nutrient input in many ecosystems, yet few studies have considered how root decomposition is regulated at the landscape scale and how this is mediated by land-use management practices. Large herbivores can potentially influence below-ground decomposition through changes in soil microclimate (temperature and moisture) and changes in plant species composition (root traits). To investigate such herbivore-induced changes, we quantified annual root decomposition of upland grassland species in situ across a landscape-scale livestock grazing experiment, in a common-garden experiment and in laboratory microcosms evaluating the influence of key root traits on decomposition. Livestock grazing increased soil temperatures, but this did not affect root decomposition. Grazing had no effect on soil moisture, but wetter soils retarded root decomposition. Species-specific decomposition rates were similar across all grazing treatments, and species differences were maintained in the common-garden experiment, suggesting an overriding importance of litter type. Supporting this, in microcosms, roots with lower specific root area (m2 g−1) or those with higher phosphorus concentrations decomposed faster. Our results suggest that large herbivores alter below-ground carbon and nitrogen dynamics more through their effects on plant species composition and associated root traits than through effects on the soil microclimate. PMID:24841886

  2. Litter decomposition rate and soil organic matter quality in a patchwork heathland of Southern Norway

    NASA Astrophysics Data System (ADS)

    Certini, G.; Vestgarden, L. S.; Forte, C.; Tau Strand, L.

    2014-07-01

    Norwegian heathland soils, although scant and shallow, are major reservoirs of carbon (C). We aimed at assessing whether vegetation cover and, indirectly, its driving factor soil drainage are good proxies for soil organic matter (SOM) composition and dynamics in a typical heathland area of Southern Norway consisting in a patchwork of three different types of vegetation, dominated by Calluna, Molinia, or Sphagnum. Such vegetation covers were clearly associated to microtopographic differences, which in turn dictated differences in soil moisture regime, Calluna growing in the driest sites, Sphagnum in the wettest, and Molinia in sites with intermediate moisture. Litter decomposition was followed over a period of 1 year, by placing litterbags filled with biomass from each dominant species under each type of vegetation cover. The composition of the living biomass, the bulk SOM and some extractable fractions of SOM were investigated by chemical methods and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Litter decomposition was faster for Molinia and Calluna, irrespective of the vegetation cover of the site where they were placed. Sphagnum litter decomposed very slowly, especially under Calluna, where the soil environment is by far more oxidising than under itself. In terms of SOM quality, Calluna covered areas showed the greatest differences from the others, in particular a much higher contribution from lipids and aliphatic biopolymers, apparently related to biomass composition. Our findings showed that in the studied environment litter decomposition rate and SOM composition are actually dependent on vegetation cover and/or soil drainage. On this basis, monitoring changes in the patchwork of vegetation types in boreal heathlands could be a reliable cost-effective way to account for modifications in the SOM potential to last induced by climate change.

  3. Human versus animal: contrasting decomposition dynamics of mammalian analogues in experimental taphonomy.

    PubMed

    Stokes, Kathryn L; Forbes, Shari L; Tibbett, Mark

    2013-05-01

    Taphonomic studies regularly employ animal analogues for human decomposition due to ethical restrictions relating to the use of human tissue. However, the validity of using animal analogues in soil decomposition studies is still questioned. This study compared the decomposition of skeletal muscle tissues (SMTs) from human (Homo sapiens), pork (Sus scrofa), beef (Bos taurus), and lamb (Ovis aries) interred in soil microcosms. Fixed interval samples were collected from the SMT for microbial activity and mass tissue loss determination; samples were also taken from the underlying soil for pH, electrical conductivity, and nutrient (potassium, phosphate, ammonium, and nitrate) analysis. The overall patterns of nutrient fluxes and chemical changes in nonhuman SMT and the underlying soil followed that of human SMT. Ovine tissue was the most similar to human tissue in many of the measured parameters. Although no single analogue was a precise predictor of human decomposition in soil, all models offered close approximations in decomposition dynamics. © 2013 American Academy of Forensic Sciences.

  4. A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

    NASA Astrophysics Data System (ADS)

    Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

    The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid

  5. 9 CFR 354.131 - Decomposition.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Decomposition. 354.131 Section 354.131 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... Carcasses and Parts § 354.131 Decomposition. Carcasses of rabbits deleteriously affected by post-mortem...

  6. 9 CFR 354.131 - Decomposition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Decomposition. 354.131 Section 354.131 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... Carcasses and Parts § 354.131 Decomposition. Carcasses of rabbits deleteriously affected by post-mortem...

  7. 9 CFR 354.131 - Decomposition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Decomposition. 354.131 Section 354.131 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... Carcasses and Parts § 354.131 Decomposition. Carcasses of rabbits deleteriously affected by post-mortem...

  8. 9 CFR 381.93 - Decomposition.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Decomposition. 381.93 Section 381.93 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... § 381.93 Decomposition. Carcasses of poultry deleteriously affected by post mortem changes shall be...

  9. 9 CFR 381.93 - Decomposition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Decomposition. 381.93 Section 381.93 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... § 381.93 Decomposition. Carcasses of poultry deleteriously affected by post mortem changes shall be...

  10. 9 CFR 381.93 - Decomposition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Decomposition. 381.93 Section 381.93 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... § 381.93 Decomposition. Carcasses of poultry deleteriously affected by post mortem changes shall be...

  11. 9 CFR 381.93 - Decomposition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Decomposition. 381.93 Section 381.93 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... § 381.93 Decomposition. Carcasses of poultry deleteriously affected by post mortem changes shall be...

  12. 9 CFR 354.131 - Decomposition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Decomposition. 354.131 Section 354.131 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE AGENCY... Carcasses and Parts § 354.131 Decomposition. Carcasses of rabbits deleteriously affected by post-mortem...

  13. Glycerol electro-oxidation on a carbon-supported platinum catalyst at intermediate temperatures

    NASA Astrophysics Data System (ADS)

    Ishiyama, Keisuke; Kosaka, Fumihiko; Shimada, Iori; Oshima, Yoshito; Otomo, Junichiro

    2013-03-01

    The electro-oxidation of glycerol on a carbon-supported platinum catalyst (Pt/C) in combination with a reaction products analysis was investigated at intermediate temperatures (235-260 °C) using a single cell with a CsH2PO4 proton conducting solid electrolyte. A high current density was achieved. The main products were H2, CO2 and CO but the formation of C2 compounds, such as glycolic acid and ethane, was also observed. In addition, several C3 compounds were detected as minor products. A reaction products analysis revealed that the C-C bond dissociation ratio of glycerol was 70-80% at both low and high potentials (>200 mV vs. reversible hydrogen electrode) at 250 °C, suggesting that rapid dissociation occurs on Pt/C. The reaction products analysis also suggested that hydrogen production via thermal decomposition and/or steam reforming of glycerol (indirect path) and direct electro-oxidation of glycerol (direct path) proceed in parallel. More detailed reaction paths involving C1, C2 and C3 reaction products are discussed as well as the possible rate-determining step in glycerol electro-oxidation at intermediate temperatures.

  14. Validation of intermediate end points in cancer research.

    PubMed

    Schatzkin, A; Freedman, L S; Schiffman, M H; Dawsey, S M

    1990-11-21

    Investigations using intermediate end points as cancer surrogates are quicker, smaller, and less expensive than studies that use malignancy as the end point. We present a strategy for determining whether a given biomarker is a valid intermediate end point between an exposure and incidence of cancer. Candidate intermediate end points may be selected from case series, ecologic studies, and animal experiments. Prospective cohort and sometimes case-control studies may be used to quantify the intermediate end point-cancer association. The most appropriate measure of this association is the attributable proportion. The intermediate end point is a valid cancer surrogate if the attributable proportion is close to 1.0, but not if it is close to 0. Usually, the attributable proportion is close to neither 1.0 nor 0; in this case, valid surrogacy requires that the intermediate end point mediate an established exposure-cancer relation. This would in turn imply that the exposure effect would vanish if adjusted for the intermediate end point. We discuss the relative advantages of intervention and observational studies for the validation of intermediate end points. This validation strategy also may be applied to intermediate end points for adverse reproductive outcomes and chronic diseases other than cancer.

  15. Bullying during the Intermediate School Phase: A South African Study

    ERIC Educational Resources Information Center

    Greeff, P.; Grobler, A. A.

    2008-01-01

    Bullying in the intermediate school phase was studied, using the Revised Olweus Bully/Victim Questionnaire (R-OBVQ). The total sample comprised 360 grade 4 to 6 pupils from English-medium, single-sex schools in Bloemfontein, South Africa. To ensure a more homogeneous sample, the grade (grades 4 to 6) and race (black and white) of the participants…

  16. Assessing the effect of different treatments on decomposition rate of dairy manure.

    PubMed

    Khalil, Tariq M; Higgins, Stewart S; Ndegwa, Pius M; Frear, Craig S; Stöckle, Claudio O

    2016-11-01

    Confined animal feeding operations (CAFOs) contribute to greenhouse gas emission, but the magnitude of these emissions as a function of operation size, infrastructure, and manure management are difficult to assess. Modeling is a viable option to estimate gaseous emission and nutrient flows from CAFOs. These models use a decomposition rate constant for carbon mineralization. However, this constant is usually determined assuming a homogenous mix of manure, ignoring the effects of emerging manure treatments. The aim of this study was to measure and compare the decomposition rate constants of dairy manure in single and three-pool decomposition models, and to develop an empirical model based on chemical composition of manure for prediction of a decomposition rate constant. Decomposition rate constants of manure before and after an anaerobic digester (AD), following coarse fiber separation, and fine solids removal were determined under anaerobic conditions for single and three-pool decomposition models. The decomposition rates of treated manure effluents differed significantly from untreated manure for both single and three-pool decomposition models. In the single-pool decomposition model, AD effluent containing only suspended solids had a relatively high decomposition rate of 0.060 d(-1), while liquid with coarse fiber and fine solids removed had the lowest rate of 0.013 d(-1). In the three-pool decomposition model, fast and slow decomposition rate constants (0.25 d(-1) and 0.016 d(-1) respectively) of untreated AD influent were also significantly different from treated manure fractions. A regression model to predict the decomposition rate of treated dairy manure fitted well (R(2) = 0.83) to observed data. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Interacting effects of insects and flooding on wood decomposition.

    Treesearch

    Michael Ulyshen

    2014-01-01

    Saproxylic arthropods are thought to play an important role in wood decomposition but very few efforts have been made to quantify their contributions to the process and the factors controlling their activities are not well understood. In the current study, mesh exclusion bags were used to quantify how arthropods affect loblolly pine (Pinus taeda L.) decomposition rates...

  18. Structural system identification based on variational mode decomposition

    NASA Astrophysics Data System (ADS)

    Bagheri, Abdollah; Ozbulut, Osman E.; Harris, Devin K.

    2018-03-01

    In this paper, a new structural identification method is proposed to identify the modal properties of engineering structures based on dynamic response decomposition using the variational mode decomposition (VMD). The VMD approach is a decomposition algorithm that has been developed as a means to overcome some of the drawbacks and limitations of the empirical mode decomposition method. The VMD-based modal identification algorithm decomposes the acceleration signal into a series of distinct modal responses and their respective center frequencies, such that when combined their cumulative modal responses reproduce the original acceleration response. The decaying amplitude of the extracted modal responses is then used to identify the modal damping ratios using a linear fitting function on modal response data. Finally, after extracting modal responses from available sensors, the mode shape vector for each of the decomposed modes in the system is identified from all obtained modal response data. To demonstrate the efficiency of the algorithm, a series of numerical, laboratory, and field case studies were evaluated. The laboratory case study utilized the vibration response of a three-story shear frame, whereas the field study leveraged the ambient vibration response of a pedestrian bridge to characterize the modal properties of the structure. The modal properties of the shear frame were computed using analytical approach for a comparison with the experimental modal frequencies. Results from these case studies demonstrated that the proposed method is efficient and accurate in identifying modal data of the structures.

  19. Structural optimization by multilevel decomposition

    NASA Technical Reports Server (NTRS)

    Sobieszczanski-Sobieski, J.; James, B.; Dovi, A.

    1983-01-01

    A method is described for decomposing an optimization problem into a set of subproblems and a coordination problem which preserves coupling between the subproblems. The method is introduced as a special case of multilevel, multidisciplinary system optimization and its algorithm is fully described for two level optimization for structures assembled of finite elements of arbitrary type. Numerical results are given for an example of a framework to show that the decomposition method converges and yields results comparable to those obtained without decomposition. It is pointed out that optimization by decomposition should reduce the design time by allowing groups of engineers, using different computers to work concurrently on the same large problem.

  20. 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.

  1. Mixing effects on litter decomposition rates in a young tree diversity experiment

    NASA Astrophysics Data System (ADS)

    Setiawan, Nuri Nurlaila; Vanhellemont, Margot; De Schrijver, An; Schelfhout, Stephanie; Baeten, Lander; Verheyen, Kris

    2016-01-01

    Litter decomposition is an essential process for biogeochemical cycling and for the formation of new soil organic matter. Mixing litter from different tree species has been reported to increase litter decomposition rates through synergistic effects. We assessed the decomposition rates of leaf litter from five tree species in a recently established tree diversity experiment on a post-agriculture site in Belgium. We used 20 different leaf litter compositions with diversity levels ranging from 1 up to 4 species. Litter mass loss in litterbags was assessed 10, 20, 25, 35, and 60 weeks after installation in the field. We found that litter decomposition rates were higher for high-quality litters, i.e., with high nitrogen content and low lignin content. The decomposition rates of mixed litter were more affected by the identity of the litter species within the mixture than by the diversity of the litter per se, but the variability in litter decomposition rates decreased as the litter diversity increased. Among the 15 different mixed litter compositions in our study, only three litter combinations showed synergistic effects. Our study suggests that admixing tree species with high-quality litter in post-agricultural plantations helps in increasing the mixture's early-stage litter decomposition rate.

  2. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ripmeester, J. A.

    2010-04-01

    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  3. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

    PubMed

    Alavi, Saman; Ripmeester, J A

    2010-04-14

    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  4. Ionization-Enhanced Decomposition of 2,4,6-Trinitrotoluene (TNT) Molecules

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

    Wang, Bin; Wright, David; Cliffel, David

    2011-01-01

    The unimolecular decomposition reaction of TNT can in principle be used to design ways to either detect or remove TNT from the environment. Here, we report the results of a density functional theory study of possible ways to lower the reaction barrier for this decomposition process by ionization, so that decomposition and/or detection can occur at room temperature. We find that ionizing TNT lowers the reaction barrier for the initial step of this decomposition. We further show that a similar effect can occur if a positive moiety is bound to the TNT molecule. The positive charge produces a pronounced electronmore » redistribution and dipole formation in TNT with minimal charge transfer from TNT to the positive moiety.« less

  5. The intermediate endpoint effect in logistic and probit regression

    PubMed Central

    MacKinnon, DP; Lockwood, CM; Brown, CH; Wang, W; Hoffman, JM

    2010-01-01

    Background An intermediate endpoint is hypothesized to be in the middle of the causal sequence relating an independent variable to a dependent variable. The intermediate variable is also called a surrogate or mediating variable and the corresponding effect is called the mediated, surrogate endpoint, or intermediate endpoint effect. Clinical studies are often designed to change an intermediate or surrogate endpoint and through this intermediate change influence the ultimate endpoint. In many intermediate endpoint clinical studies the dependent variable is binary, and logistic or probit regression is used. Purpose The purpose of this study is to describe a limitation of a widely used approach to assessing intermediate endpoint effects and to propose an alternative method, based on products of coefficients, that yields more accurate results. Methods The intermediate endpoint model for a binary outcome is described for a true binary outcome and for a dichotomization of a latent continuous outcome. Plots of true values and a simulation study are used to evaluate the different methods. Results Distorted estimates of the intermediate endpoint effect and incorrect conclusions can result from the application of widely used methods to assess the intermediate endpoint effect. The same problem occurs for the proportion of an effect explained by an intermediate endpoint, which has been suggested as a useful measure for identifying intermediate endpoints. A solution to this problem is given based on the relationship between latent variable modeling and logistic or probit regression. Limitations More complicated intermediate variable models are not addressed in the study, although the methods described in the article can be extended to these more complicated models. Conclusions Researchers are encouraged to use an intermediate endpoint method based on the product of regression coefficients. A common method based on difference in coefficient methods can lead to distorted

  6. Anaerobic decomposition of humic substances by Clostridium from the deep subsurface

    PubMed Central

    Ueno, Akio; Shimizu, Satoru; Tamamura, Shuji; Okuyama, Hidetoshi; Naganuma, Takeshi; Kaneko, Katsuhiko

    2016-01-01

    Decomposition of humic substances (HSs) is a slow and cryptic but non-negligible component of carbon cycling in sediments. Aerobic decomposition of HSs by microorganisms in the surface environment has been well documented; however, the mechanism of anaerobic microbial decomposition of HSs is not completely understood. Moreover, no microorganisms capable of anaerobic decomposition of HSs have been isolated. Here, we report the anaerobic decomposition of humic acids (HAs) by the anaerobic bacterium Clostridium sp. HSAI-1 isolated from the deep terrestrial subsurface. The use of 14C-labelled polycatechol as an HA analogue demonstrated that the bacterium decomposed this substance up to 7.4% over 14 days. The decomposition of commercial and natural HAs by the bacterium yielded lower molecular mass fractions, as determined using high-performance size-exclusion chromatography. Fourier transform infrared spectroscopy revealed the removal of carboxyl groups and polysaccharide-related substances, as well as the generation of aliphatic components, amide and aromatic groups. Therefore, our results suggest that Clostridium sp. HSAI-1 anaerobically decomposes and transforms HSs. This study improves our understanding of the anaerobic decomposition of HSs in the hidden carbon cycling in the Earth’s subsurface. PMID:26743007

  7. 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.

  8. Hydrated electron based decomposition of perfluorooctane sulfonate (PFOS) in the VUV/sulfite system.

    PubMed

    Gu, Yurong; Liu, Tongzhou; Wang, Hongjie; Han, Huili; Dong, Wenyi

    2017-12-31

    As one of the most reactive species, hydrated electron (e aq - ) is promising for reductive decomposition of recalcitrant organic pollutants, such as perfluorooctane sulfonate (PFOS). In this study, PFOS decomposition using a vacuum ultraviolet (VUV)/sulfite system was systematically investigated in comparison with sole VUV and ultraviolet (UV)/sulfite systems. A fast and nearly complete (97.3%) PFOS decomposition was observed within 4h from its initial concentration of 37.2μM in the VUV/sulfite system. The observed rate constant (k obs ) for PFOS decomposition in the studied system was 0.87±0.0060h -1 , which was nearly 7.5 and 2 folds faster than that in sole VUV and UV/sulfite systems, respectively. Compared to previously studied UV/sulfite system, VUV/sulfite system enhanced PFOS decomposition in both weak acidic and alkaline pH conditions. In weak acidic condition (pH6.0), PFOS predominantly decomposed via direct VUV photolysis, whereas in alkaline condition (pH>9.0), PFOS decomposition was mainly induced by e aq - generated from both sulfite and VUV photolytic reactions. At a fixed initial solution pH (pH10.0), PFOS decomposition kinetics showed a positive linear dependence with sulfite dosage. The co-presence of humic acid (HA) and NO 3 - obviously suppressed PFOS decomposition, whereas HCO 3 - showed marginal inhibition. A few amount of short chain perfluorocarboxylic acids (PFCAs) were detected in PFOS decomposition process, and a high defluorination efficiency (75.4%) was achieved. These results suggested most fluorine atoms in PFOS molecule ultimately mineralized into fluoride ions, and the mechanisms for PFOS decomposition in the VUV/sulfite system were proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. 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.

  10. Thermal decomposition of cyanate ester resins

    DOT National Transportation Integrated Search

    2001-09-01

    Polycyanurate networks were prepared by thermal polymerization of cyanate ester monomers containing two or more cyanate ester : (O-CN) functional groups. The thermal decomposition chemistry of nine different polycyanurates was studied by : ther...

  11. 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.

  12. Influence of different forest system management practices on leaf litter decomposition rates, nutrient dynamics and the activity of ligninolytic enzymes: a case study from central European forests.

    PubMed

    Purahong, Witoon; Kapturska, Danuta; Pecyna, Marek J; Schulz, Elke; Schloter, Michael; Buscot, François; Hofrichter, Martin; Krüger, Dirk

    2014-01-01

    Leaf litter decomposition is the key ecological process that determines the sustainability of managed forest ecosystems, however very few studies hitherto have investigated this process with respect to silvicultural management practices. The aims of the present study were to investigate the effects of forest management practices on leaf litter decomposition rates, nutrient dynamics (C, N, Mg, K, Ca, P) and the activity of ligninolytic enzymes. We approached these questions using a 473 day long litterbag experiment. We found that age-class beech and spruce forests (high forest management intensity) had significantly higher decomposition rates and nutrient release (most nutrients) than unmanaged deciduous forest reserves (P<0.05). The site with near-to-nature forest management (low forest management intensity) exhibited no significant differences in litter decomposition rate, C release, lignin decomposition, and C/N, lignin/N and ligninolytic enzyme patterns compared to the unmanaged deciduous forest reserves, but most nutrient dynamics examined in this study were significantly faster under such near-to-nature forest management practices. Analyzing the activities of ligninolytic enzymes provided evidence that different forest system management practices affect litter decomposition by changing microbial enzyme activities, at least over the investigated time frame of 473 days (laccase, P<0.0001; manganese peroxidase (MnP), P = 0.0260). Our results also indicate that lignin decomposition is the rate limiting step in leaf litter decomposition and that MnP is one of the key oxidative enzymes of litter degradation. We demonstrate here that forest system management practices can significantly affect important ecological processes and services such as decomposition and nutrient cycling.

  13. 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.

  14. 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.

  15. Theoretical studies on the unimolecular decomposition of ethylene glycol.

    PubMed

    Ye, Lili; Zhao, Long; Zhang, Lidong; Qi, Fei

    2012-01-12

    The unimolecular decomposition processes of ethylene glycol have been investigated with the QCISD(T) method with geometries optimized at the B3LYP/6-311++G(d,p) level. Among the decomposition channels identified, the H(2)O-elimination channels have the lowest barriers, and the C-C bond dissociation is the lowest-energy dissociation channel among the barrierless reactions (the direct bond cleavage reactions). The temperature and pressure dependent rate constant calculations show that the H(2)O-elimination reactions are predominant at low temperature, whereas at high temperature, the direct C-C bond dissociation reaction is dominant. At 1 atm, in the temperature range 500-2000 K, the calculated rate constant is expressed to be 7.63 × 10(47)T(-10.38) exp(-42262/T) for the channel CH(2)OHCH(2)OH → CH(2)CHOH + H(2)O, and 2.48 × 10(51)T(-11.58) exp(-43593/T) for the channel CH(2)OHCH(2)OH → CH(3)CHO + H(2)O, whereas for the direct bond dissociation reaction CH(2)OHCH(2)OH → CH(2)OH + CH(2)OH the rate constant expression is 1.04 × 10(71)T(-16.16) exp(-52414/T).

  16. Inter-Rater Reliability of Total Body Score-A Scale for Quantification of Corpse Decomposition.

    PubMed

    Nawrocka, Marta; Frątczak, Katarzyna; Matuszewski, Szymon

    2016-05-01

    The degree of body decomposition can be quantified using Total Body Score (TBS), a scale frequently used in taphonomic or entomological studies of decomposition. Here, the inter-rater reliability of the scale is analyzed. The study was made on 120 laymen, which were trained in the use of the scale. Participants scored decomposition of pig carcasses from photographs. It was found that the scale, when used by different people, gives homogeneous results irrespective of the user qualifications (the Krippendorff's alfa for all participants was 0.818). The study also indicated that carcasses in advanced decomposition receive significantly less accurate scores. Moreover, it was found that scores for cadavers in mosaic decomposition (i.e., representing signs of at least two stages of decomposition) are less accurate. These results demonstrate that the scale may be regarded as inter-rater reliable. Some propositions for refinement of the scale were also discussed. © 2016 American Academy of Forensic Sciences.

  17. 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.

  18. Microbial interactions during carrion decomposition

    USDA-ARS?s Scientific Manuscript database

    This addresses the microbial ecology of carrion decomposition in the age of metagenomics. It describes what is known about the microbial communities on carrion, including a brief synopsis about the communities on other organic matter sources. It provides a description of studies using state-of-the...

  19. Solvent decompositions and physical properties of decomposition compounds in Li-ion battery electrolytes studied by DFT calculations and molecular dynamics simulations.

    PubMed

    Tasaki, Ken

    2005-02-24

    The density functional theory (DFT) calculations have been performed for the reduction decompositions of solvents widely used in Li-ion secondary battery electrolytes, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonates (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), including a typical electrolyte additive, vinylene carbonate (VC), at the level of B3LYP/6-311+G(2d,p), both in the gas phase and solution using the polarizable conductor calculation model. In the gas phase, the first electron reduction for the cyclic carbonates and for the linear carbonates is found to be exothermic and endothermic, respectively, while the second electron reduction is endothermic for all the compounds examined. On the contrary, in solution both first and second electron reductions are exothermic for all the compounds. Among the solvents and the additive examined, the likelihood of undergoing the first electron reduction in solution was found in the order of EC > PC > VC > DMC > EMC > DEC with EC being the most likely reduced. VC, on the other hand, is most likely to undergo the second electron reduction among the compounds, in the order of VC > EC > PC. Based on the results, the experimentally demonstrated effectiveness of VC as an excellent electrolyte additive was discussed. The bulk thermodynamic properties of two dilithium alkylene glycol dicarbonates, dilithium ethylene glycol dicarbonate (Li-EDC) and dilithium 1,2-propylene glycol dicarbonate (Li-PDC), as the major component of solid-electrolyte interface (SEI) films were also examined through molecular dynamics (MD) simulations in order to understand the stability of the SEI film. It was found that film produced from a decomposition of EC, modeled by Li-EDC, has a higher density, more cohesive energy, and less solubility to the solvent than the film produced from decomposition of PC, Li-PDC. Further, MD simulations of the interface between the decomposition compound and graphite suggested

  20. Unimolecular thermal decomposition of phenol and d5-phenol: Direct observation of cyclopentadiene formation via cyclohexadienone

    NASA Astrophysics Data System (ADS)

    Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.; Nimlos, Mark R.; Carstensen, Hans-Heinrich; Barney Ellison, G.

    2012-01-01

    The pyrolyses of phenol and d5-phenol (C6H5OH and C6D5OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the μtubular reactor of approximately 50-100 μs. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C6H5OH → c-C6H6 = O → c-C5H6 + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C5H6 → c-C5H5 + H → HC≡CH + HCCCH2. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C6H5O-H → C6H5O + H → c-C5H5 + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C6H4-OH) and hydroquinone (p-HO-C6H4-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.

  1. Interrelationships among shrub encroachment, land management, and litter decomposition in a semidesert grassland.

    PubMed

    Throop, Heather L; Archer, Steven R

    2007-09-01

    Encroachment of woody plants into grasslands, and subsequent brush management, are among the most prominent changes to occur in arid and semiarid systems over the past century. Despite the resulting widespread changes in landcover, substantial uncertainty about the biogeochemical impacts of woody proliferation and brush management exists. We explored the role of shrub encroachment and brush management on leaf litter decomposition in a semidesert grassland where velvet mesquite (Prosopis velutina) abundance has increased over the past 100 years. This change in physiognomy may affect decomposition directly, through altered litter quality or quantity, and indirectly through altered canopy structure. To assess the direct and indirect impacts of shrubs on decomposition, we quantified changes in mass, nitrogen, and carbon in litterbags deployed under mesquite canopies and in intercanopy zones. Litterbags contained foliage from mesquite and Lehmann lovegrass (Eragrostis lehmanniana), a widespread, nonnative grass in southern Arizona. To explore short- and long-term influences of brush management on the initial stages of decomposition, litterbags were deployed at sites where mesquite canopies were removed three weeks, 45 years, or 70 years prior to study initiation. Mesquite litter decomposed more rapidly than lovegrass, but negative indirect influences of mesquite canopies counteracted positive direct effects. Decomposition was positively correlated with soil infiltration into litterbags, which varied with microsite placement, and was lowest under canopies. Low under-canopy decomposition was ostensibly due to decreased soil movement associated with high under-canopy herbaceous biomass. Decomposition rates where canopies were removed three weeks prior to study initiation were comparable to those beneath intact canopies, suggesting that decomposition was driven by mesquite legacy effects on herbaceous cover-soil movement linkages. Decomposition rates where shrubs were

  2. Direct Sum Decomposition of Groups

    ERIC Educational Resources Information Center

    Thaheem, A. B.

    2005-01-01

    Direct sum decomposition of Abelian groups appears in almost all textbooks on algebra for undergraduate students. This concept plays an important role in group theory. One simple example of this decomposition is obtained by using the kernel and range of a projection map on an Abelian group. The aim in this pedagogical note is to establish a direct…

  3. An NN-Based SRD Decomposition Algorithm and Its Application in Nonlinear Compensation

    PubMed Central

    Yan, Honghang; Deng, Fang; Sun, Jian; Chen, Jie

    2014-01-01

    In this study, a neural network-based square root of descending (SRD) order decomposition algorithm for compensating for nonlinear data generated by sensors is presented. The study aims at exploring the optimized decomposition of data 1.00,0.00,0.00 and minimizing the computational complexity and memory space of the training process. A linear decomposition algorithm, which automatically finds the optimal decomposition of N subparts and reduces the training time to 1N and memory cost to 1N, has been implemented on nonlinear data obtained from an encoder. Particular focus is given to the theoretical access of estimating the numbers of hidden nodes and the precision of varying the decomposition method. Numerical experiments are designed to evaluate the effect of this algorithm. Moreover, a designed device for angular sensor calibration is presented. We conduct an experiment that samples the data of an encoder and compensates for the nonlinearity of the encoder to testify this novel algorithm. PMID:25232912

  4. Intermediate treatments

    Treesearch

    John R. Jones; Wayne D. Shepperd

    1985-01-01

    Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

  5. Basic dye decomposition kinetics in a photocatalytic slurry reactor.

    PubMed

    Wu, Chun-Hsing; Chang, Hung-Wei; Chern, Jia-Ming

    2006-09-01

    Wastewater effluent from textile plants using various dyes is one of the major water pollutants to the environment. Traditional chemical, physical and biological processes for treating textile dye wastewaters have disadvantages such as high cost, energy waste and generating secondary pollution during the treatment process. The photocatalytic process using TiO2 semiconductor particles under UV light illumination has been shown to be potentially advantageous and applicable in the treatment of wastewater pollutants. In this study, the dye decomposition kinetics by nano-size TiO2 suspension at natural solution pH was experimentally studied by varying the agitation speed (50-200 rpm), TiO2 suspension concentration (0.25-1.71 g/L), initial dye concentration (10-50 ppm), temperature (10-50 degrees C), and UV power intensity (0-96 W). The experimental results show the agitation speed, varying from 50 to 200 rpm, has a slight influence on the dye decomposition rate and the pH history; the dye decomposition rate increases with the TiO2 suspension concentration up to 0.98 g/L, then decrease with increasing TiO2 suspension concentration; the initial dye decomposition rate increases with the initial dye concentration up to a certain value depending upon the temperature, then decreases with increasing initial dye concentration; the dye decomposition rate increases with the UV power intensity up to 64 W to reach a plateau. Kinetic models have been developed to fit the experimental kinetic data well.

  6. Resolving the intermediate and deep advective flows in the Indian Ocean by using temperature, salinity, oxygen and phosphate data: the interplay of biogeochemical and geophysical tracers

    NASA Astrophysics Data System (ADS)

    Metzl, N.; Moore, B.; Poisson, A.

    1990-10-01

    For computing large-scale advective flow in the Indian ocean (including the Indian-Antarctic sector), we use a box-model approach and perturbed inverse method. The top 400 meters is not considered in this study, in view of the dominant seasonal dynamics. We use 1244 hydrographic stations, to estimate mean values for temperature, salinity, oxygen and phosphate concentratons. Fifty perturbed inversions of steady-state tracers conservations and thermal-wind equations are done using box-averages standard deviations and a 25% perturbation on the thermal-wind coefficients. The mean solutions represent the large-scale advective flow and carbon-decomposition rates in which we are interested. Solutions with only advective processes are first considered. The broad features of the circulation in the Indian Ocean are resolved in the intermediate levels, but in deeper layers, an input from North Atlantic Deep Water (NADW) is not apparent. Inspection of oxygen and phosphate residuals reveals a biochemical signal. Therefore, we introduce in the oxygen and phosphate budgets a linear parameterization (Redfield ratios) for the organic-decomposition processes. The structure of the residuals for oxygen and phosphate is changed in that the biochemical signal vanishes. The advective solutions are nearly the same in intermediate waters; however, in deep layers the new solution shows an inflow of 11 (±8) Sv of NADW south of Africa. The calculated total organic decomposition of 0.93 (±0.25) 10 15g C year -1 is about one fifth of the estimated world ocean amount, but total residuals of oxygen and phosphate lead to an unexplained 0.5 10 15g C year -1 missing carbon sink. The new solution does contain unrealistic elements (e.g. large deep flow between Indonesia and Australia). Finally, to investigate this last result, we add one advective constraint at the Indonesia-Australia boundary. This addition changes the circulation in the northeastern part of the Indian Ocean. The circumpolar flow

  7. Influence of Different Forest System Management Practices on Leaf Litter Decomposition Rates, Nutrient Dynamics and the Activity of Ligninolytic Enzymes: A Case Study from Central European Forests

    PubMed Central

    Schulz, Elke; Schloter, Michael; Buscot, François; Hofrichter, Martin; Krüger, Dirk

    2014-01-01

    Leaf litter decomposition is the key ecological process that determines the sustainability of managed forest ecosystems, however very few studies hitherto have investigated this process with respect to silvicultural management practices. The aims of the present study were to investigate the effects of forest management practices on leaf litter decomposition rates, nutrient dynamics (C, N, Mg, K, Ca, P) and the activity of ligninolytic enzymes. We approached these questions using a 473 day long litterbag experiment. We found that age-class beech and spruce forests (high forest management intensity) had significantly higher decomposition rates and nutrient release (most nutrients) than unmanaged deciduous forest reserves (P<0.05). The site with near-to-nature forest management (low forest management intensity) exhibited no significant differences in litter decomposition rate, C release, lignin decomposition, and C/N, lignin/N and ligninolytic enzyme patterns compared to the unmanaged deciduous forest reserves, but most nutrient dynamics examined in this study were significantly faster under such near-to-nature forest management practices. Analyzing the activities of ligninolytic enzymes provided evidence that different forest system management practices affect litter decomposition by changing microbial enzyme activities, at least over the investigated time frame of 473 days (laccase, P<0.0001; manganese peroxidase (MnP), P = 0.0260). Our results also indicate that lignin decomposition is the rate limiting step in leaf litter decomposition and that MnP is one of the key oxidative enzymes of litter degradation. We demonstrate here that forest system management practices can significantly affect important ecological processes and services such as decomposition and nutrient cycling. PMID:24699676

  8. Geometric decomposition of the conformation tensor in viscoelastic turbulence

    NASA Astrophysics Data System (ADS)

    Hameduddin, Ismail; Meneveau, Charles; Zaki, Tamer A.; Gayme, Dennice F.

    2018-05-01

    This work introduces a mathematical approach to analysing the polymer dynamics in turbulent viscoelastic flows that uses a new geometric decomposition of the conformation tensor, along with associated scalar measures of the polymer fluctuations. The approach circumvents an inherent difficulty in traditional Reynolds decompositions of the conformation tensor: the fluctuating tensor fields are not positive-definite and so do not retain the physical meaning of the tensor. The geometric decomposition of the conformation tensor yields both mean and fluctuating tensor fields that are positive-definite. The fluctuating tensor in the present decomposition has a clear physical interpretation as a polymer deformation relative to the mean configuration. Scalar measures of this fluctuating conformation tensor are developed based on the non-Euclidean geometry of the set of positive-definite tensors. Drag-reduced viscoelastic turbulent channel flow is then used an example case study. The conformation tensor field, obtained using direct numerical simulations, is analysed using the proposed framework.

  9. Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

    NASA Astrophysics Data System (ADS)

    Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

    2018-05-01

    Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

  10. Nutrient-enhanced decomposition of plant biomass in a freshwater wetland

    USGS Publications Warehouse

    Bodker, James E.; Turner, Robert Eugene; Tweel, Andrew; Schulz, Christopher; Swarzenski, Christopher M.

    2015-01-01

    We studied soil decomposition in a Panicum hemitomon (Schultes)-dominated freshwater marsh located in southeastern Louisiana that was unambiguously changed by secondarily-treated municipal wastewater effluent. We used four approaches to evaluate how belowground biomass decomposition rates vary under different nutrient regimes in this marsh. The results of laboratory experiments demonstrated how nutrient enrichment enhanced the loss of soil or plant organic matter by 50%, and increased gas production. An experiment demonstrated that nitrogen, not phosphorus, limited decomposition. Cellulose decomposition at the field site was higher in the flowfield of the introduced secondarily treated sewage water, and the quality of the substrate (% N or % P) was directly related to the decomposition rates. We therefore rejected the null hypothesis that nutrient enrichment had no effect on the decomposition rates of these organic soils. In response to nutrient enrichment, plants respond through biomechanical or structural adaptations that alter the labile characteristics of plant tissue. These adaptations eventually change litter type and quality (where the marsh survives) as the % N content of plant tissue rises and is followed by even higher decomposition rates of the litter produced, creating a positive feedback loop. Marsh fragmentation will increase as a result. The assumptions and conditions underlying the use of unconstrained wastewater flow within natural wetlands, rather than controlled treatment within the confines of constructed wetlands, are revealed in the loss of previously sequestered carbon, habitat, public use, and other societal benefits.

  11. 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.

  12. Reducing conditions can alter the source of respired carbon and stimulate decomposition in mineral soils

    NASA Astrophysics Data System (ADS)

    Huang, W.; Hall, S. J.

    2016-12-01

    Soil organic matter decomposition is widely thought to be constrained by reducing conditions in flooded wetland ecosystems. However, the potential impact of periodic reducing conditions on carbon (C) mineralization in terrestrial mineral soils that experience transient moisture saturation has received less attention. Here we incubated three Mollisols amended with C4 leaf litter at three different soil moisture levels (field capacity for the control, intermediate, and saturation) over three months in the laboratory. Soil CO2 and CH4 production and isotope ratios of CO2 (δ13CO2) were measured daily using a tunable diode laser for the first two weeks and weekly thereafter. Soil Eh dropped from 516 mV to -184 mV in the intermediate and saturated soils during the first seventeen days; iron (Fe) reduction occurred in both intermediate and saturated soils after the seventh day. Total CO2 production rate in the intermediate and saturated soils was initially lower than the control, but exceeded the control after the eleventh day. After three months, mean cumulative CO2 production was significantly higher in the intermediate soil moisture treatment (152 μmol CO2 g-1 soil, P < 0.01) and equivalent between the saturated and control soils (128 and 141 μmol CO2 g-1 soil, P = 0.11). The intermediate and saturated soils also induced substantial CH4 production. Differences in mean δ13CO2 (-14.0‰ for the control and -22.7‰ for the saturated soils) over the first two weeks (before CH4 production began) showed that CO2 production from the saturated soils was derived from different C source(s) compared to the control. These findings challenge traditional paradigms by showing that reducing conditions can enhance C mineralization, perhaps by facilitating microbial access to alternative or occluded C sources. We suggest that Fe reduction could be an important mechanism of C loss in mineral soils due to the release of adsorbed or co-precipitated organic matter during Fe

  13. Simulated nitrogen deposition affects wood decomposition by cord-forming fungi.

    PubMed

    Bebber, Daniel P; Watkinson, Sarah C; Boddy, Lynne; Darrah, Peter R

    2011-12-01

    Anthropogenic nitrogen (N) deposition affects many natural processes, including forest litter decomposition. Saprotrophic fungi are the only organisms capable of completely decomposing lignocellulosic (woody) litter in temperate ecosystems, and therefore the responses of fungi to N deposition are critical in understanding the effects of global change on the forest carbon cycle. Plant litter decomposition under elevated N has been intensively studied, with varying results. The complexity of forest floor biota and variability in litter quality have obscured N-elevation effects on decomposers. Field experiments often utilize standardized substrates and N-levels, but few studies have controlled the decay organisms. Decomposition of beech (Fagus sylvatica) blocks inoculated with two cord-forming basidiomycete fungi, Hypholoma fasciculare and Phanerochaete velutina, was compared experimentally under realistic levels of simulated N deposition at Wytham Wood, Oxfordshire, UK. Mass loss was greater with P. velutina than with H. fasciculare, and with N treatment than in the control. Decomposition was accompanied by growth of the fungal mycelium and increasing N concentration in the remaining wood. We attribute the N effect on wood decay to the response of cord-forming wood decay fungi to N availability. Previous studies demonstrated the capacity of these fungi to scavenge and import N to decaying wood via a translocating network of mycelium. This study shows that small increases in N availability can increase wood decomposition by these organisms. Dead wood is an important carbon store and habitat. The responses of wood decomposers to anthropogenic N deposition should be considered in models of forest carbon dynamics.

  14. Optimal cost design of water distribution networks using a decomposition approach

    NASA Astrophysics Data System (ADS)

    Lee, Ho Min; Yoo, Do Guen; Sadollah, Ali; Kim, Joong Hoon

    2016-12-01

    Water distribution network decomposition, which is an engineering approach, is adopted to increase the efficiency of obtaining the optimal cost design of a water distribution network using an optimization algorithm. This study applied the source tracing tool in EPANET, which is a hydraulic and water quality analysis model, to the decomposition of a network to improve the efficiency of the optimal design process. The proposed approach was tested by carrying out the optimal cost design of two water distribution networks, and the results were compared with other optimal cost designs derived from previously proposed optimization algorithms. The proposed decomposition approach using the source tracing technique enables the efficient decomposition of an actual large-scale network, and the results can be combined with the optimal cost design process using an optimization algorithm. This proves that the final design in this study is better than those obtained with other previously proposed optimization algorithms.

  15. Ultrasound-Guided Intermediate Site Greater Occipital Nerve Infiltration: A Technical Feasibility Study.

    PubMed

    Zipfel, Jonathan; Kastler, Adrian; Tatu, Laurent; Behr, Julien; Kechidi, Rachid; Kastler, Bruno

    2016-01-01

    Two studies recently reported that computed tomography (CT) guided infiltration of the greater occipital nerve at its intermediate site allows a high efficacy rate with long-lasting pain relief following procedure in occipital neuralgia and in various craniofacial pain syndromes. The purpose of our study was to evaluate the technical feasibility and safety of ultrasound-guided intermediate site greater occipital nerve infiltration. Retrospective study. This study was conducted at the imaging department of a 1,409 bed university hospital. Local institutional review board approval was obtained and written consent was waived. In this retrospective study, 12 patients suffering from refractory occipital neuralgia or craniofacial pain syndromes were included between April and October 2014. They underwent a total of 21 ultrasound-guided infiltrations. Infiltration of the greater occipital nerve was performed at the intermediate site of the greater occipital nerve, at its first bend between obliqus capitis inferior and semispinalis capitis muscles with local anestetics and cortivazol. Technical success was defined as satisfactory diffusion of added iodinated contrast media in the fatty space between these muscles depicted on control CT scan. We also reported first data of immediate block test efficacy and initial clinical efficacy at 7 days, one month, and 3 months, defined by a decrease of at least 50% of visual analog scale (VAS) scores. Technical success rate was 95.24%. Patients suffered from right unilateral occipital neuralgia in 3 cases, left unilateral occipital neuralgia in 2 cases, bilateral occipital neuralgia in 2 cases, migraine in one case, cervicogenic headache in one case, tension-type headache in 2 cases, and cluster headache in one case. Block test efficacy was found in 93.3% (14/15) cases. Clinical efficacy was found in 80% of cases at 7 days, in 66.7% of cases at one month and in 60% of cases at 3 months. No major complications were noted. Some of the

  16. Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

    PubMed

    Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

    2014-11-01

    Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

  17. An analysis of scatter decomposition

    NASA Technical Reports Server (NTRS)

    Nicol, David M.; Saltz, Joel H.

    1990-01-01

    A formal analysis of a powerful mapping technique known as scatter decomposition is presented. Scatter decomposition divides an irregular computational domain into a large number of equal sized pieces, and distributes them modularly among processors. A probabilistic model of workload in one dimension is used to formally explain why, and when scatter decomposition works. The first result is that if correlation in workload is a convex function of distance, then scattering a more finely decomposed domain yields a lower average processor workload variance. The second result shows that if the workload process is stationary Gaussian and the correlation function decreases linearly in distance until becoming zero and then remains zero, scattering a more finely decomposed domain yields a lower expected maximum processor workload. Finally it is shown that if the correlation function decreases linearly across the entire domain, then among all mappings that assign an equal number of domain pieces to each processor, scatter decomposition minimizes the average processor workload variance. The dependence of these results on the assumption of decreasing correlation is illustrated with situations where a coarser granularity actually achieves better load balance.

  18. 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.

  19. Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis.

    PubMed

    Valverde, Jose Manuel; Perejon, Antonio; Medina, Santiago; Perez-Maqueda, Luis A

    2015-11-28

    Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs when the reaction is thermodynamically favorable and sufficiently fast at a temperature depending on the CO2 partial pressure in the calcination atmosphere. Decarbonation of this dolomitic calcite occurs at a lower temperature than limestone decarbonation due to the relatively low crystallinity of the former. Full decomposition of dolomite leads also to a relatively low crystalline CaO, which exhibits a high reactivity as compared to limestone derived CaO. Under CO2 capture conditions in the Calcium-Looping (CaL) process, MgO grains remain inert yet favor the carbonation reactivity of dolomitic CaO especially in the solid-state diffusion controlled phase. The fundamental mechanism that drives the crystallographic transformation of dolomite in the presence of CO2 is thus responsible for its fast calcination kinetics and the high carbonation reactivity of dolomitic CaO, which makes natural dolomite a potentially advantageous alternative to limestone for CO2 capture in the CaL technology as well as SO2in situ removal in oxy-combustion fluidized bed reactors.

  20. Decomposition of toxicity emission changes on the demand and supply sides: empirical study of the US industrial sector

    NASA Astrophysics Data System (ADS)

    Fujii, Hidemichi; Okamoto, Shunsuke; Kagawa, Shigemi; Managi, Shunsuke

    2017-12-01

    This study investigated the changes in the toxicity of chemical emissions from the US industrial sector over the 1998-2009 period. Specifically, we employed a multiregional input-output analysis framework and integrated a supply-side index decomposition analysis (IDA) with a demand-side structural decomposition analysis (SDA) to clarify the main drivers of changes in the toxicity of production- and consumption-based chemical emissions. The results showed that toxic emissions from the US industrial sector decreased by 83% over the studied period because of pollution abatement efforts adopted by US industries. A variety of pollution abatement efforts were used by different industries, and cleaner production in the mining sector and the use of alternative materials in the manufacture of transportation equipment represented the most important efforts.

  1. Climate fails to predict wood decomposition at regional scales

    NASA Astrophysics Data System (ADS)

    Bradford, Mark A.; Warren, Robert J., II; Baldrian, Petr; Crowther, Thomas W.; Maynard, Daniel S.; Oldfield, Emily E.; Wieder, William R.; Wood, Stephen A.; King, Joshua R.

    2014-07-01

    Decomposition of organic matter strongly influences ecosystem carbon storage. In Earth-system models, climate is a predominant control on the decomposition rates of organic matter. This assumption is based on the mean response of decomposition to climate, yet there is a growing appreciation in other areas of global change science that projections based on mean responses can be irrelevant and misleading. We test whether climate controls on the decomposition rate of dead wood--a carbon stock estimated to represent 73 +/- 6 Pg carbon globally--are sensitive to the spatial scale from which they are inferred. We show that the common assumption that climate is a predominant control on decomposition is supported only when local-scale variation is aggregated into mean values. Disaggregated data instead reveal that local-scale factors explain 73% of the variation in wood decomposition, and climate only 28%. Further, the temperature sensitivity of decomposition estimated from local versus mean analyses is 1.3-times greater. Fundamental issues with mean correlations were highlighted decades ago, yet mean climate-decomposition relationships are used to generate simulations that inform management and adaptation under environmental change. Our results suggest that to predict accurately how decomposition will respond to climate change, models must account for local-scale factors that control regional dynamics.

  2. The decomposition of fine and coarse roots: their global patterns and controlling factors

    PubMed Central

    Zhang, Xinyue; Wang, Wei

    2015-01-01

    Fine root decomposition represents a large carbon (C) cost to plants, and serves as a potential soil C source, as well as a substantial proportion of net primary productivity. Coarse roots differ markedly from fine roots in morphology, nutrient concentrations, functions, and decomposition mechanisms. Still poorly understood is whether a consistent global pattern exists between the decomposition of fine (<2 mm root diameter) and coarse (≥2 mm) roots. A comprehensive terrestrial root decomposition dataset, including 530 observations from 71 sampling sites, was thus used to compare global patterns of decomposition of fine and coarse roots. Fine roots decomposed significantly faster than coarse roots in middle latitude areas, but their decomposition in low latitude regions was not significantly different from that of coarse roots. Coarse root decomposition showed more dependence on climate, especially mean annual temperature (MAT), than did fine roots. Initial litter lignin content was the most important predictor of fine root decomposition, while lignin to nitrogen ratios, MAT, and mean annual precipitation were the most important predictors of coarse root decomposition. Our study emphasizes the necessity of separating fine roots and coarse roots when predicting the response of belowground C release to future climate changes. PMID:25942391

  3. Soil organic matter decomposition follows plant productivity response to sea-level rise

    NASA Astrophysics Data System (ADS)

    Mueller, Peter; Jensen, Kai; Megonigal, James Patrick

    2015-04-01

    The accumulation of soil organic matter (SOM) is an important mechanism for many tidal wetlands to keep pace with sea-level rise. SOM accumulation is governed by the rates of production and decomposition of organic matter. While plant productivity responses to sea-level rise are well understood, far less is known about the response of SOM decomposition to accelerated sea-level rise. Here we quantified the effects of sea-level rise on SOM decomposition by exposing planted and unplanted tidal marsh monoliths to experimentally manipulated flood duration. The study was performed in a field-based mesocosm facility at the Smithsonian Global Change Research Wetland, a micro tidal brackish marsh in Maryland, US. SOM decomposition was quantified as CO2 efflux, with plant- and SOM-derived CO2 separated using a stable carbon isotope approach. Despite the dogma that decomposition rates are inversely related to flooding, SOM mineralization was not sensitive to varying flood duration over a 35 cm range in surface elevation in unplanted mesocoms. In the presence of plants, decomposition rates were strongly and positively related to aboveground biomass (p≤0.01, R2≥0.59). We conclude that rates of soil carbon loss through decomposition are driven by plant responses to sea level in this intensively studied tidal marsh. If our result applies more generally to tidal wetlands, it has important implications for modeling carbon sequestration and marsh accretion in response to accelerated sea-level rise.

  4. Reducing variation in decomposition odour profiling using comprehensive two-dimensional gas chromatography.

    PubMed

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

    2015-01-01

    Challenges in decomposition odour profiling have led to variation in the documented odour profile by different research groups worldwide. Background subtraction and use of controls are important considerations given the variation introduced by decomposition studies conducted in different geographical environments. The collection of volatile organic compounds (VOCs) from soil beneath decomposing remains is challenging due to the high levels of inherent soil VOCs, further confounded by the use of highly sensitive instrumentation. This study presents a method that provides suitable chromatographic resolution for profiling decomposition odour in soil by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry using appropriate controls and field blanks. Logarithmic transformation and t-testing of compounds permitted the generation of a compound list of decomposition VOCs in soil. Principal component analysis demonstrated the improved discrimination between experimental and control soil, verifying the value of the data handling method. Data handling procedures have not been well documented in this field and standardisation would thereby reduce misidentification of VOCs present in the surrounding environment as decomposition byproducts. Uniformity of data handling and instrumental procedures will reduce analytical variation, increasing confidence in the future when investigating the effect of taphonomic variables on the decomposition VOC profile. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

    PubMed

    Park, J; Lin, M C

    2009-12-03

    The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  6. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    NASA Astrophysics Data System (ADS)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  7. A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

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

    Nguyen, Trong-Nghia; Department of Physical Chemistry, Hanoi University of Science and Technology, Hanoi; Putikam, Raghunath

    2015-03-28

    We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH{sub 2}OO and anti/syn-CH{sub 3}C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH{sub 2}OO and anti-CH{sub 3}C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH{sub 3}C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C–H bonds. For syn-CH{sub 3}C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH{sub 3} groupmore » by the terminal O atom producing CH{sub 2}C(H)O–OH. At 298 K, the intramolecular insertion process in CH{sub 2}OO was found to be 600 times faster than the commonly assumed ring-closing reaction.« less

  8. Pilot-scale UV/H2O2 study for emerging organic contaminants decomposition.

    PubMed

    Chu, Xiaona; Xiao, Yan; Hu, Jiangyong; Quek, Elaine; Xie, Rongjin; Pang, Thomas; Xing, Yongjie

    2016-03-01

    Human behaviors including consumption of drugs and use of personal care products, climate change, increased international travel, and the advent of water reclamation for direct potable use have led to the introduction of significant amounts of emerging organic contaminants into the aqueous environment. In addition, the lower detection limits associated with improved scientific methods of chemical analysis have resulted in a recent increase in documented incidences of these contaminants which previously were not routinely monitored in water. Such contaminants may cause known or suspected adverse ecological and/or human health effects at very low concentrations. Conventional drinking water treatment processes may not effectively remove these organic contaminants. Advanced oxidation process (AOP) is a promising treatment process for the removal of most of these emerging organic contaminants, and has been accepted worldwide as a suitable treatment process. In this study, different groups of emerging contaminants were studied for decomposition efficiency using pilot-scale UV/H2O2 oxidation setup, including EDCs, PPCPs, taste and odor (T&O), and perfluorinated compounds. Results found that MP UV/H2O2 AOP was efficient in removing all the selected contaminants except perfluorinated compounds. Study of the kinetics of the process showed that both light absorption and quantum yield of each compound affected the decomposition performance. Analysis of water quality parameters of the treated water indicated that the outcome of both UV photolysis and UV/H2O2 processes can be affected by changes in the feed water quality.

  9. Reactive Goal Decomposition Hierarchies for On-Board Autonomy

    NASA Astrophysics Data System (ADS)

    Hartmann, L.

    2002-01-01

    As our experience grows, space missions and systems are expected to address ever more complex and demanding requirements with fewer resources (e.g., mass, power, budget). One approach to accommodating these higher expectations is to increase the level of autonomy to improve the capabilities and robustness of on- board systems and to simplify operations. The goal decomposition hierarchies described here provide a simple but powerful form of goal-directed behavior that is relatively easy to implement for space systems. A goal corresponds to a state or condition that an operator of the space system would like to bring about. In the system described here goals are decomposed into simpler subgoals until the subgoals are simple enough to execute directly. For each goal there is an activation condition and a set of decompositions. The decompositions correspond to different ways of achieving the higher level goal. Each decomposition contains a gating condition and a set of subgoals to be "executed" sequentially or in parallel. The gating conditions are evaluated in order and for the first one that is true, the corresponding decomposition is executed in order to achieve the higher level goal. The activation condition specifies global conditions (i.e., for all decompositions of the goal) that need to hold in order for the goal to be achieved. In real-time, parameters and state information are passed between goals and subgoals in the decomposition; a termination indication (success, failure, degree) is passed up when a decomposition finishes executing. The lowest level decompositions include servo control loops and finite state machines for generating control signals and sequencing i/o. Semaphores and shared memory are used to synchronize and coordinate decompositions that execute in parallel. The goal decomposition hierarchy is reactive in that the generated behavior is sensitive to the real-time state of the system and the environment. That is, the system is able to react

  10. Soil Microarthropod Community Structure and Litter Decomposition Dynamics: A Study of Tropical and Temperate Sites

    Treesearch

    L. Heneghan; D.C. Coleman; X. Zou; D.A. Crossley; B.L. Hines

    1998-01-01

    The influence of climate, substrate quality and microarthropods on decomposition was studied by comparing the mass loss of litter at three forested sites: two tropical and one temperate. At each site,litter bags containing a dominant local litter were placed in the field in replicated plots. Half the bags were treated with naphthalene to reduce microarthropod...

  11. Canonical decomposition of magnetotelluric responses: Experiment on 1D anisotropic structures

    NASA Astrophysics Data System (ADS)

    Guo, Ze-qiu; Wei, Wen-bo; Ye, Gao-feng; Jin, Sheng; Jing, Jian-en

    2015-08-01

    Horizontal electrical heterogeneity of subsurface earth is mostly originated from structural complexity and electrical anisotropy, and local near-surface electrical heterogeneity will severely distort regional electromagnetic responses. Conventional distortion analyses for magnetotelluric soundings are primarily physical decomposition methods with respect to isotropic models, which mostly presume that the geoelectric distribution of geological structures is of local and regional patterns represented by 3D/2D models. Due to the widespread anisotropy of earth media, the confusion between 1D anisotropic responses and 2D isotropic responses, and the defects of physical decomposition methods, we propose to conduct modeling experiments with canonical decomposition in terms of 1D layered anisotropic models, and the method is one of the mathematical decomposition methods based on eigenstate analyses differentiated from distortion analyses, which can be used to recover electrical information such as strike directions, and maximum and minimum conductivity. We tested this method with numerical simulation experiments on several 1D synthetic models, which turned out that canonical decomposition is quite effective to reveal geological anisotropic information. Finally, for the background of anisotropy from previous study by geological and seismological methods, canonical decomposition is applied to real data acquired in North China Craton for 1D anisotropy analyses, and the result shows that, with effective modeling and cautious interpretation, canonical decomposition could be another good method to detect anisotropy of geological media.

  12. Study of SF6 gas decomposition products based on spectroscopy technology

    NASA Astrophysics Data System (ADS)

    Cai, Ji-xing; Na, Yan-xiang; Ni, Wei-yuan; Li, Guo-wei; Feng, Ke-cheng; Song, Gui-cai

    2011-08-01

    With the rapid development of power industry, the number of SF6 electrical equipment are increasing, it has gradually replaced the traditional insulating oil material as insulation and arc media in the high-voltage electrical equipment. Pure SF6 gas has excellent insulating properties and arc characteristics; however, under the effect of the strong arc, SF6 gas will decompose and generate toxic substances, then corroding electrical equipment, thereby affecting the insulation and arc ability of electrical equipment. If excessive levels of impurities in the gas that will seriously affect the mechanical properties, breaking performance and electrical performance of electrical equipment, it will cause many serious consequences, even threaten the safe operation of the grid. This paper main analyzes the basic properties of SF6 gas and the basic situation of decomposition in the discharge conditions, in order to simulate the actual high-voltage electrical equipment, designed and produced a simulation device that can simulate the decomposition of SF6 gas under a high voltage discharge, and using fourier transform infrared spectroscopy to analyze the sample that produced by the simulation device. The result show that the main discharge decomposition product is SO2F2 (sulfuryl fluoride), the substance can react with water and generate corrosive H2SO4(sulfuric acid) and HF (hydrogen fluoride), also found that the increase in the number with the discharge, SO2F2concentration levels are on the rise. Therefore, the material can be used as one of the main characteristic gases to determine the SF6 electrical equipment failure, and to monitor their concentration levels.

  13. 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.

  14. Adaptive Fourier decomposition based ECG denoising.

    PubMed

    Wang, Ze; Wan, Feng; Wong, Chi Man; Zhang, Liming

    2016-10-01

    A novel ECG denoising method is proposed based on the adaptive Fourier decomposition (AFD). The AFD decomposes a signal according to its energy distribution, thereby making this algorithm suitable for separating pure ECG signal and noise with overlapping frequency ranges but different energy distributions. A stop criterion for the iterative decomposition process in the AFD is calculated on the basis of the estimated signal-to-noise ratio (SNR) of the noisy signal. The proposed AFD-based method is validated by the synthetic ECG signal using an ECG model and also real ECG signals from the MIT-BIH Arrhythmia Database both with additive Gaussian white noise. Simulation results of the proposed method show better performance on the denoising and the QRS detection in comparing with major ECG denoising schemes based on the wavelet transform, the Stockwell transform, the empirical mode decomposition, and the ensemble empirical mode decomposition. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Iterative image-domain decomposition for dual-energy CT

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

    Niu, Tianye; Dong, Xue; Petrongolo, Michael

    2014-04-15

    as the proposed method but with an edge-preserving regularization term. Results: On the Catphan phantom, the method maintains the same spatial resolution on the decomposed images as that of the CT images before decomposition (8 pairs/cm) while significantly reducing their noise standard deviation. Compared to that obtained by the direct matrix inversion, the noise standard deviation in the images decomposed by the proposed algorithm is reduced by over 98%. Without considering the noise correlation properties in the formulation, the denoising scheme degrades the spatial resolution to 6 pairs/cm for the same level of noise suppression. Compared to the edge-preserving algorithm, the method achieves better low-contrast detectability. A quantitative study is performed on the contrast-rod slice of Catphan phantom. The proposed method achieves lower electron density measurement error as compared to that by the direct matrix inversion, and significantly reduces the error variation by over 97%. On the head phantom, the method reduces the noise standard deviation of decomposed images by over 97% without blurring the sinus structures. Conclusions: The authors propose an iterative image-domain decomposition method for DECT. The method combines noise suppression and material decomposition into an iterative process and achieves both goals simultaneously. By exploring the full variance-covariance properties of the decomposed images and utilizing the edge predetection, the proposed algorithm shows superior performance on noise suppression with high image spatial resolution and low-contrast detectability.« less

  16. Electron attachment to trinitrotoluene (TNT) embedded in He droplets: complete freezing of dissociation intermediates in an extended range of electron energies.

    PubMed

    Mauracher, Andreas; Schöbel, Harald; Ferreira da Silva, Filipe; Edtbauer, Achim; Mitterdorfer, Christian; Denifl, Stephan; Märk, Tilmann D; Illenberger, Eugen; Scheier, Paul

    2009-10-01

    Electron attachment to the explosive trinitrotoluene (TNT) embedded in Helium droplets (TNT@He) generates the non-decomposed complexes (TNT)(n)(-), but no fragment ions in the entire energy range 0-12 eV. This strongly contrasts the behavior of single TNT molecules in the gas phase at ambient temperatures, where electron capture leads to a variety of different fragmentation products via different dissociative electron attachment (DEA) reactions. Single TNT molecules decompose by attachment of an electron at virtually no extra energy reflecting the explosive nature of the compound. The complete freezing of dissociation intermediates in TNT embedded in the droplet is explained by the particular mechanisms of DEA in nitrobenzenes, which is characterized by complex rearrangement processes in the transient negative ion (TNI) prior to decomposition. These mechanisms provide the condition for effective energy withdrawal from the TNI into the dissipative environment thereby completely suppressing its decomposition.

  17. 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.

  18. a Novel Two-Component Decomposition for Co-Polar Channels of GF-3 Quad-Pol Data

    NASA Astrophysics Data System (ADS)

    Kwok, E.; Li, C. H.; Zhao, Q. H.; Li, Y.

    2018-04-01

    Polarimetric target decomposition theory is the most dynamic and exploratory research area in the field of PolSAR. But most methods of target decomposition are based on fully polarized data (quad pol) and seldom utilize dual-polar data for target decomposition. Given this, we proposed a novel two-component decomposition method for co-polar channels of GF-3 quad-pol data. This method decomposes the data into two scattering contributions: surface, double bounce in dual co-polar channels. To save this underdetermined problem, a criterion for determining the model is proposed. The criterion can be named as second-order averaged scattering angle, which originates from the H/α decomposition. and we also put forward an alternative parameter of it. To validate the effectiveness of proposed decomposition, Liaodong Bay is selected as research area. The area is located in northeastern China, where it grows various wetland resources and appears sea ice phenomenon in winter. and we use the GF-3 quad-pol data as study data, which which is China's first C-band polarimetric synthetic aperture radar (PolSAR) satellite. The dependencies between the features of proposed algorithm and comparison decompositions (Pauli decomposition, An&Yang decomposition, Yamaguchi S4R decomposition) were investigated in the study. Though several aspects of the experimental discussion, we can draw the conclusion: the proposed algorithm may be suitable for special scenes with low vegetation coverage or low vegetation in the non-growing season; proposed decomposition features only using co-polar data are highly correlated with the corresponding comparison decomposition features under quad-polarization data. Moreover, it would be become input of the subsequent classification or parameter inversion.

  19. Methodologies in forensic and decomposition microbiology

    USDA-ARS?s Scientific Manuscript database

    Culturable microorganisms represent only 0.1-1% of the total microbial diversity of the biosphere. This has severely restricted the ability of scientists to study the microbial biodiversity associated with the decomposition of ephemeral resources in the past. Innovations in technology are bringing...

  20. Nitrosonium-Catalyzed Decomposition of S-Nitrosothiols in Solution

    PubMed Central

    Zhao, Yi-Lei; McCarren, Patrick R.; Houk, K. N.; Choi, Bo Yoon; Toone, Eric J.

    2008-01-01

    The decomposition of S-nitrosothiols (RSNO) in solution under oxidative conditions is significantly faster than can be accounted for by homolysis of the S-N bond. Here we propose a cationic chain mechanism in which nitrosylation of nitrosothiol produces a nitrosylated cation that, in turn, reacts with a second nitrosothiol to produce disulfide and the NO dimer. Nitrosylated dimer acts as a source of nitrosonium for nitrosothiol nitrosylation, completing the catalytic cycle. The mechanism accounts for several unexplained facets of nitrosothiol chemistry in solution, including the observation that the decomposition of an RSNO is accelerated by O2, mixtures of O2 and NO, and other oxidants, that decomposition is inhibited by thiols and other antioxidants, that decomposition is dependent on sulfur substitution, and that decomposition often shows non-integral kinetic orders. PMID:16076198

  1. Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin

    NASA Astrophysics Data System (ADS)

    Scheer, Adam Michael

    Lignin is a complex, aromatic polymer abundant in cellulosic biomass (trees, switchgrass etc.). Thermochemical breakdown of lignin for liquid fuel production results in undesirable polycyclic aromatic hydrocarbons that lead to tar and soot byproducts. The fundamental chemistry governing these processes is not well understood. We have studied the unimolecular thermal decomposition mechanisms of aromatic lignin model compounds using a miniature SiC tubular reactor. Products are detected and characterized using time-of-flight mass spectrometry with both single photon (118.2 nm; 10.487 eV) and 1 + 1 resonance-enhanced multiphoton ionization (REMPI) as well as matrix isolation infrared spectroscopy. Gas exiting the heated reactor (300 K--1600 K) is subject to a free expansion after a residence time of approximately 100 micros. The expansion into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. By understanding the unimolecular fragmentation patterns of phenol (C6H5OH), anisole (C6H 5OCH3) and benzaldehyde (C6H5CHO), the more complicated thermocracking processes of the catechols (HO-C 6H4-OH), methoxyphenols (HO-C6H4-OCH 3) and hydroxybenzaldehydes (HO-C6H4-CHO) can be interpreted. These studies have resulted in a predictive model that allows the interpretation of vanillin, a complex phenolic ether containing methoxy, hydroxy and aldehyde functional groups. This model will serve as a guide for the pyrolyses of larger systems including lignin monomers such as coniferyl alcohol. The pyrolysis mechanisms of the dimethoxybenzenes (H3C-C 6H4-OCH3) and syringol, a hydroxydimethoxybenzene have also been studied. These results will aid in the understanding of the thermal fragmentation of sinapyl alcohol, the most complex lignin monomer. In addition to the model compound work, pyrolyisis of biomass has been studied via the pulsed laser ablation of poplar wood. With the REMPI scheme, aromatic lignin decomposition

  2. Decomposition patterns of buried remains at different intervals in the Central Highveld region of South Africa.

    PubMed

    Marais-Werner, A; Myburgh, J; Meyer, A; Nienaber, W C; Steyn, M

    2017-07-01

    Burial of remains is an important factor when one attempts to establish the post-mortem interval as it reduces, and in extreme cases, excludes oviposition by Diptera species. This in turn leads to modification of the decomposition process. The aim of this study was to record decomposition patterns of buried remains using a pig model. The pattern of decomposition was evaluated at different intervals and recorded according to existing guidelines. In order to contribute to our knowledge on decomposition in different settings, a quantifiable approach was followed. Results indicated that early stages of decomposition occurred rapidly for buried remains within 7-33 days. Between 14 and 33 days, buried pigs displayed common features associated with the early to middle stages of decomposition, such as discoloration and bloating. From 33 to 90 days advanced decomposition manifested on the remains, and pigs then reached a stage of advanced decomposition where little change was observed in the next ±90-183 days after interment. Throughout this study, total body scores remained higher for surface remains. Overall, buried pigs followed a similar pattern of decomposition to those of surface remains, although at a much slower rate when compared with similar post-mortem intervals in surface remains. In this study, the decomposition patterns and rates of buried remains were mostly influenced by limited insect activity and adipocere formation which reduces the rate of decay in a conducive environment (i.e. burial in soil).

  3. Decomposition of amino diazeniumdiolates (NONOates): molecular mechanisms.

    PubMed

    Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V

    2014-12-01

    Although diazeniumdiolates (X[N(O)NO](-)) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO](-), where R=N(C2H5)2 (1), N(C3H4NH2)2 (2), or N(C2H4NH2)2 (3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO](-) group with the apparent pKa and decomposition rate constants of 4.6 and 1 s(-1) for 1; 3.5 and 0.083 s(-1) for 2; and 3.8 and 0.0033 s(-1) for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~10(-7), for 1) undergoes the NN heterolytic bond cleavage (kd~10(7) s(-1) for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. The bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH<2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO](-) group. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms

    DOE PAGES

    Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V.

    2014-08-23

    Although diazeniumdiolates (X[N(O)NO] -) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R 2N[N(O)NO] -, where R = —N(C 2H 5) 2(1), —N(C 3H 4NH 2) 2(2), or —N(C 2H 4NH 2) 2(3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO] - group with the apparent pKa and decomposition ratemore » constants of 4.6 and 1 s -1 for 1; 3.5 and 0.083 s -1 for 2; and 3.8 and 0.0033 s -1 for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R 2N(H)N(O)NO tautomer (population ~ 10 -7, for 1) undergoes the N—N heterolytic bond cleavage (k d ~ 107 s -1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. Thus, the bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO] - group.« less

  5. 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.

  6. 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.

  7. Plant litter decomposition and nutrient release in peatlands

    NASA Astrophysics Data System (ADS)

    Bragazza, Luca; Buttler, Alexandre; Siegenthaler, Andy; Mitchell, Edward A. D.

    Decomposition of plant litter is a crucial process in controlling the carbon balance of peatlands. Indeed, as long as the rate of litter decomposition remains lower than the rate of above- and belowground litter production, a net accumulation of peat and, thus, carbon will take place. In addition, decomposition controls the release of important nutrients such as nitrogen, phosphorus, and potassium, the availability of which affects the structure and the functioning of plant communities. This chapter describes the role of the main drivers in affecting mass loss and nutrient release from recently deposited plant litter. In particular, the rate of mass loss of Sphagnum litter and vascular plant litter is reviewed in relation to regional climatic conditions, aerobic/anaerobic conditions, and litter chemistry. The rate of nutrient release is discussed in relation to the rate of mass loss and associated litter chemistry by means of a specific case study.

  8. Production and decomposition of forest litter fall on the Apalachicola River flood plain, Florida: Chapter B, Apalachicola River quality assessment

    USGS Publications Warehouse

    Elder, John F.; Cairns, Duncan J.

    1982-01-01

    Measurements of litter fall (leaves and other particulate organic material) and leaf decomposition were made on the bottom-land hardwood swamp of the Apalachicola River flood plain in 1979-80. Litter fall was collected monthly from nets located in 16 study plots. The plots represented five forest types in the swamp and levee areas of the Apalachicola River flood plain. Forty-three species of trees, vines, and other plants contributed to the total litter fall, but more than 90 percent of the leaf material originated from 12 species. Nonleaf material made up 42 percent of the total litter fall. Average litter fall was determined to be 800 grams per square meter per year, resulting in an annual deposition of 3.6 ? 105 metric tons of organic material in the 454-square-kilometer flood plain. The levee communities have less tree biomass but greater tree diversity than do swamp communities. The levee vegetation, containing less tree biomass, produces slightly more litter fall per unit of ground surface area than does the swamp vegetation. The swamps are dominated by three genera: tupelo (Nyssa), cypress (Taxodium) and ash (Fraxinus). These genera account for more than 50 percent of the total leaf fall in the flood plain, but they are the least productive, on a weight-perbiomass basis, of any of the 12 major leaf producers. Decomposition rates of leaves from five common floodplain tree species were measured using a standard leaf-bag technique. Leaf decomposition was highly species dependent. Tupelo (Nyssa spp.) and sweetgum (Liquidambar styraciflua) leaves decomposed completely in 6 months when flooded by river water. Leaves of baldcypress (Taxodium distichum) and diamond-leaf oak (Quercus laurifolia) were much more resistant. Water hickory (Carya aquatica) leaves showed intermediate decomposition rates. Decomposition of all species was greatly reduced in dry environments. Carbon and biomass loss rates from the leaves were nearly linear over a 6-month period, but nitrogen

  9. On the hadron mass decomposition

    NASA Astrophysics Data System (ADS)

    Lorcé, Cédric

    2018-02-01

    We argue that the standard decompositions of the hadron mass overlook pressure effects, and hence should be interpreted with great care. Based on the semiclassical picture, we propose a new decomposition that properly accounts for these pressure effects. Because of Lorentz covariance, we stress that the hadron mass decomposition automatically comes along with a stability constraint, which we discuss for the first time. We show also that if a hadron is seen as made of quarks and gluons, one cannot decompose its mass into more than two contributions without running into trouble with the consistency of the physical interpretation. In particular, the so-called quark mass and trace anomaly contributions appear to be purely conventional. Based on the current phenomenological values, we find that in average quarks exert a repulsive force inside nucleons, balanced exactly by the gluon attractive force.

  10. Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

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

    Everett, Susan M; Rawn, Claudia J; Keffer, David J.

    Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot.more » Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.« less

  11. Small Angle Neutron Scattering Study in Multi-Component Polymer Systems: Spinodal Decomposition and Beyond

    NASA Astrophysics Data System (ADS)

    Han, Charles

    Institute for Advanced Study, Shenzhen University, Shenzhen, China In memory of Professor John Kohn at this symposium, a time resolved SANS study for the early stage of spinodal decomposition kinetics of deuterated polycarbonate/poly(methylmethacrylate) blend will be reviewed which gives a clear proof of the Cahn-Hillard-Cook theory. This early stage of spinodal decomposition kinetics has been observed starting from the dimension (q-l) comparable to the single chain radius of gyration, Rg\\ , for a binary polymer mixture. The results provide an unequivocal quantitative measure of the virtual structure factor, S (q, ∞); the relationship of qm and qc through rate of growth, Cahn-plot analysis, and singularity in S (q, ∞); the growth of fluctuation of qRg <1 and intra-chain relaxation of qRg >1. More recent study of using mixed suspensions of polystyrene microspheres and poly(N-isopropylacrylamide) microgels as a molecular model system which has a long range repulsive interaction potential and a short range attractive potential, will also be discussed. In this model system, dynamic gelation, transition to soft glass state and cross-over to hard glass state will be demonstrated and compared with available theories for glass transition in structural materials. Acknowledgements go to: Polymers Division, and NCNR of NIST, and to ICCAS, Beijing, China. Also to my colleagues: M. Motowoka, H. Jinnai, T. Hashimoto, G.C. Yuan and H. Cheng.

  12. Conductimetric determination of decomposition of silicate melts

    NASA Technical Reports Server (NTRS)

    Kroeger, C.; Lieck, K.

    1986-01-01

    A description of a procedure is given to detect decomposition of silicate systems in the liquid state by conductivity measurements. Onset of decomposition can be determined from the temperature curves of resistances measured on two pairs of electrodes, one above the other. Degree of decomposition can be estimated from temperature and concentration dependency of conductivity of phase boundaries. This procedure was tested with systems PbO-B2O3 and PbO-B2O3-SiO2.

  13. 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

  14. 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

  15. Traits drive global wood decomposition rates more than climate.

    PubMed

    Hu, Zhenhong; Michaletz, Sean T; Johnson, Daniel J; McDowell, Nate G; Huang, Zhiqun; Zhou, Xuhui; Xu, Chonggang

    2018-06-14

    Wood decomposition is a major component of the global carbon cycle. Decomposition rates vary across climate gradients, which is thought to reflect the effects of temperature and moisture on the metabolic kinetics of decomposers. However, decomposition rates also vary with wood traits, which may reflect the influence of stoichiometry on decomposer metabolism as well as geometry relating the surface areas that decomposers colonize with the volumes they consume. In this paper, we combined metabolic and geometric scaling theories to formalize hypotheses regarding the drivers of wood decomposition rates, and assessed these hypotheses using a global compilation of data on climate, wood traits, and wood decomposition rates. Our results are consistent with predictions from both metabolic and geometric scaling theories. Approximately half of the global variation in decomposition rates was explained by wood traits (nitrogen content and diameter), while only a fifth was explained by climate variables (air temperature, precipitation, and relative humidity). These results indicate that global variation in wood decomposition rates is best explained by stoichiometric and geometric wood traits. Our findings suggest that inclusion of wood traits in global carbon cycle models can improve predictions of carbon fluxes from wood decomposition. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  16. The initial changes of fat deposits during the decomposition of human and pig remains.

    PubMed

    Notter, Stephanie J; Stuart, Barbara H; Rowe, Rebecca; Langlois, Neil

    2009-01-01

    The early stages of adipocere formation in both pig and human adipose tissue in aqueous environments have been investigated. The aims were to determine the short-term changes occurring to fat deposits during decomposition and to ascertain the suitability of pigs as models for human decomposition. Subcutaneous adipose tissue from both species after immersion in distilled water for up to six months was compared using Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry and inductively coupled plasma-mass spectrometry. Changes associated with decomposition were observed, but no adipocere was formed during the initial month of decomposition for either tissue type. Early-stage adipocere formation in pig samples during later months was detected. The variable time courses for adipose tissue decomposition were attributed to differences in the distribution of total fatty acids between species. Variations in the amount of sodium, potassium, calcium, and magnesium were also detected between species. The study shows that differences in total fatty acid composition between species need to be considered when interpreting results from experimental decomposition studies using pigs as human body analogs.

  17. Pollutant content in marine debris and characterization by thermal decomposition.

    PubMed

    Iñiguez, M E; Conesa, J A; Fullana, A

    2017-04-15

    Marine debris (MDs) produces a wide variety of negative environmental, economic, safety, health and cultural impacts. Most marine litter has a very low decomposition rate (plastics), leading to a gradual accumulation in the coastal and marine environment. Characterization of the MDs has been done in terms of their pollutant content: PAHs, ClBzs, ClPhs, BrPhs, PCDD/Fs and PCBs. The results show that MDs is not a very contaminated waste. Also, thermal decomposition of MDs materials has been studied in a thermobalance at different atmospheres and heating rates. Below 400-500K, the atmosphere does not affect the thermal degradation of the mentioned waste. However, at temperatures between 500 and 800K the presence of oxygen accelerates the decomposition. Also, a kinetic model is proposed for the combustion of the MDs, and the decomposition is compared with that of their main constituents, i.e., polyethylene (PE), polystyrene (PS), polypropylene (PP), nylon and polyethylene-terephthalate (PET). Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Involving older people in intermediate care.

    PubMed

    Andrews, JoyAnn; Manthorpe, Jill; Watson, Roger

    2004-05-01

    Intermediate care has become a crucial part of the United Kingdom government's programme for improving services for older people. Older people comprise a substantial part of the user base for these services, and it is increasingly recognized that there is a need for greater user involvement in service development for intermediate care. National initiatives undertaken in intermediate care have sought to widen and deepen the remit of such services, and in this way promote greater independence and improved quality of care for older people. In particular, the government has set out clear plans for reshaping services for older people in the National Health Service Plan and the rationale for greater involvement of older people in service development. This article considers ways in which these national and local objectives may be achieved and considers some of the implications for nursing. This paper aims to explore the concept of intermediate care and to identify trends and existing evidence of user involvement in care. In this way it charts a possible way forward for the development of a more 'user sensitive' approach. The following databases were searched: Medline, Cochrane Library, the Social Science Citation Index and CINAHL. Key words were 'intermediate care', 'older people', 'formal care', 'primary care', 'social services' and 'geriatrics', used in combination. The findings from this study indicate that there is considerable scope for increased user involvement in service development for intermediate care. Such challenges may be more effectively met through greater clarity of the concept of intermediate care, and a bridging of user involvement at the practice and policy levels. Nurses are key providers of intermediate care in the community. The involvement of older people in intermediate care service development must be premised on a shared comprehension of the purpose and function of intermediate care. Nurses must be involved in shifting intermediate care from

  19. Effect of CaO on the selectivity of N2O decomposition products: A combined experimental and DFT study

    NASA Astrophysics Data System (ADS)

    Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Gao, Pan; Dong, Changqing; Yang, Yongping

    2016-09-01

    The effect of CaO on N2O decomposition and the selectivity of its decomposition products (NO and N2) was investigated using a fixed-bed flow reactor with varying temperatures from 317 °C to 947 °C. The selectivity of NO from CaO-catalyzed N2O decomposition is much lower than the N2 selectivity with the N2/NO products ratio greater than 12.1. Compared to N2O homogeneous decomposition with the minimum N2/NO products ratio of 6.2 at 718 °C, CaO also decreases the NO selectivity from 718 °C to 947 °C. Density functional theory calculations provide possible N2O decomposition routes on the CaO (1 0 0) surface considering both N2 and NO as N2O decomposition products. The N2 formation route is more favorable than the NO formation route in terms of energy barrier and reaction energy, and NO formation on the CaO (1 0 0) surface is likely to proceed via N2O + Osurf2- → N2 + O2 , surf2- and N2O + O2 , surf2- → 2NO + Osurf2-.

  20. A Study of Japan for the Intermediate Grades.

    ERIC Educational Resources Information Center

    Sauer, Susan

    Arranged in outline form, this unit on Japan contains over 40 activities for intermediate grade students. Subjects covered are human and physical geography, social history, life style, communication and travel, occupations, recreation, art, education, government, and relations with the United States. Four to 10 activities are described under each…

  1. 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.

  2. [Study of methicillin-resistant Staphylococcus aureus colonization among intermediate-care facility patients].

    PubMed

    Giret, P; Roblot, F; Poupet, J Y; Thomas, P; Lussier-Bonneau, M D; Pradère, C; Becq-Giraudon, B; Fauchère, J L; Castel, O

    2001-08-01

    Prevalence of methicillin-resistant Staphylococcus aureus is high in the Poitiers teaching hospital, particularly in the intermediate care facilities. We performed a survey of methicillin-resistant Staphylococcus aureus colonization in the intermediate care facilities and 265 patients were included. Nasal, cutaneous and wound swab cultures were done at the time of admission and at the time of the patients' departure. A decolonization procedure of methicillin-resistant Staphylococcus aureus carriers was performed using nasal application of fusidic acid and different soaps for the skin. At entry, 17.7% of patients were methicillin-resistant Staphylococcus aureus carriers (of at least one location). At departure, 30.4% were methicillin-resistant Staphylococcus aureus carriers. Among methicillin-resistant Staphylococcus aureus non-carriers at entry, 24.3% became methicillin-resistant Staphylococcus aureus carriers. The principal risk factor of carriage was the initial presence of a wound (RR = 3.6). The incidence rate of methicillin-resistant Staphylococcus aureus infection among the 265 patients included was 3%. The systematic screening of patients at the time of admission is expensive and isolation technically hard to manage in the intermediate care facilities. The risk factor we found in this study allow us to propose a 'light' screening limited to patients with wounds.

  3. Optimization by nonhierarchical asynchronous decomposition

    NASA Technical Reports Server (NTRS)

    Shankar, Jayashree; Ribbens, Calvin J.; Haftka, Raphael T.; Watson, Layne T.

    1992-01-01

    Large scale optimization problems are tractable only if they are somehow decomposed. Hierarchical decompositions are inappropriate for some types of problems and do not parallelize well. Sobieszczanski-Sobieski has proposed a nonhierarchical decomposition strategy for nonlinear constrained optimization that is naturally parallel. Despite some successes on engineering problems, the algorithm as originally proposed fails on simple two dimensional quadratic programs. The algorithm is carefully analyzed for quadratic programs, and a number of modifications are suggested to improve its robustness.

  4. Simulating the Atmospheric Impact of Criegee Intermediates: Implementation of new understanding in atmospheric chemical mechanisms

    NASA Astrophysics Data System (ADS)

    Bloss, William; Newland, Mike; Rickard, Andrew; Vereecken, Luc; Evans, Mathew; Munoz, Amalia; Rodenas, Mila

    2016-04-01

    Unsaturated hydrocarbons - alkenes - account for about 90% of global VOC. Stabilized Criegee Intermediates (SCI) are thought to be formed in the atmosphere mainly from reactions of unsaturated hydrocarbons with ozone. SCI have been shown in laboratory and chamber experiments to rapidly oxidise SO2 and NO2, providing a potentially important gas phase oxidation route for these species in the atmosphere. They have also been implicated in the formation of aerosol and organic acids. However, the importance of SCI reactions with traces gases is critically dependent on the relative ratio of the rate constants for the reactions of the SCI with these and other trace gases, with H2O, and for unimolecular decomposition, which vary between SCIs, and between geometric isomers. The selection of reactions and rate constants is critically important in determining the calculated impact of SCI processes upon atmospheric composition and chemistry. Since the recent resurgence in interest in this chemistry, a number of model studies have been performed, with SCI mechanisms of varying comprehensiveness and accuracy, as the understanding of the community has evolved from new laboratory, theoretical and chamber studies, and field observations. Here we present an assessment of the dependence of modelled SCI abundance, behaviour and impacts upon the Criegee mechanism adopted, in the context of (a) the accepted status quo prior to the laboratory and field studies of Welz et al. and Mauldin et al., (b) changes to the SCI mechanism reflecting new kinetics for key bimolecular reactions, e.g. with SO2 and NO2; (c) emerging understanding of the interactions of SCI with water vapour and their unimolecular decomposition and (d) reactions with other atmospheric trace gases. The modelled SCI behaviour is compared with the results from recent chamber studies, and the resulting calculated SCI abundance and impacts evaluated for urban and forested atmospheric boundary layer scenarios.

  5. Investigation of automated task learning, decomposition and scheduling

    NASA Technical Reports Server (NTRS)

    Livingston, David L.; Serpen, Gursel; Masti, Chandrashekar L.

    1990-01-01

    The details and results of research conducted in the application of neural networks to task planning and decomposition are presented. Task planning and decomposition are operations that humans perform in a reasonably efficient manner. Without the use of good heuristics and usually much human interaction, automatic planners and decomposers generally do not perform well due to the intractable nature of the problems under consideration. The human-like performance of neural networks has shown promise for generating acceptable solutions to intractable problems such as planning and decomposition. This was the primary reasoning behind attempting the study. The basis for the work is the use of state machines to model tasks. State machine models provide a useful means for examining the structure of tasks since many formal techniques have been developed for their analysis and synthesis. It is the approach to integrate the strong algebraic foundations of state machines with the heretofore trial-and-error approach to neural network synthesis.

  6. Laboratory study of nitrogen and phosphorus remineralization during the decomposition of coastal plankton and seston

    NASA Astrophysics Data System (ADS)

    Garber, Jonathan H.

    1984-06-01

    The decomposition of cultured marine phytoplankton ( Skeletonema costatum) and natural estuarine seston from Narragansett Bay, RI, was studied at two temperatures (8°C and 18°C) in bottles containing sterile bay-water (30‰) and in bay-water with micro-organisms small enough to pass through a glass fibre filter (nominally < 1μ). About 50% of the particulate organic nitrogen (PON) and particulate phosphorus (PP) was immediately released to the water in dissolved organic forms from both types of organic matter. Comparison of changes in the dissolved organic nitrogen (DON) fraction in the sterile and non-sterile systems indicated that nearly all of the DON initially released was subsequently remineralized. Ammonification proceeded only in non-sterile bay-water. 20-25% of the PP was converted to dissolved inorganic-P (DIP) fraction after only 7 h in both sterile and non-sterile bay-water. Following autolytic releases of DON, DOP and DIP the initial rates of N and P remineralization were temperature dependent: Q 10 values for PON and PP decay during first phase of microbially mediated decomposition ranged from 1·3 to 6·4. Rates of remineralization then slowed so that about equal amounts of nutrients were remineralized (45-50% of the N and 57-60% of the P in the phytoplankton and 60-63% of the N and 36-60% of the P in the natural seston) after 30 days storage at either temperature. During 30 days of decomposition in non-sterile seawater the N/P ratios in the dissolved inorganic fractions converged on the ratios of total-N/total-P initially present in the bottles. Kinetic analysis of the decay of total organic-N (TON) and total organic-P (TOP) in the non-sterile systems and analysis of similar sets found in the literature showed that the initial stages of the decomposition of N and P from planktonic POM in vitro could be modelled as the sequential decay, at first-order rates, of two particulate fractions. The first, more labile, fraction comprised about 60% of the

  7. The physical chemistry of Criegee intermediates in the gas phase

    DOE PAGES

    Osborn, David L.; Taatjes, Craig A.

    2015-07-24

    Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular andmore » bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.« less

  8. Observations of Glide and Decomposition of a<101> Dislocations at High Temperatures in Ni-Al Single Crystals Deformed along the Hard Orientation

    NASA Technical Reports Server (NTRS)

    Srinivasan, R.; Daw, M. S.; Noebe, R. D.; Mills, M. J.

    2003-01-01

    Ni-44at.% Al and Ni-50at.% single crystals were tested in compression in the hard (001) orientations. The dislocation processes and deformation behavior were studied as a function of temperature, strain and strain rate. A slip transition in NiAl occurs from alpha(111) slip to non-alphaaaaaaaaaaa9111) slip at intermediate temperatures. In Ni-50at.% Al single crystal, only alpha(010) dislocations are observed above the slip transition temperature. In contrast, alpha(101)(101) glide has been observed to control deformation beyond the slip transition temperature in Ni-44at.%Al. alpha(101) dislocations are observed primarily along both (111) directions in the glide plane. High-resolution transmission electron microscopy observations show that the core of the alpha(101) dislocations along these directions is decomposed into two alpha(010) dislocations, separated by a distance of approximately 2nm. The temperature window of stability for these alpha(101) dislocations depends upon the strain rate. At a strain rate of 1.4 x 10(exp -4)/s, lpha(101) dislocations are observed between 800 and 1000K. Complete decomposition of a alpha(101) dislocations into alpha(010) dislocations occurs beyond 1000K, leading to alpha(010) climb as the deformation mode at higher temperature. At lower strain rates, decomposition of a alpha(101) dislocations has been observed to occur along the edge orientation at temperatures below 1000K. Embedded-atom method calculations and experimental results indicate that alpha(101) dislocation have a large Peieris stress at low temperature. Based on the present microstructural observations and a survey of the literature with respect to vacancy content and diffusion in NiAl, a model is proposed for alpha(101)(101) glide in Ni-44at.%Al, and for the observed yield strength versus temperature behavior of Ni-Al alloys at intermediate and high temperatures.

  9. The persistence of human DNA in soil following surface decomposition.

    PubMed

    Emmons, Alexandra L; DeBruyn, Jennifer M; Mundorff, Amy Z; Cobaugh, Kelly L; Cabana, Graciela S

    2017-09-01

    Though recent decades have seen a marked increase in research concerning the impact of human decomposition on the grave soil environment, the fate of human DNA in grave soil has been relatively understudied. With the purpose of supplementing the growing body of literature in forensic soil taphonomy, this study assessed the relative persistence of human DNA in soil over the course of decomposition. Endpoint PCR was used to assess the presence or absence of human nuclear and mitochondrial DNA, while qPCR was used to evaluate the quantity of human DNA recovered from the soil beneath four cadavers at the University of Tennessee's Anthropology Research Facility (ARF). Human nuclear DNA from the soil was largely unrecoverable, while human mitochondrial DNA was detectable in the soil throughout all decomposition stages. Mitochondrial DNA copy abundances were not significantly different between decomposition stages and were not significantly correlated to soil edaphic parameters tested. There was, however, a significant positive correlation between mitochondrial DNA copy abundances and the human associated bacteria, Bacteroides, as estimated by 16S rRNA gene abundances. These results show that human mitochondrial DNA can persist in grave soil and be consistently detected throughout decomposition. Copyright © 2017 The Chartered Society of Forensic Sciences. Published by Elsevier B.V. All rights reserved.

  10. Randomized Dynamic Mode Decomposition

    NASA Astrophysics Data System (ADS)

    Erichson, N. Benjamin; Brunton, Steven L.; Kutz, J. Nathan

    2017-11-01

    The dynamic mode decomposition (DMD) is an equation-free, data-driven matrix decomposition that is capable of providing accurate reconstructions of spatio-temporal coherent structures arising in dynamical systems. We present randomized algorithms to compute the near-optimal low-rank dynamic mode decomposition for massive datasets. Randomized algorithms are simple, accurate and able to ease the computational challenges arising with `big data'. Moreover, randomized algorithms are amenable to modern parallel and distributed computing. The idea is to derive a smaller matrix from the high-dimensional input data matrix using randomness as a computational strategy. Then, the dynamic modes and eigenvalues are accurately learned from this smaller representation of the data, whereby the approximation quality can be controlled via oversampling and power iterations. Here, we present randomized DMD algorithms that are categorized by how many passes the algorithm takes through the data. Specifically, the single-pass randomized DMD does not require data to be stored for subsequent passes. Thus, it is possible to approximately decompose massive fluid flows (stored out of core memory, or not stored at all) using single-pass algorithms, which is infeasible with traditional DMD algorithms.

  11. Interactions between soil and tree roots accelerate long-term soil carbon decomposition.

    PubMed

    Dijkstra, Feike A; Cheng, Weixin

    2007-11-01

    Decomposition of soil organic carbon (SOC) is the main process governing the release of CO(2) into the atmosphere from terrestrial systems. Although the importance of soil-root interactions for SOC decomposition has increasingly been recognized, their long-term effect on SOC decomposition remains poorly understood. Here we provide experimental evidence for a rhizosphere priming effect, in which interactions between soil and tree roots substantially accelerate SOC decomposition. In a 395-day greenhouse study with Ponderosa pine and Fremont cottonwood trees grown in three different soils, SOC decomposition in the planted treatments was significantly greater (up to 225%) than in soil incubations alone. This rhizosphere priming effect persisted throughout the experiment, until well after initial soil disturbance, and increased with a greater amount of root-derived SOC formed during the experiment. Loss of old SOC was greater than the formation of new C, suggesting that increased C inputs from roots could result in net soil C loss.

  12. Cadaver decomposition in terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Carter, David O.; Yellowlees, David; Tibbett, Mark

    2007-01-01

    A dead mammal (i.e. cadaver) is a high quality resource (narrow carbon:nitrogen ratio, high water content) that releases an intense, localised pulse of carbon and nutrients into the soil upon decomposition. Despite the fact that as much as 5,000 kg of cadaver can be introduced to a square kilometre of terrestrial ecosystem each year, cadaver decomposition remains a neglected microsere. Here we review the processes associated with the introduction of cadaver-derived carbon and nutrients into soil from forensic and ecological settings to show that cadaver decomposition can have a greater, albeit localised, effect on belowground ecology than plant and faecal resources. Cadaveric materials are rapidly introduced to belowground floral and faunal communities, which results in the formation of a highly concentrated island of fertility, or cadaver decomposition island (CDI). CDIs are associated with increased soil microbial biomass, microbial activity (C mineralisation) and nematode abundance. Each CDI is an ephemeral natural disturbance that, in addition to releasing energy and nutrients to the wider ecosystem, acts as a hub by receiving these materials in the form of dead insects, exuvia and puparia, faecal matter (from scavengers, grazers and predators) and feathers (from avian scavengers and predators). As such, CDIs contribute to landscape heterogeneity. Furthermore, CDIs are a specialised habitat for a number of flies, beetles and pioneer vegetation, which enhances biodiversity in terrestrial ecosystems.

  13. 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.

  14. A test of the hierarchical model of litter decomposition.

    PubMed

    Bradford, Mark A; Veen, G F Ciska; Bonis, Anne; Bradford, Ella M; Classen, Aimee T; Cornelissen, J Hans C; Crowther, Thomas W; De Long, Jonathan R; Freschet, Gregoire T; Kardol, Paul; Manrubia-Freixa, Marta; Maynard, Daniel S; Newman, Gregory S; Logtestijn, Richard S P; Viketoft, Maria; Wardle, David A; Wieder, William R; Wood, Stephen A; van der Putten, Wim H

    2017-12-01

    Our basic understanding of plant litter decomposition informs the assumptions underlying widely applied soil biogeochemical models, including those embedded in Earth system models. Confidence in projected carbon cycle-climate feedbacks therefore depends on accurate knowledge about the controls regulating the rate at which plant biomass is decomposed into products such as CO 2 . Here we test underlying assumptions of the dominant conceptual model of litter decomposition. The model posits that a primary control on the rate of decomposition at regional to global scales is climate (temperature and moisture), with the controlling effects of decomposers negligible at such broad spatial scales. Using a regional-scale litter decomposition experiment at six sites spanning from northern Sweden to southern France-and capturing both within and among site variation in putative controls-we find that contrary to predictions from the hierarchical model, decomposer (microbial) biomass strongly regulates decomposition at regional scales. Furthermore, the size of the microbial biomass dictates the absolute change in decomposition rates with changing climate variables. Our findings suggest the need for revision of the hierarchical model, with decomposers acting as both local- and broad-scale controls on litter decomposition rates, necessitating their explicit consideration in global biogeochemical models.

  15. Photogenerated radical intermediates of vitamin K 1: a time-resolved resonance Raman study

    NASA Astrophysics Data System (ADS)

    Balakrishnan, G.; Umapathy, S.

    1999-01-01

    Quinones play a vital role in the process of electron transfer in bacterial photosynthetic reaction centers. It is of interest to investigate the photochemical reactions involving quinones with a view to elucidating the structure-function relationships in the biological processes. Resonance Raman spectra of radical anions and the time-resolved resonance Raman spectra of vitamin K 1 (model compound for Q A in Rhodopseudomonas viridis, a bacterial photosynthetic reception center) are presented. The photochemical intermediates of vitamin K 1, viz. radical anion, ketyl radical and o-quinone methide have been identified. The vibrational assignments of all these intermediates are made on the basis of comparison with our earlier TR3 studies on radical anions of naphthoquinone and menaquinone.

  16. Protein vivisection reveals elusive intermediates in folding

    PubMed Central

    Zheng, Zhongzhou; Sosnick, Tobin R.

    2010-01-01

    Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu→Glu−) to destabilize and unfold a specific region of the protein. We apply this strategy to Ubiquitin, reversibly trapping a folding intermediate in which the β5 strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high energy states. PMID:20144618

  17. Chemical, physical and biological factors affecting wood decomposition in forest soils

    Treesearch

    Martin Jurgensen; Peter Laks; David Reed; Anne Collins; Deborah Page-Dumroese; Douglas Crawford

    2004-01-01

    Organic matter (OM) decomposition is an important variable in forest productivity and determining the potential of forest soils to sequester atmospheric CO2 (Grigal and Vance 2000; Kimble et al. 2003). Studies using OM from a particular location gives site-specific decomposition information, but differences in OM type and quality make it difficult to compare results...

  18. Decomposition of Fuzzy Soft Sets with Finite Value Spaces

    PubMed Central

    Jun, Young Bae

    2014-01-01

    The notion of fuzzy soft sets is a hybrid soft computing model that integrates both gradualness and parameterization methods in harmony to deal with uncertainty. The decomposition of fuzzy soft sets is of great importance in both theory and practical applications with regard to decision making under uncertainty. This study aims to explore decomposition of fuzzy soft sets with finite value spaces. Scalar uni-product and int-product operations of fuzzy soft sets are introduced and some related properties are investigated. Using t-level soft sets, we define level equivalent relations and show that the quotient structure of the unit interval induced by level equivalent relations is isomorphic to the lattice consisting of all t-level soft sets of a given fuzzy soft set. We also introduce the concepts of crucial threshold values and complete threshold sets. Finally, some decomposition theorems for fuzzy soft sets with finite value spaces are established, illustrated by an example concerning the classification and rating of multimedia cell phones. The obtained results extend some classical decomposition theorems of fuzzy sets, since every fuzzy set can be viewed as a fuzzy soft set with a single parameter. PMID:24558342

  19. Decomposition of fuzzy soft sets with finite value spaces.

    PubMed

    Feng, Feng; Fujita, Hamido; Jun, Young Bae; Khan, Madad

    2014-01-01

    The notion of fuzzy soft sets is a hybrid soft computing model that integrates both gradualness and parameterization methods in harmony to deal with uncertainty. The decomposition of fuzzy soft sets is of great importance in both theory and practical applications with regard to decision making under uncertainty. This study aims to explore decomposition of fuzzy soft sets with finite value spaces. Scalar uni-product and int-product operations of fuzzy soft sets are introduced and some related properties are investigated. Using t-level soft sets, we define level equivalent relations and show that the quotient structure of the unit interval induced by level equivalent relations is isomorphic to the lattice consisting of all t-level soft sets of a given fuzzy soft set. We also introduce the concepts of crucial threshold values and complete threshold sets. Finally, some decomposition theorems for fuzzy soft sets with finite value spaces are established, illustrated by an example concerning the classification and rating of multimedia cell phones. The obtained results extend some classical decomposition theorems of fuzzy sets, since every fuzzy set can be viewed as a fuzzy soft set with a single parameter.

  20. Through-wall image enhancement using fuzzy and QR decomposition.

    PubMed

    Riaz, Muhammad Mohsin; Ghafoor, Abdul

    2014-01-01

    QR decomposition and fuzzy logic based scheme is proposed for through-wall image enhancement. QR decomposition is less complex compared to singular value decomposition. Fuzzy inference engine assigns weights to different overlapping subspaces. Quantitative measures and visual inspection are used to analyze existing and proposed techniques.

  1. Decomposition Odour Profiling in the Air and Soil Surrounding Vertebrate Carrion

    PubMed Central

    2014-01-01

    Chemical profiling of decomposition odour is conducted in the environmental sciences to detect malodourous target sources in air, water or soil. More recently decomposition odour profiling has been employed in the forensic sciences to generate a profile of the volatile organic compounds (VOCs) produced by decomposed remains. The chemical profile of decomposition odour is still being debated with variations in the VOC profile attributed to the sample collection technique, method of chemical analysis, and environment in which decomposition occurred. To date, little consideration has been given to the partitioning of odour between different matrices and the impact this has on developing an accurate VOC profile. The purpose of this research was to investigate the decomposition odour profile surrounding vertebrate carrion to determine how VOCs partition between soil and air. Four pig carcasses (Sus scrofa domesticus L.) were placed on a soil surface to decompose naturally and their odour profile monitored over a period of two months. Corresponding control sites were also monitored to determine the VOC profile of the surrounding environment. Samples were collected from the soil below and the air (headspace) above the decomposed remains using sorbent tubes and analysed using gas chromatography-mass spectrometry. A total of 249 compounds were identified but only 58 compounds were common to both air and soil samples. This study has demonstrated that soil and air samples produce distinct subsets of VOCs that contribute to the overall decomposition odour. Sample collection from only one matrix will reduce the likelihood of detecting the complete spectrum of VOCs, which further confounds the issue of determining a complete and accurate decomposition odour profile. Confirmation of this profile will enhance the performance of cadaver-detection dogs that are tasked with detecting decomposition odour in both soil and air to locate victim remains. PMID:24740412

  2. Decomposition odour profiling in the air and soil surrounding vertebrate carrion.

    PubMed

    Forbes, Shari L; Perrault, Katelynn A

    2014-01-01

    Chemical profiling of decomposition odour is conducted in the environmental sciences to detect malodourous target sources in air, water or soil. More recently decomposition odour profiling has been employed in the forensic sciences to generate a profile of the volatile organic compounds (VOCs) produced by decomposed remains. The chemical profile of decomposition odour is still being debated with variations in the VOC profile attributed to the sample collection technique, method of chemical analysis, and environment in which decomposition occurred. To date, little consideration has been given to the partitioning of odour between different matrices and the impact this has on developing an accurate VOC profile. The purpose of this research was to investigate the decomposition odour profile surrounding vertebrate carrion to determine how VOCs partition between soil and air. Four pig carcasses (Sus scrofa domesticus L.) were placed on a soil surface to decompose naturally and their odour profile monitored over a period of two months. Corresponding control sites were also monitored to determine the VOC profile of the surrounding environment. Samples were collected from the soil below and the air (headspace) above the decomposed remains using sorbent tubes and analysed using gas chromatography-mass spectrometry. A total of 249 compounds were identified but only 58 compounds were common to both air and soil samples. This study has demonstrated that soil and air samples produce distinct subsets of VOCs that contribute to the overall decomposition odour. Sample collection from only one matrix will reduce the likelihood of detecting the complete spectrum of VOCs, which further confounds the issue of determining a complete and accurate decomposition odour profile. Confirmation of this profile will enhance the performance of cadaver-detection dogs that are tasked with detecting decomposition odour in both soil and air to locate victim remains.

  3. Investigation of shock-induced chemical decomposition of sensitized nitromethane through time-resolved Raman spectroscopy

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

    Pangilinan, G.I.; Constantinou, C.P.; Gruzdkov, Y.A.

    1996-07-01

    Molecular processes associated with shock induced chemical decomposition of a mixture of nitromethane with ethylenediamine (0.1 wt%) are examined using time-resolved, Raman scattering. When shocked by stepwise loading to 14.2 GPa pressure, changes in the nitromethane vibrational modes and the spectral background characterize the onset of reaction. The CN stretch mode softens and disappears even as the NO{sub 2} and CH{sub 3} stretch modes, though modified, retain their identities. The shape and intensity of the spectral background also shows changes characteristic of reaction. Changes in the background, which are observed even at lower peak pressures of 11.4 GPa, are assignedmore » to luminescence from reaction intermediates. The implications of these results to various molecular models of sensitization are discussed.« less

  4. 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.

  5. Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

    NASA Astrophysics Data System (ADS)

    Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

    2013-09-01

    The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

  6. Organic Carbon Sorption and Decomposition in Selected Global Soils

    DOE Data Explorer

    Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Wang, G.; Post, W. M.

    2014-01-01

    This data set reports the results of lab-scale experiments conducted to investigate the dynamics of organic carbon (C) decomposition from several soils from temperate, tropical, arctic, and sub-arctic environments. Results were used to test the newly developed soil microbe decomposition C model--Microbial-ENzyme-medicated Decomposition (MEND).

  7. Isothermal Decomposition of Hydrogen Peroxide Dihydrate

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Baragiola, R. A.

    2011-01-01

    We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H2O2 and H2O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.

  8. Domain Decomposition By the Advancing-Partition Method

    NASA Technical Reports Server (NTRS)

    Pirzadeh, Shahyar Z.

    2008-01-01

    A new method of domain decomposition has been developed for generating unstructured grids in subdomains either sequentially or using multiple computers in parallel. Domain decomposition is a crucial and challenging step for parallel grid generation. Prior methods are generally based on auxiliary, complex, and computationally intensive operations for defining partition interfaces and usually produce grids of lower quality than those generated in single domains. The new technique, referred to as "Advancing Partition," is based on the Advancing-Front method, which partitions a domain as part of the volume mesh generation in a consistent and "natural" way. The benefits of this approach are: 1) the process of domain decomposition is highly automated, 2) partitioning of domain does not compromise the quality of the generated grids, and 3) the computational overhead for domain decomposition is minimal. The new method has been implemented in NASA's unstructured grid generation code VGRID.

  9. Thermal Decomposition Behavior of Hydroxytyrosol (HT) in Nitrogen Atmosphere Based on TG-FTIR Methods.

    PubMed

    Tu, Jun-Ling; Yuan, Jiao-Jiao

    2018-02-13

    The thermal decomposition behavior of olive hydroxytyrosol (HT) was first studied using thermogravimetry (TG). Cracked chemical bond and evolved gas analysis during the thermal decomposition process of HT were also investigated using thermogravimetry coupled with infrared spectroscopy (TG-FTIR). Thermogravimetry-Differential thermogravimetry (TG-DTG) curves revealed that the thermal decomposition of HT began at 262.8 °C and ended at 409.7 °C with a main mass loss. It was demonstrated that a high heating rate (over 20 K·min -1 ) restrained the thermal decomposition of HT, resulting in an obvious thermal hysteresis. Furthermore, a thermal decomposition kinetics investigation of HT indicated that the non-isothermal decomposition mechanism was one-dimensional diffusion (D1), integral form g ( x ) = x ², and differential form f ( x ) = 1/(2 x ). The four combined approaches were employed to calculate the activation energy ( E = 128.50 kJ·mol -1 ) and Arrhenius preexponential factor (ln A = 24.39 min -1 ). In addition, a tentative mechanism of HT thermal decomposition was further developed. The results provide a theoretical reference for the potential thermal stability of HT.

  10. Effects of decomposition on gunshot wound characteristics: under moderate temperatures with insect activity.

    PubMed

    MacAulay, Lauren E; Barr, Darryl G; Strongman, Doug B

    2009-03-01

    Previous studies document characteristics of gunshot wounds shortly after they were inflicted. This study was conducted to determine if the early stages of decomposition obscure or alter the physical surface characteristics of gunshot wounds, thereby affecting the quantity and quality of information retrievable from such evidence. The study was conducted in August and September, 2005 in Nova Scotia, Canada in forested and exposed environments. Recently killed pigs were used as research models and were shot six times each at three different ranges (contact, 2.5 cm, and 1.5 m). Under these test conditions, the gunshot wounds maintained the characteristics unique to each gunshot range and changes that occurred during decomposition were not critical to the interpretation of the evidence. It was concluded that changes due to decomposition under the conditions tested would not affect the collection and interpretation of gunshot wound evidence until the skin was degraded in the late active or advanced decay stage of decomposition.

  11. 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

  12. 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

  13. Distributed Prognostics based on Structural Model Decomposition

    NASA Technical Reports Server (NTRS)

    Daigle, Matthew J.; Bregon, Anibal; Roychoudhury, I.

    2014-01-01

    Within systems health management, prognostics focuses on predicting the remaining useful life of a system. In the model-based prognostics paradigm, physics-based models are constructed that describe the operation of a system and how it fails. Such approaches consist of an estimation phase, in which the health state of the system is first identified, and a prediction phase, in which the health state is projected forward in time to determine the end of life. Centralized solutions to these problems are often computationally expensive, do not scale well as the size of the system grows, and introduce a single point of failure. In this paper, we propose a novel distributed model-based prognostics scheme that formally describes how to decompose both the estimation and prediction problems into independent local subproblems whose solutions may be easily composed into a global solution. The decomposition of the prognostics problem is achieved through structural decomposition of the underlying models. The decomposition algorithm creates from the global system model a set of local submodels suitable for prognostics. Independent local estimation and prediction problems are formed based on these local submodels, resulting in a scalable distributed prognostics approach that allows the local subproblems to be solved in parallel, thus offering increases in computational efficiency. Using a centrifugal pump as a case study, we perform a number of simulation-based experiments to demonstrate the distributed approach, compare the performance with a centralized approach, and establish its scalability. Index Terms-model-based prognostics, distributed prognostics, structural model decomposition ABBREVIATIONS

  14. Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO.

    PubMed

    Raghunath, P; Lee, Yuan-Pern; Lin, M C

    2017-05-25

    The kinetics and mechanisms for the reaction of the Criegee intermediate CH 2 OO with HNO 3 and the unimolecular decomposition of its reaction product CH 2 (O)NO 3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO 3 CH 2 OOH* with internal energy ∼44 kcal mol -1 . A fragmentation of this excited intermediate produces CH 2 (O)NO 3 + OH with its transition state located 5.0 kcal mol -1 below that of the reactants. Further decomposition of CH 2 (O)NO 3 produces HCO + HNO 3 , forming a catalytic cycle for destruction of CH 2 OO by HNO 3 . The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N 2 ) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH 2 OO + HNO 3 at 295 K, 5.1 × 10 -10 cm 3 molecule -1 s -1 , agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10 -10 cm 3 molecule -1 s -1 . The predicted branching ratios at 295 K are 0.21 for the formation of NO 3 CH 2 OOH and 0.79 for CH 2 (O)NO 3 + OH at a pressure of 40 Torr (N 2 ), and 0.79 for the formation of NO 3 CH 2 OOH and 0.21 for CH 2 (O)NO 3 + OH at 760 Torr (N 2 ). This new catalytic conversion of CH 2 OO to HCO + OH by HNO 3 might have significant impact on atmospheric chemistry.

  15. Theoretical study of gas hydrate decomposition kinetics--model development.

    PubMed

    Windmeier, Christoph; Oellrich, Lothar R

    2013-10-10

    In order to provide an estimate of the order of magnitude of intrinsic gas hydrate dissolution and dissociation kinetics, the "Consecutive Desorption and Melting Model" (CDM) is developed by applying only theoretical considerations. The process of gas hydrate decomposition is assumed to comprise two consecutive and repetitive quasi chemical reaction steps. These are desorption of the guest molecule followed by local solid body melting. The individual kinetic steps are modeled according to the "Statistical Rate Theory of Interfacial Transport" and the Wilson-Frenkel approach. All missing required model parameters are directly linked to geometric considerations and a thermodynamic gas hydrate equilibrium model.

  16. Modal decomposition of turbulent supersonic cavity

    NASA Astrophysics Data System (ADS)

    Soni, R. K.; Arya, N.; De, A.

    2018-06-01

    Self-sustained oscillations in a Mach 3 supersonic cavity with a length-to-depth ratio of three are investigated using wall-modeled large eddy simulation methodology for ReD = 3.39× 105 . The unsteady data obtained through computation are utilized to investigate the spatial and temporal evolution of the flow field, especially the second invariant of the velocity tensor, while the phase-averaged data are analyzed over a feedback cycle to study the spatial structures. This analysis is accompanied by the proper orthogonal decomposition (POD) data, which reveals the presence of discrete vortices along the shear layer. The POD analysis is performed in both the spanwise and streamwise planes to extract the coherence in flow structures. Finally, dynamic mode decomposition is performed on the data sequence to obtain the dynamic information and deeper insight into the self-sustained mechanism.

  17. Biogeochemistry of Decomposition and Detrital Processing

    NASA Astrophysics Data System (ADS)

    Sanderman, J.; Amundson, R.

    2003-12-01

    Decomposition is a key ecological process that roughly balances net primary production in terrestrial ecosystems and is an essential process in resupplying nutrients to the plant community. Decomposition consists of three concurrent processes: communition or fragmentation, leaching of water-soluble compounds, and microbial catabolism. Decomposition can also be viewed as a sequential process, what Eijsackers and Zehnder (1990) compare to a Russian matriochka doll. Soil macrofauna fragment and partially solubilize plant residues, facilitating establishment of a community of decomposer microorganisms. This decomposer community will gradually shift as the most easily degraded plant compounds are utilized and the more recalcitrant materials begin to accumulate. Given enough time and the proper environmental conditions, most naturally occurring compounds can completely be mineralized to inorganic forms. Simultaneously with mineralization, the process of humification acts to transform a fraction of the plant residues into stable soil organic matter (SOM) or humus. For reference, Schlesinger (1990) estimated that only ˜0.7% of detritus eventually becomes stabilized into humus.Decomposition plays a key role in the cycling of most plant macro- and micronutrients and in the formation of humus. Figure 1 places the roles of detrital processing and mineralization within the context of the biogeochemical cycling of essential plant nutrients. Chapin (1991) found that while the atmosphere supplied 4% and mineral weathering supplied no nitrogen and <1% of phosphorus, internal nutrient recycling is the source for >95% of all the nitrogen and phosphorus uptake by tundra species in Barrow, Alaska. In a cool temperate forest, nutrient recycling accounted for 93%, 89%, 88%, and 65% of total sources for nitrogen, phosphorus, potassium, and calcium, respectively ( Chapin, 1991). (13K)Figure 1. A decomposition-centric biogeochemical model of nutrient cycling. Although there is significant

  18. 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

  19. Accuracy assessment of a surface electromyogram decomposition system in human first dorsal interosseus muscle

    NASA Astrophysics Data System (ADS)

    Hu, Xiaogang; Rymer, William Z.; Suresh, Nina L.

    2014-04-01

    Objective. The aim of this study is to assess the accuracy of a surface electromyogram (sEMG) motor unit (MU) decomposition algorithm during low levels of muscle contraction. Approach. A two-source method was used to verify the accuracy of the sEMG decomposition system, by utilizing simultaneous intramuscular and surface EMG recordings from the human first dorsal interosseous muscle recorded during isometric trapezoidal force contractions. Spike trains from each recording type were decomposed independently utilizing two different algorithms, EMGlab and dEMG decomposition algorithms. The degree of agreement of the decomposed spike timings was assessed for three different segments of the EMG signals, corresponding to specified regions in the force task. A regression analysis was performed to examine whether certain properties of the sEMG and force signal can predict the decomposition accuracy. Main results. The average accuracy of successful decomposition among the 119 MUs that were common to both intramuscular and surface records was approximately 95%, and the accuracy was comparable between the different segments of the sEMG signals (i.e., force ramp-up versus steady state force versus combined). The regression function between the accuracy and properties of sEMG and force signals revealed that the signal-to-noise ratio of the action potential and stability in the action potential records were significant predictors of the surface decomposition accuracy. Significance. The outcomes of our study confirm the accuracy of the sEMG decomposition algorithm during low muscle contraction levels and provide confidence in the overall validity of the surface dEMG decomposition algorithm.

  20. The effects of temperature on decomposition and allelopathic phytotoxicity of boneseed litter.

    PubMed

    Al Harun, Md Abdullah Yousuf; Johnson, Joshua; Uddin, Md Nazim; Robinson, Randall W

    2015-07-01

    Decomposition of plant litter is a fundamental process in ecosystem function, carbon and nutrient cycling and, by extension, climate change. This study aimed to investigate the role of temperature on the decomposition of water soluble phenolics (WSP), carbon and soil nutrients in conjunction with the phytotoxicity dynamics of Chrysanthemoides monilifera subsp. monilifera (boneseed) litter. Treatments consisted of three factors including decomposition materials (litter alone, litter with soil and soil alone), decomposition periods and temperatures (5-15, 15-25 and 25-35°C (night/day)). Leachates were collected on 0, 5, 10, 20, 40 and 60th days to analyse physico-chemical parameters and phytotoxicity. Water soluble phenolics and dissolved organic carbon (DOC) increased with increasing temperature while nutrients like SO4(-2) and NO3(-1) decreased. Speed of germination, hypocotyl and radical length and weight of Lactuca sativa exposed to leachates were decreased with increasing decomposition temperature. All treatment components had significant effects on these parameters. There had a strong correlation between DOC and WSP, and WSP content of the leachates with radical length of test species. This study identified complex interactivity among temperature, WSP, DOC and soil nutrient dynamics of litter occupied soil and that these factors work together to influence phytotoxicity. Copyright © 2015. Published by Elsevier B.V.

  1. Aflatoxin decomposition in various soils

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

    Angle, J.S.

    The persistence of aflatoxin in the soil environment could potentially result in a number of adverse environmental consequences. To determine the persistence of aflatoxin in soil, /sup 14/C-labeled aflatoxin B1, was added to silt loam, sandy loam, and silty clay loam soils and the subsequent release of /sup 14/CO/sub 2/ was determined. After 120 days of incubation, 8.1% of the original aflatoxin added to the silt loam soil was released as CO/sub 2/. Aflatoxin decomposition in the sandy loam soil proceeded more quickly than the other two soils for the first 20 days of incubation. After this time, the decompositionmore » rate declined and by the end of the study, 4.9% of the aflatoxin was released as CO/sub 2/. Aflatoxin decomposition proceeded most slowly in the silty clay loam soil. Only 1.4% of aflatoxin added to the soil was released as CO/sub 2/ after 120 days incubation. To determine whether aflatoxin was bound to the silty clay loam soil, aflatoxin B1 was added to this soil and incubated for 20 days. The soil was periodically extracted and the aflatoxin species present were determined using thin layer chromatographic (TLC) procedures. After one day of incubation, the degradation products, aflatoxins B2 and G2, were observed. It was also found that much of the aflatoxin extracted from the soil was not mobile with the TLC solvent system used. This indicated that a conjugate may have formed and thus may be responsible for the lack of aflatoxin decomposition.« less

  2. Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

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

    Scheer, A. M.; Mukarakate, C.; Robichaud, D. J.

    The pyrolyses of phenol and d{sub 5}-phenol (C{sub 6}H{sub 5}OH and C{sub 6}D{sub 5}OH) have been studied using a high temperature, microtubular ({mu}tubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the {mu}tubular reactor of approximately 50-100 {micro}s. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at themore » onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C{sub 6}H{sub 5}OH {yields} c-C{sub 6}H{sub 6} = O {yields} c-C{sub 5}H{sub 6} + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C{sub 5}H{sub 6} {yields} c-C{sub 5}H{sub 5} + H {yields} HC {triple_bond} CH + HCCCH{sub 2}. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C{sub 6}H{sub 5}O-H {yields} C{sub 6}H{sub 5}O + H {yields} c-C{sub 5}H{sub 5} + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C{sub 6}H{sub 4}-OH) and hydroquinone (p-HO-C{sub 6}H{sub 4}-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.« less

  3. An experimental and theoretical study of the thermal decomposition of C 4H 6 isomers

    DOE PAGES

    Lockhart, James P. A.; Goldsmith, C. Franklin; Randazzo, John B.; ...

    2017-04-25

    The chemistry of small unsaturated hydrocarbons, such as 1,3–butadiene (1,3–C 4H 6), 1,2–butadiene (1,2–C 4H 6), 2–butyne (2–C 4H 6) and 1–butyne (1–C 4H 6), is of central importance to the modeling of combustion systems. These species are important intermediates in combustion processes, and yet their high-temperature chemistry remains poorly understood, with various dissociation and isomerization pathways proposed in the literature. Here we investigate the thermal decompositions of 1,3–C 4H 6, 1,2–C 4H 6, 2–C 4H 6 and 1–C 4H 6 inside a diaphragmless shock tube, at post shock total pressures of 26–261 Torr and temperatures ranging from 1428–2354 K,more » using laser schlieren densitometry. The experimental work has been complemented by high-level ab initio calculations, which collectively provide strong evidence that formally direct dissociation is the major channel for pyrolysis of 1,3–C 4H 6 and 2–C 4H 6; these paths have not been previously reported but are critical to reconciling the current work and disparate literature reports. The reaction mechanism presented here simulates the current experiments and experimental data from the literature very well. As a result, pressure and temperature dependent rate coefficients are given for the isomerization, formally direct and direct dissociation paths.« less

  4. An experimental and theoretical study of the thermal decomposition of C 4H 6 isomers

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

    Lockhart, James P. A.; Goldsmith, C. Franklin; Randazzo, John B.

    The chemistry of small unsaturated hydrocarbons, such as 1,3–butadiene (1,3–C 4H 6), 1,2–butadiene (1,2–C 4H 6), 2–butyne (2–C 4H 6) and 1–butyne (1–C 4H 6), is of central importance to the modeling of combustion systems. These species are important intermediates in combustion processes, and yet their high-temperature chemistry remains poorly understood, with various dissociation and isomerization pathways proposed in the literature. Here we investigate the thermal decompositions of 1,3–C 4H 6, 1,2–C 4H 6, 2–C 4H 6 and 1–C 4H 6 inside a diaphragmless shock tube, at post shock total pressures of 26–261 Torr and temperatures ranging from 1428–2354 K,more » using laser schlieren densitometry. The experimental work has been complemented by high-level ab initio calculations, which collectively provide strong evidence that formally direct dissociation is the major channel for pyrolysis of 1,3–C 4H 6 and 2–C 4H 6; these paths have not been previously reported but are critical to reconciling the current work and disparate literature reports. The reaction mechanism presented here simulates the current experiments and experimental data from the literature very well. As a result, pressure and temperature dependent rate coefficients are given for the isomerization, formally direct and direct dissociation paths.« less

  5. Decomposition of silicon carbide at high pressures and temperatures

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

    Daviau, Kierstin; Lee, Kanani K. M.

    We measure the onset of decomposition of silicon carbide, SiC, to silicon and carbon (e.g., diamond) at high pressures and high temperatures in a laser-heated diamond-anvil cell. We identify decomposition through x-ray diffraction and multiwavelength imaging radiometry coupled with electron microscopy analyses on quenched samples. We find that B3 SiC (also known as 3C or zinc blende SiC) decomposes at high pressures and high temperatures, following a phase boundary with a negative slope. The high-pressure decomposition temperatures measured are considerably lower than those at ambient, with our measurements indicating that SiC begins to decompose at ~ 2000 K at 60more » GPa as compared to ~ 2800 K at ambient pressure. Once B3 SiC transitions to the high-pressure B1 (rocksalt) structure, we no longer observe decomposition, despite heating to temperatures in excess of ~ 3200 K. The temperature of decomposition and the nature of the decomposition phase boundary appear to be strongly influenced by the pressure-induced phase transitions to higher-density structures in SiC, silicon, and carbon. The decomposition of SiC at high pressure and temperature has implications for the stability of naturally forming moissanite on Earth and in carbon-rich exoplanets.« less

  6. The processes of formation and epitaxial alignment of SrTiO3 thin films prepared by metallo-organic decomposition

    NASA Astrophysics Data System (ADS)

    Braunstein, G.; Paz-Pujalt, G. R.; Mason, M. G.; Blanton, T.; Barnes, C. L.; Margevich, D.

    1993-01-01

    The processes of formation and crystallization of thin films of SrTiO3 prepared by the method of metallo-organic decomposition have been studied with particular emphasis on the relationship between the thermal decomposition of the metallo-organic precursors and the eventual epitaxial alignment of the crystallized films. The films are deposited by spin coating onto single-crystalline silicon and SrTiO3 substrates, pyrolyzed on a hot plate at temperatures ranging from 200 to 450 °C, and subsequently heat treated in a quartz tube furnace at temperatures ranging from 300 to 1200 °C. Heat treatment at temperatures up to 450-500 °C results in the evaporation of solvents and other organic addenda, thermal decomposition of the metallo-organic (primarily metal-carboxylates) precursors, and formation of a carbonate species. This carbonate appears to be an intermediate phase in the reaction of SrCO3 and TiO2 to form SrTiO3. Relevant to this work is the fact that the carbonate species exhibits diffraction lines, indicating the formation of grains that can serve as seeds for the nucleation and growth of randomly oriented SrTiO3 crystallites, thereby leading to a polycrystalline film. Deposition on silicon substrates indeed results in the formation of polycrystalline SrTiO3. However, when the precursor solution is deposited on single-crystalline SrTiO3 substrates, the crystallization process involves a competition between two mechanisms: the random nucleation and growth of crystallites just described, and layer-by-layer solid phase epitaxy. Epitaxial alignment on SrTiO3 substrates can be achieved when the samples are heat treated at temperatures of 1100-1200 °C or at temperatures as low as 600-650 °C when the substrate is heated to about 1100 °C before spin coating.

  7. Mössbauer study on the thermal decomposition of potassium tris (oxalato) ferrate(III) trihydrate and bis (oxalato) ferrate(II) dihydrate

    NASA Astrophysics Data System (ADS)

    Ladriere, J.

    1992-04-01

    The thermal decompositions of K3Fe(ox)3 3 H2O and K2Fe(ox)2 2 H2O in nitrogen have been studied using Mössbauer spectroscopy, X-ray diffraction and thermal analysis methods in order to determine the nature of the solid residues obtained after each stage of decomposition. Particularly, after dehydration at 113°C, the ferric complex is reduced into a ferrous compound, with a quadrupole splitting of 3.89 mm/s, which corresponds to the anhydrous form of K2Fe(ox)2 2 H2O.

  8. Mixed fuel strategy for carbon deposition mitigation in solid oxide fuel cells at intermediate temperatures.

    PubMed

    Su, Chao; Chen, Yubo; Wang, Wei; Ran, Ran; Shao, Zongping; Diniz da Costa, João C; Liu, Shaomin

    2014-06-17

    In this study, we propose and experimentally verified that methane and formic acid mixed fuel can be employed to sustain solid oxide fuel cells (SOFCs) to deliver high power outputs at intermediate temperatures and simultaneously reduce the coke formation over the anode catalyst. In this SOFC system, methane itself was one part of the fuel, but it also played as the carrier gas to deliver the formic acid to reach the anode chamber. On the other hand, the products from the thermal decomposition of formic acid helped to reduce the carbon deposition from methane cracking. In order to clarify the reaction pathways for carbon formation and elimination occurring in the anode chamber during the SOFC operation, O2-TPO and SEM analysis were carried out together with the theoretical calculation. Electrochemical tests demonstrated that stable and high power output at an intermediate temperature range was well-maintained with a peak power density of 1061 mW cm(-2) at 750 °C. With the synergic functions provided by the mixed fuel, the SOFC was running for 3 days without any sign of cell performance decay. In sharp contrast, fuelled by pure methane and tested at similar conditions, the SOFC immediately failed after running for only 30 min due to significant carbon deposition. This work opens a new way for SOFC to conquer the annoying problem of carbon deposition just by properly selecting the fuel components to realize their synergic effects.

  9. Measurement of the energy dependence of X-ray-induced decomposition of potassium chlorate.

    PubMed

    Pravica, Michael; Bai, Ligang; Sneed, Daniel; Park, Changyong

    2013-03-21

    We report the first measurements of the X-ray induced decomposition of KClO3 as a function of energy in two experiments. KClO3 was pressurized to 3.5 GPa and irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 35 keV in 5 keV increments. A systematic increase in the decomposition rate as the energy was decreased was observed, which agrees with the 1/E(3) trend for the photoelectric process, except at the lowest energy studied. A second experiment was performed to access lower energies (10 and 12 keV) using a beryllium gasket; suggesting an apparent resonance near 15 keV or 0.83 Ǻ maximizing the chemical decomposition rate. A third experiment was performed using KIO3 to ascertain the anionic dependence of the decomposition rate, which was observed to be far slower than in KClO3, suggesting that the O-O distance is the critical factor in chemical reactions. These results will be important for more efficiently initiating chemical decomposition in materials using selected X-ray wavelengths that maximize decomposition to aid useful hard X-ray-induced chemistry and contribute understanding of the mechanism of X-ray-induced decomposition of the chlorates.

  10. Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

    PubMed

    Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

    2010-09-02

    Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

  11. Young Children's Thinking About Decomposition: Early Modeling Entrees to Complex Ideas in Science

    NASA Astrophysics Data System (ADS)

    Ero-Tolliver, Isi; Lucas, Deborah; Schauble, Leona

    2013-10-01

    This study was part of a multi-year project on the development of elementary students' modeling approaches to understanding the life sciences. Twenty-three first grade students conducted a series of coordinated observations and investigations on decomposition, a topic that is rarely addressed in the early grades. The instruction included in-class observations of different types of soil and soil profiling, visits to the school's compost bin, structured observations of decaying organic matter of various kinds, study of organisms that live in the soil, and models of environmental conditions that affect rates of decomposition. Both before and after instruction, students completed a written performance assessment that asked them to reason about the process of decomposition. Additional information was gathered through one-on-one interviews with six focus students who represented variability of performance across the class. During instruction, researchers collected video of classroom activity, student science journal entries, and charts and illustrations produced by the teacher. After instruction, the first-grade students showed a more nuanced understanding of the composition and variability of soils, the role of visible organisms in decomposition, and environmental factors that influence rates of decomposition. Through a variety of representational devices, including drawings, narrative records, and physical models, students came to regard decomposition as a process, rather than simply as an end state that does not require explanation.

  12. Scare Tactics: Evaluating Problem Decompositions Using Failure Scenarios

    NASA Technical Reports Server (NTRS)

    Helm, B. Robert; Fickas, Stephen

    1992-01-01

    Our interest is in the design of multi-agent problem-solving systems, which we refer to as composite systems. We have proposed an approach to composite system design by decomposition of problem statements. An automated assistant called Critter provides a library of reusable design transformations which allow a human analyst to search the space of decompositions for a problem. In this paper we describe a method for evaluating and critiquing problem decompositions generated by this search process. The method uses knowledge stored in the form of failure decompositions attached to design transformations. We suggest the benefits of our critiquing method by showing how it could re-derive steps of a published development example. We then identify several open issues for the method.

  13. Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

    PubMed

    Glascoe, Elizabeth A; Zaug, Joseph M; Burnham, Alan K

    2009-12-03

    The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

  14. Effect of Intermediate Hosts on Emerging Zoonoses.

    PubMed

    Cui, Jing-An; Chen, Fangyuan; Fan, Shengjie

    2017-08-01

    Most emerging zoonotic pathogens originate from animals. They can directly infect humans through natural reservoirs or indirectly through intermediate hosts. As a bridge, an intermediate host plays different roles in the transmission of zoonotic pathogens. In this study, we present three types of pathogen transmission to evaluate the effect of intermediate hosts on emerging zoonotic diseases in human epidemics. These types are identified as follows: TYPE 1, pathogen transmission without an intermediate host for comparison; TYPE 2, pathogen transmission with an intermediate host as an amplifier; and TYPE 3, pathogen transmission with an intermediate host as a vessel for genetic variation. In addition, we established three mathematical models to elucidate the mechanisms underlying zoonotic disease transmission according to these three types. Stability analysis indicated that the existence of intermediate hosts increased the difficulty of controlling zoonotic diseases because of more difficult conditions to satisfy for the disease to die out. The human epidemic would die out under the following conditions: TYPE 1: [Formula: see text] and [Formula: see text]; TYPE 2: [Formula: see text], [Formula: see text], and [Formula: see text]; and TYPE 3: [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] Simulation with similar parameters demonstrated that intermediate hosts could change the peak time and number of infected humans during a human epidemic; intermediate hosts also exerted different effects on controlling the prevalence of a human epidemic with natural reservoirs in different periods, which is important in addressing problems in public health. Monitoring and controlling the number of natural reservoirs and intermediate hosts at the right time would successfully manage and prevent the prevalence of emerging zoonoses in humans.

  15. 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.

  16. Parallel processing for pitch splitting decomposition

    NASA Astrophysics Data System (ADS)

    Barnes, Levi; Li, Yong; Wadkins, David; Biederman, Steve; Miloslavsky, Alex; Cork, Chris

    2009-10-01

    Decomposition of an input pattern in preparation for a double patterning process is an inherently global problem in which the influence of a local decomposition decision can be felt across an entire pattern. In spite of this, a large portion of the work can be massively distributed. Here, we discuss the advantages of geometric distribution for polygon operations with limited range of influence. Further, we have found that even the naturally global "coloring" step can, in large part, be handled in a geometrically local manner. In some practical cases, up to 70% of the work can be distributed geometrically. We also describe the methods for partitioning the problem into local pieces and present scaling data up to 100 CPUs. These techniques reduce DPT decomposition runtime by orders of magnitude.

  17. Nucleon Momentum and Spin Decompositions

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

    Cho, Y. M.

    We construct a gauge invariant canonical momentum operator which satisfies the canonical commutation relation to resolve the old controversy on the canonical versus kinematic momentum of a charged particle in gauge theories. With this we show how to obtain the gauge independent momentum and spin decompositions of composite particles to those of the constituents in QED and QCD, which has been thought to be impossible. Moerover, we show that there are two logically acceptable nucleom momentum and spin decompositions, depending on which gluons we identify as the constituent of nucleons.

  18. Bright compact bulges at intermediate redshifts

    NASA Astrophysics Data System (ADS)

    Sachdeva, Sonali; Saha, Kanak

    2018-07-01

    Studying bright (MB < -20), intermediate-redshift (0.4 < z< 1.0), disc-dominated (nB < 2.5) galaxies from Hubble Space Telescope/Advanced Camera for Surveys and Wide Field Camera 3 in Chandra Deep Field-South, in rest-frame B and I band, we found a new class of bulges that is brighter and more compact than ellipticals. We refer to them as `bright, compact bulges' (BCBs) - they resemble neither classical nor pseudo-bulges and constitute ˜12 per cent of the total bulge population at these redshifts. Examining free-bulge + disc decomposition sample and elliptical galaxy sample from Simard et al., we find that only ˜0.2 per cent of the bulges can be classified as BCBs in the local Universe. Bulge to total light ratio of disc galaxies with BCBs is (at ˜0.4) a factor of ˜2 and ˜4 larger than for those with classical and pseudo-bulges. BCBs are ˜2.5 and ˜6 times more massive than classical and pseudo-bulges. Although disc galaxies with BCBs host the most massive and dominant bulge type, their specific star formation rate is 1.5-2 times higher than other disc galaxies. This is contrary to the expectations that a massive compact bulge would lead to lower star formation rates. We speculate that our BCB host disc galaxies are descendant of massive, compact, and passive elliptical galaxies observed at higher redshifts. Those high-redshift ellipticals lack local counterparts and possibly evolved by acquiring a compact disc around them. The overall properties of BCBs support a picture of galaxy assembly in which younger discs are being accreted around massive pre-existing spheroids.

  19. Climate fails to predict wood decomposition at regional scales

    Treesearch

    Mark A. Bradford; Robert J. Warren; Petr Baldrian; Thomas W. Crowther; Daniel S. Maynard; Emily E. Oldfield; William R. Wieder; Stephen A. Wood; Joshua R. King

    2014-01-01

    Decomposition of organic matter strongly influences ecosystem carbon storage1. In Earth-system models, climate is a predominant control on the decomposition rates of organic matter2, 3, 4, 5. This assumption is based on the mean response of decomposition to climate, yet there is a growing appreciation in other areas of global change science that projections based on...

  20. Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

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

    Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim

    The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH){sub 3}) to bixbyite-type indium oxide (c-In{sub 2}O{sub 3}). The electron beam is focused onto a single cube-shaped In(OH){sub 3} crystal of {l_brace}100{r_brace} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turnmore » enables the evaluation of the kinetics of c-In{sub 2}O{sub 3} crystallization. Supplementary material (video of the transformation) related to this article can be found online at (10.1016/j.jssc.2012.09.022). After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH){sub 3} is transformed to a diffuse strongly textured ring-like pattern of c-In{sub 2}O{sub 3} that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In{sub 2}O{sub 3} domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In{sub 2}O{sub 3}), calculated from the shrinkage of the parent c-In(OH){sub 3} crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In{sub 2}O{sub 3} crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of {approx}3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three

  1. [Effects of tree species fine root decomposition on soil active organic carbon].

    PubMed

    Liu, Yan; Wang, Si-Long; Wang, Xiao-Wei; Yu, Xiao-Jun; Yang, Yue-Jun

    2007-03-01

    With incubation test, this paper studied the effects of fine root decomposition of Alnus cremastogyne, Cunninghamia lanceolata and Michelia macclurei on the content of soil active organic carbon at 9 degrees C , 14 degrees C , 24 degrees C and 28 degrees C. The results showed that the decomposition rate of fine root differed significantly with test tree species, which was decreased in the order of M. macclurei > A. cremastogyne > C. lanceolata. The decomposition rate was increased with increasing temperature, but declined with prolonged incubation time. Fine root source, incubation temperature, and incubation time all affected the contents of soil microbial biomass carbon and water-soluble organic carbon. The decomposition of fine root increased soil microbial biomass carbon and water-soluble organic carbon significantly, and the effect decreased in the order of M. macclurei > A. cremastogyne > C. lanceolata. Higher contents of soil microbial biomass carbon and water-soluble organic carbon were observed at medium temperature and middle incubation stage. Fine root decomposition had less effect on the content of soil readily oxidized organic carbon.

  2. Study of thermal decomposition mechanisms and low-level detection of explosives using pulsed photoacoustic technique

    NASA Astrophysics Data System (ADS)

    Yehya, F.; Chaudhary, A. K.; Srinivas, D.; Muralidharan, K.

    2015-11-01

    We report a novel time-resolved photoacoustic-based technique for studying the thermal decomposition mechanisms of some secondary explosives such as RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), picric acid, 4,6-dinitro-5-(4-nitro-1 H-imidazol-1-yl)-1 H-benzo[ d] [1-3] triazole, and 5-chloro-1-(4-nitrophenyl)-1 H-tetrazole. A comparison of the thermal decomposition mechanisms of these secondary explosives was made by detecting NO2 molecules released under controlled pyrolysis between 25 and 350 °C. The results show excellent agreement with the thermogravimetric and differential thermal analysis (TGA-DTA) results. A specially designed PA cell made of stainless steel was filled with explosive vapor and pumped using second harmonic, i.e., λ = 532 nm, pulses of duration 7 ns at a 10 Hz repetition rate, obtained using a Q-switched Nd:YAG laser. The use of a combination of PA and TGA-DTA techniques enables the study of NO2 generation, and this method can be used to scale the performance of these explosives as rocket fuels. The minimum detection limits of the four explosives were 38 ppmv to 69 ppbv, depending on their respective vapor pressures.

  3. Further insights into the kinetics of thermal decomposition during continuous cooling.

    PubMed

    Liavitskaya, Tatsiana; Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey

    2017-07-26

    Following the previous work (Phys. Chem. Chem. Phys., 2016, 18, 32021), this study continues to investigate the intriguing phenomenon of thermal decomposition during continuous cooling. The phenomenon can be detected and its kinetics can be measured by means of thermogravimetric analysis (TGA). The kinetics of the thermal decomposition of ammonium nitrate (NH 4 NO 3 ), nickel oxalate (NiC 2 O 4 ), and lithium sulfate monohydrate (Li 2 SO 4 ·H 2 O) have been measured upon heating and cooling and analyzed by means of the isoconversional methodology. The results have confirmed the hypothesis that the respective kinetics should be similar for single-step processes (NH 4 NO 3 decomposition) but different for multi-step ones (NiC 2 O 4 decomposition and Li 2 SO 4 ·H 2 O dehydration). It has been discovered that the differences in the kinetics can be either quantitative or qualitative. Physical insights into the nature of the differences have been proposed.

  4. Retrofit photovoltaic systems for intermediate sized applications - A design and market study

    NASA Astrophysics Data System (ADS)

    Noel, G. T.; Hagely, J. R.

    An assessment of the technical and economic feasibility of retrofitting a significant portion of the existing intermediate sector building/application inventory with photovoltaic systems is presented. The assessment includes the development of detailed engineering and architectural designs as well as cost estimates for 12 representative installations. Promising applications include retail stores, warehouses, office buildings, religious buildings, shopping centers, education buildings, hospitals, and industrial sites. A market study indicates that there is a national invetory of 1.5 to 2.0 million feasible intermediate sector applications, with the majority being in the 20 to 400 kW size range. The present cost of the major systems components and the cost of necessary building modifications are the primary current barriers to the realization of a large retrofit photovoltaic system market. The development of standardized modular system designs and installation techniques are feasible ways to minimize costs.

  5. 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.

  6. 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

  7. 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.

  8. Plant traits and decomposition: are the relationships for roots comparable to those for leaves?

    PubMed Central

    Birouste, Marine; Kazakou, Elena; Blanchard, Alain; Roumet, Catherine

    2012-01-01

    Background and Aims Fine root decomposition is an important determinant of nutrient and carbon cycling in grasslands; however, little is known about the factors controlling root decomposition among species. Our aim was to investigate whether interspecific variation in the potential decomposition rate of fine roots could be accounted for by root chemical and morphological traits, life history and taxonomic affiliation. We also investigated the co-ordinated variation in root and leaf traits and potential decomposition rates. Methods We analysed potential decomposition rates and the chemical and morphological traits of fine roots on 18 Mediterranean herbaceous species grown in controlled conditions. The results were compared with those obtained for leaves in a previous study conducted on similar species. Key Results Differences in the potential decomposition rates of fine roots between species were accounted for by root chemical composition, but not by morphological traits. The root potential decomposition rate varied with taxonomy, but not with life history. Poaceae, with high cellulose concentration and low concentrations of soluble compounds and phosphorus, decomposed more slowly than Asteraceae and Fabaceae. Patterns of root traits, including decomposition rate, mirrored those of leaf traits, resulting in a similar species clustering. Conclusions The highly co-ordinated variation of roots and leaves in terms of traits and potential decomposition rate suggests that changes in the functional composition of communities in response to anthropogenic changes will strongly affect biogeochemical cycles at the ecosystem level. PMID:22143881

  9. Comparing intra- and inter-specific effects on litter decomposition in an old-field ecosystem

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

    Crutsinger, Greg; Sanders, Dr. Nathan James; Classen, Aimee T

    2009-09-01

    Plant species can differ in the quantity and quality of leaf litter they produce, and many studies have examined whether plant species diversity affects leaf-litter decomposition and nutrient release. A growing number of studies have indicated that intra-specific variation within plant species can also affect key ecosystem processes. However, the relative importance of intra- versus inter-specific variation for the functioning of ecosystems remains poorly known. Here, we investigate the effects of intra-specific variation in a dominant old-field plant species, tall goldenrod (Solidago altissima), and inter-specific variation among goldenrod species on litter quality, decomposition, and nitrogen (N) release. We found thatmore » the nutrient concentration of leaf litter varied among genotypes, which translated into 50% difference in decomposition rates. Variation among other goldenrod species in decomposition rate was more than twice that of genetic variation within S. altissima. Furthermore, by manipulating litterbags to contain 1, 3, 6, or 9 genotypes, we found that S. altissima genotype identity had much stronger effects than did genotypic diversity on leaf-litter quality, decomposition, and N release. Taken together, these results suggest that the order of ecological importance for controlling leaf-litter decomposition and N release dynamics is plant species identitygenotype identity>genotypic diversity.« less

  10. Domain decomposition: A bridge between nature and parallel computers

    NASA Technical Reports Server (NTRS)

    Keyes, David E.

    1992-01-01

    Domain decomposition is an intuitive organizing principle for a partial differential equation (PDE) computation, both physically and architecturally. However, its significance extends beyond the readily apparent issues of geometry and discretization, on one hand, and of modular software and distributed hardware, on the other. Engineering and computer science aspects are bridged by an old but recently enriched mathematical theory that offers the subject not only unity, but also tools for analysis and generalization. Domain decomposition induces function-space and operator decompositions with valuable properties. Function-space bases and operator splittings that are not derived from domain decompositions generally lack one or more of these properties. The evolution of domain decomposition methods for elliptically dominated problems has linked two major algorithmic developments of the last 15 years: multilevel and Krylov methods. Domain decomposition methods may be considered descendants of both classes with an inheritance from each: they are nearly optimal and at the same time efficiently parallelizable. Many computationally driven application areas are ripe for these developments. A progression is made from a mathematically informal motivation for domain decomposition methods to a specific focus on fluid dynamics applications. To be introductory rather than comprehensive, simple examples are provided while convergence proofs and algorithmic details are left to the original references; however, an attempt is made to convey their most salient features, especially where this leads to algorithmic insight.

  11. Kinetics of the cellular decomposition of supersaturated solid solutions

    NASA Astrophysics Data System (ADS)

    Ivanov, M. A.; Naumuk, A. Yu.

    2014-09-01

    A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

  12. The Feasibility of Using Hydrogen Peroxide Decomposition Studies for High School Chemistry.

    ERIC Educational Resources Information Center

    Carter, Gillian E.

    1986-01-01

    Highlights difficulties that occur when teachers attempt to devise new experiments (use of hydrogen peroxide decomposition) and how seemingly useless results can be turned into productive student projects. Considers effects of ions present in tap water, pH, dust, and nature of vessel's surface. Reaction order and safety precautions are noted. (JN)

  13. Using Microwave Sample Decomposition in Undergraduate Analytical Chemistry

    NASA Astrophysics Data System (ADS)

    Griff Freeman, R.; McCurdy, David L.

    1998-08-01

    A shortcoming of many undergraduate classes in analytical chemistry is that students receive little exposure to sample preparation in chemical analysis. This paper reports the progress made in introducing microwave sample decomposition into several quantitative analysis experiments at Truman State University. Two experiments being performed in our current laboratory rotation include closed vessel microwave decomposition applied to the classical gravimetric determination of nickel and the determination of sodium in snack foods by flame atomic emission spectrometry. A third lab, using open-vessel microwave decomposition for the Kjeldahl nitrogen determination is now ready for student trial. Microwave decomposition reduces the time needed to complete these experiments and significantly increases the student awareness of the importance of sample preparation in quantitative chemical analyses, providing greater breadth and realism in the experiments.

  14. Steganography based on pixel intensity value decomposition

    NASA Astrophysics Data System (ADS)

    Abdulla, Alan Anwar; Sellahewa, Harin; Jassim, Sabah A.

    2014-05-01

    This paper focuses on steganography based on pixel intensity value decomposition. A number of existing schemes such as binary, Fibonacci, Prime, Natural, Lucas, and Catalan-Fibonacci (CF) are evaluated in terms of payload capacity and stego quality. A new technique based on a specific representation is proposed to decompose pixel intensity values into 16 (virtual) bit-planes suitable for embedding purposes. The proposed decomposition has a desirable property whereby the sum of all bit-planes does not exceed the maximum pixel intensity value, i.e. 255. Experimental results demonstrate that the proposed technique offers an effective compromise between payload capacity and stego quality of existing embedding techniques based on pixel intensity value decomposition. Its capacity is equal to that of binary and Lucas, while it offers a higher capacity than Fibonacci, Prime, Natural, and CF when the secret bits are embedded in 1st Least Significant Bit (LSB). When the secret bits are embedded in higher bit-planes, i.e., 2nd LSB to 8th Most Significant Bit (MSB), the proposed scheme has more capacity than Natural numbers based embedding. However, from the 6th bit-plane onwards, the proposed scheme offers better stego quality. In general, the proposed decomposition scheme has less effect in terms of quality on pixel value when compared to most existing pixel intensity value decomposition techniques when embedding messages in higher bit-planes.

  15. Phlogopite Decomposition, Water, and Venus

    NASA Technical Reports Server (NTRS)

    Johnson, N. M.; Fegley, B., Jr.

    2005-01-01

    Venus is a hot and dry planet with a surface temperature of 660 to 740 K and 30 parts per million by volume (ppmv) water vapor in its lower atmosphere. In contrast Earth has an average surface temperature of 288 K and 1-4% water vapor in its troposphere. The hot and dry conditions on Venus led many to speculate that hydrous minerals on the surface of Venus would not be there today even though they might have formed in a potentially wetter past. Thermodynamic calculations predict that many hydrous minerals are unstable under current Venusian conditions. Thermodynamics predicts whether a particular mineral is stable or not, but we need experimental data on the decomposition rate of hydrous minerals to determine if they survive on Venus today. Previously, we determined the decomposition rate of the amphibole tremolite, and found that it could exist for billions of years at current surface conditions. Here, we present our initial results on the decomposition of phlogopite mica, another common hydrous mineral on Earth.

  16. An experimental study of furan adsorption and decomposition on vicinal palladium surfaces using scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Loui, A.; Chiang, S.

    2018-04-01

    The intact adsorption and decomposition of furan (C4H4O) on vicinal palladium surfaces with (111)-oriented terraces has been studied by scanning tunneling microscopy (STM) over a range of temperatures. STM images at 225 K show that furan molecules lie flat and prefer to adsorb at upper step edges. At 225 K, furan molecules adsorbed on "narrow" terraces of 20 to 45 Å in width appear to diffuse more readily than those adsorbed on "wide" terraces of 160 to 220 Å. A distinct population of smaller features appears in STM images on "narrow" terraces at 288 K and on "wide" terraces at 415 K and is identified with the C3H3 decomposition product, agreeing with prior studies which demonstrated that furan dissociates on Pd(111) to yield carbon monoxide (CO) and a C3H3 moiety in the 280 to 320 K range. Based on our direct visualization of this reaction using STM, we propose a spatial mechanism in which adsorption of furan at upper step edges allows catalysis of the dissociation, followed by diffusion of the product to lower step edges.

  17. The processing of aluminum gasarites via thermal decomposition of interstitial hydrides

    NASA Astrophysics Data System (ADS)

    Licavoli, Joseph J.

    Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

  18. Wood decomposition as influenced by invertebrates

    Treesearch

    Michael D. Ulyshen

    2014-01-01

    The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial...

  19. Study of nonlinear interaction between bunched beam and intermediate cavities in a relativistic klystron amplifier

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Xu, Z.; Li, Z. H.; Tang, C. X.

    2012-07-01

    In intermediate cavities of a relativistic klystron amplifier (RKA) driven by intense relativistic electron beam, the equivalent circuit model, which is widely adopted to investigate the interaction between bunched beam and the intermediate cavity in a conventional klystron design, is invalid due to the high gap voltage and the nonlinear beam loading in a RKA. According to Maxwell equations and Lorentz equation, the self-consistent equations for beam-wave interaction in the intermediate cavity are introduced to study the nonlinear interaction between bunched beam and the intermediate cavity in a RKA. Based on the equations, the effects of modulation depth and modulation frequency of the beam on the gap voltage amplitude and its phase are obtained. It is shown that the gap voltage is significantly lower than that estimated by the equivalent circuit model when the beam modulation is high. And the bandwidth becomes wider as the beam modulation depth increases. An S-band high gain relativistic klystron amplifier is designed based on the result. And the corresponding experiment is carried out on the linear transformer driver accelerator. The peak output power has achieved 1.2 GW with an efficiency of 28.6% and a gain of 46 dB in the corresponding experiment.

  20. Critical Analysis of Nitramine Decomposition Data: Activation Energies and Frequency Factors for HMX and RDX Decomposition

    DTIC Science & Technology

    1985-09-01

    larger than the net energies of reaction for the same transitions ) represent energy needed for "freeing-up" of HMX or RDX molecules 70E. R. Lee, R. H...FACTORS FOR HMX AND RDX DECOMPOSITION Michael A. Schroeder DT!C .AECTE September 1985 SEP 3 0 8 * APPROVED FOR PUBUC RELEASE; DISTIR!UTION UNLIMITED. US...Final Activation Energies and Frequency Factors for HMX and RDX Decomposition b PERFORMING ORG. REPORT N, %1ER 7. AUTHOR(@) 6 CONTRACT OR GRANT NuMP

  1. Analysis of cured carbon-phenolic decomposition products to investigate the thermal decomposition of nozzle materials

    NASA Technical Reports Server (NTRS)

    Thompson, James M.; Daniel, Janice D.

    1989-01-01

    The development of a mass spectrometer/thermal analyzer/computer (MS/TA/Computer) system capable of providing simultaneous thermogravimetry (TG), differential thermal analysis (DTA), derivative thermogravimetry (DTG) and evolved gas detection and analysis (EGD and EGA) under both atmospheric and high pressure conditions is described. The combined system was used to study the thermal decomposition of the nozzle material that constitutes the throat of the solid rocket boosters (SRB).

  2. Generalized decompositions of dynamic systems and vector Lyapunov functions

    NASA Astrophysics Data System (ADS)

    Ikeda, M.; Siljak, D. D.

    1981-10-01

    The notion of decomposition is generalized to provide more freedom in constructing vector Lyapunov functions for stability analysis of nonlinear dynamic systems. A generalized decomposition is defined as a disjoint decomposition of a system which is obtained by expanding the state-space of a given system. An inclusion principle is formulated for the solutions of the expansion to include the solutions of the original system, so that stability of the expansion implies stability of the original system. Stability of the expansion can then be established by standard disjoint decompositions and vector Lyapunov functions. The applicability of the new approach is demonstrated using the Lotka-Volterra equations.

  3. Litter decomposition patterns and dynamics across biomes: Initial results from the global TeaComposition initiative

    NASA Astrophysics Data System (ADS)

    Djukic, Ika; Kappel Schmidt, Inger; Steenberg Larsen, Klaus; Beier, Claus

    2017-04-01

    Litter decomposition represents one of the largest fluxes in the global terrestrial carbon cycle and a number of large-scale decomposition experiments have been conducted focusing on this fundamental soil process. However, previous studies were most often based on site-specific litters and methodologies. The contrasting litter and soil types used and the general lack of common protocols still poses a major challenge as it adds major uncertainty to meta-analyses across different experiments and sites. In the TeaComposition initiative, we aim to investigate the potential litter decomposition by using standardized substrates (tea) for comparison of temporal litter decomposition rates across different ecosystems worldwide. To this end, Lipton tea bags (Rooibos and Green Tea) has been buried in the H-A or Ah horizon and incubated over the period of 36 months within 400 sites covering diverse ecosystems in 9 zonobiomes. We measured initial litter chemistry and litter mass loss 3 months after the start of decomposition and linked the decomposition rates to site and climatic conditions as well as to the existing decompositions rates of the local litter. We will present and discuss the outcomes of this study. Acknowledgment: We are thankful to colleagues from more than 300 sites who were participating in the implementation of this initiative and who are not mentioned individually as co-authors yet.

  4. Climate history shapes contemporary leaf litter decomposition

    Treesearch

    Michael S. Strickland; Ashley D. Keiser; Mark A. Bradford

    2015-01-01

    Litter decomposition is mediated by multiple variables, of which climate is expected to be a dominant factor at global scales. However, like other organisms, traits of decomposers and their communities are shaped not just by the contemporary climate but also their climate history. Whether or not this affects decomposition rates is underexplored. Here we source...

  5. 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...

  6. Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition.

    PubMed

    Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A

    2005-10-22

    Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.

  7. Improving interMediAte Risk management. MARK study

    PubMed Central

    2011-01-01

    Background Cardiovascular risk functions fail to identify more than 50% of patients who develop cardiovascular disease. This is especially evident in the intermediate-risk patients in which clinical management becomes difficult. Our purpose is to analyze if ankle-brachial index (ABI), measures of arterial stiffness, postprandial glucose, glycosylated hemoglobin, self-measured blood pressure and presence of comorbidity are independently associated to incidence of vascular events and whether they can improve the predictive capacity of current risk equations in the intermediate-risk population. Methods/Design This project involves 3 groups belonging to REDIAPP (RETICS RD06/0018) from 3 Spanish regions. We will recruit a multicenter cohort of 2688 patients at intermediate risk (coronary risk between 5 and 15% or vascular death risk between 3-5% over 10 years) and no history of atherosclerotic disease, selected at random. We will record socio-demographic data, information on diet, physical activity, comorbidity and intermittent claudication. We will measure ABI, pulse wave velocity and cardio ankle vascular index at rest and after a light intensity exercise. Blood pressure and anthropometric data will be also recorded. We will also quantify lipids, glucose and glycosylated hemoglobin in a fasting blood sample and postprandial capillary glucose. Eighteen months after the recruitment, patients will be followed up to determine the incidence of vascular events (later follow-ups are planned at 5 and 10 years). We will analyze whether the new proposed risk factors contribute to improve the risk functions based on classic risk factors. Discussion Primary prevention of cardiovascular diseases is a priority in public health policy of developed and developing countries. The fundamental strategy consists in identifying people in a high risk situation in which preventive measures are effective and efficient. Improvement of these predictions in our country will have an immediate

  8. Model-based multiple patterning layout decomposition

    NASA Astrophysics Data System (ADS)

    Guo, Daifeng; Tian, Haitong; Du, Yuelin; Wong, Martin D. F.

    2015-10-01

    As one of the most promising next generation lithography technologies, multiple patterning lithography (MPL) plays an important role in the attempts to keep in pace with 10 nm technology node and beyond. With feature size keeps shrinking, it has become impossible to print dense layouts within one single exposure. As a result, MPL such as double patterning lithography (DPL) and triple patterning lithography (TPL) has been widely adopted. There is a large volume of literature on DPL/TPL layout decomposition, and the current approach is to formulate the problem as a classical graph-coloring problem: Layout features (polygons) are represented by vertices in a graph G and there is an edge between two vertices if and only if the distance between the two corresponding features are less than a minimum distance threshold value dmin. The problem is to color the vertices of G using k colors (k = 2 for DPL, k = 3 for TPL) such that no two vertices connected by an edge are given the same color. This is a rule-based approach, which impose a geometric distance as a minimum constraint to simply decompose polygons within the distance into different masks. It is not desired in practice because this criteria cannot completely capture the behavior of the optics. For example, it lacks of sufficient information such as the optical source characteristics and the effects between the polygons outside the minimum distance. To remedy the deficiency, a model-based layout decomposition approach to make the decomposition criteria base on simulation results was first introduced at SPIE 2013.1 However, the algorithm1 is based on simplified assumption on the optical simulation model and therefore its usage on real layouts is limited. Recently AMSL2 also proposed a model-based approach to layout decomposition by iteratively simulating the layout, which requires excessive computational resource and may lead to sub-optimal solutions. The approach2 also potentially generates too many stiches. In this

  9. Metagenomic analysis of antibiotic resistance genes (ARGs) during refuse decomposition.

    PubMed

    Liu, Xi; Yang, Shu; Wang, Yangqing; Zhao, He-Ping; Song, Liyan

    2018-04-12

    Landfill is important reservoirs of residual antibiotics and antibiotic resistance genes (ARGs), but the mechanism of landfill application influence on antibiotic resistance remains unclear. Although refuse decomposition plays a crucial role in landfill stabilization, its impact on the antibiotic resistance has not been well characterized. To better understand the impact, we studied the dynamics of ARGs and the bacterial community composition during refuse decomposition in a bench-scale bioreactor after long term operation (265d) based on metagenomics analysis. The total abundances of ARGs increased from 431.0ppm in the initial aerobic phase (AP) to 643.9ppm in the later methanogenic phase (MP) during refuse decomposition, suggesting that application of landfill for municipal solid waste (MSW) treatment may elevate the level of ARGs. A shift from drug-specific (bacitracin, tetracycline and sulfonamide) resistance to multidrug resistance was observed during the refuse decomposition and was driven by a shift of potential bacteria hosts. The elevated abundance of Pseudomonas mainly contributed to the increasing abundance of multidrug ARGs (mexF and mexW). Accordingly, the percentage of ARGs encoding an efflux pump increased during refuse decomposition, suggesting that potential bacteria hosts developed this mechanism to adapt to the carbon and energy shortage when biodegradable substances were depleted. Overall, our findings indicate that the use of landfill for MSW treatment increased antibiotic resistance, and demonstrate the need for a comprehensive investigation of antibiotic resistance in landfill. Copyright © 2018. Published by Elsevier B.V.

  10. About decomposition approach for solving the classification problem

    NASA Astrophysics Data System (ADS)

    Andrianova, A. A.

    2016-11-01

    This article describes the features of the application of an algorithm with using of decomposition methods for solving the binary classification problem of constructing a linear classifier based on Support Vector Machine method. Application of decomposition reduces the volume of calculations, in particular, due to the emerging possibilities to build parallel versions of the algorithm, which is a very important advantage for the solution of problems with big data. The analysis of the results of computational experiments conducted using the decomposition approach. The experiment use known data set for binary classification problem.

  11. Introducing the Improved Heaviside Approach to Partial Fraction Decomposition to Undergraduate Students: Results and Implications from a Pilot Study

    ERIC Educational Resources Information Center

    Man, Yiu-Kwong

    2012-01-01

    Partial fraction decomposition is a useful technique often taught at senior secondary or undergraduate levels to handle integrations, inverse Laplace transforms or linear ordinary differential equations, etc. In recent years, an improved Heaviside's approach to partial fraction decomposition was introduced and developed by the author. An important…

  12. Isothermal decay studies of intermediate energy levels in quartz.

    PubMed

    Veronese, I; Giussani, A; Göksu, H Y; Martini, M

    2004-05-01

    The recent interest in the thermoluminescence of quartz extracted from unfired building materials, such as mortar and concrete for dose reconstruction applications, led to the requirement of an accurate determination of the lifetime of the intermediate glow peaks in this mineral. The prediction of the lifetimes of these peaks is helpful in establishing the likely time range within which retrospective measurements can be carried out. These peaks, corresponding to intermediate energy levels, occur in the glow curve in the temperature range 150-250 degrees C (heating rate 2 degrees C/s). Lifetimes of 720+/-70 days and 580+/-70 years (at a temperature of 15 degrees C) were derived for the two main peaks placed in the glow curve at approximately 150 degrees C and 200 degrees C, respectively, using the isothermal decay technique. These results as well as the estimated values of the trap parameters (thermal activation energy and frequency factor) have been compared with the data already available in the literature.

  13. Solid-state graphene formation via a nickel carbide intermediate phase [Nickel carbide (Ni 3C) as an intermediate phase for graphene formation

    DOE PAGES

    Xiong, W; Zhou, Yunshen; Hou, Wenjia; ...

    2015-11-10

    Direct formation of graphene with controlled number of graphitic layers on dielectric surfaces is highly desired for practical applications. Despite significant progress achieved in understanding the formation of graphene on metallic surfaces through chemical vapor deposition (CVD) of hydrocarbons, very limited research is available elucidating the graphene formation process via rapid thermal processing (RTP) of solid-state amorphous carbon, through which graphene is formed directly on dielectric surfaces accompanied by autonomous nickel evaporation. It is suggested that a metastable hexagonal nickel carbide (Ni 3C) intermediate phase plays a critical role in transforming amorphous carbon to 2D crystalline graphene and contributing tomore » the autonomous Ni evaporation. Temperature resolved carbon and nickel evolution in the RTP process is investigated using Auger electron spectroscopic (AES) depth profiling and glancing-angle X-ray diffraction (GAXRD). Formation, migration and decomposition of the hexagonal Ni 3C are confirmed to be responsible for the formation of graphene and the evaporation of Ni at 1100 °C. The Ni 3C-assisted graphene formation mechanism expands the understanding of Ni-catalyzed graphene formation, and provides insightful guidance for controlled growth of graphene through the solid-state transformation process.« less

  14. A quantitative acoustic emission study on fracture processes in ceramics based on wavelet packet decomposition

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

    Ning, J. G.; Chu, L.; Ren, H. L., E-mail: huilanren@bit.edu.cn

    2014-08-28

    We base a quantitative acoustic emission (AE) study on fracture processes in alumina ceramics on wavelet packet decomposition and AE source location. According to the frequency characteristics, as well as energy and ringdown counts of AE, the fracture process is divided into four stages: crack closure, nucleation, development, and critical failure. Each of the AE signals is decomposed by a 2-level wavelet package decomposition into four different (from-low-to-high) frequency bands (AA{sub 2}, AD{sub 2}, DA{sub 2}, and DD{sub 2}). The energy eigenvalues P{sub 0}, P{sub 1}, P{sub 2}, and P{sub 3} corresponding to these four frequency bands are calculated. Bymore » analyzing changes in P{sub 0} and P{sub 3} in the four stages, we determine the inverse relationship between AE frequency and the crack source size during ceramic fracture. AE signals with regard to crack nucleation can be expressed when P{sub 0} is less than 5 and P{sub 3} more than 60; whereas AE signals with regard to dangerous crack propagation can be expressed when more than 92% of P{sub 0} is greater than 4, and more than 95% of P{sub 3} is less than 45. Geiger location algorithm is used to locate AE sources and cracks in the sample. The results of this location algorithm are consistent with the positions of fractures in the sample when observed under a scanning electronic microscope; thus the locations of fractures located with Geiger's method can reflect the fracture process. The stage division by location results is in a good agreement with the division based on AE frequency characteristics. We find that both wavelet package decomposition and Geiger's AE source locations are suitable for the identification of the evolutionary process of cracks in alumina ceramics.« less

  15. Effects of mesh bag enclosure and termites on fine woody debris decomposition in a subtropical forest

    Treesearch

    Allison M. Stoklosa; Michael D. Ulyshen; Zhaofei Fan; Morgan Varner; Sebastian Seibold; Jorg Muller

    2016-01-01

    The role of insects in terrestrial decomposition remains poorly resolved, particularly for infrequently studied substrates like small diameter woody debris.  Uncertainty about how mesh bags used to exclude arthropods may affect decomposition rates continues to impede progress in this area.  We sought to (1) measure how insects affect the decomposition of small diameter...

  16. 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

  17. Expert vs. novice: Problem decomposition/recomposition in engineering design

    NASA Astrophysics Data System (ADS)

    Song, Ting

    The purpose of this research was to investigate the differences of using problem decomposition and problem recomposition among dyads of engineering experts, dyads of engineering seniors, and dyads of engineering freshmen. Fifty participants took part in this study. Ten were engineering design experts, 20 were engineering seniors, and 20 were engineering freshmen. Participants worked in dyads to complete an engineering design challenge within an hour. The entire design process was video and audio recorded. After the design session, members participated in a group interview. This study used protocol analysis as the methodology. Video and audio data were transcribed, segmented, and coded. Two coding systems including the FBS ontology and "levels of the problem" were used in this study. A series of statistical techniques were used to analyze data. Interview data and participants' design sketches also worked as supplemental data to help answer the research questions. By analyzing the quantitative and qualitative data, it was found that students used less problem decomposition and problem recomposition than engineer experts in engineering design. This result implies that engineering education should place more importance on teaching problem decomposition and problem recomposition. Students were found to spend less cognitive effort when considering the problem as a whole and interactions between subsystems than engineer experts. In addition, students were also found to spend more cognitive effort when considering details of subsystems. These results showed that students tended to use dept-first decomposition and experts tended to use breadth-first decomposition in engineering design. The use of Function (F), Behavior (B), and Structure (S) among engineering experts, engineering seniors, and engineering freshmen was compared on three levels. Level 1 represents designers consider the problem as an integral whole, Level 2 represents designers consider interactions between

  18. First-principles-based kinetic Monte Carlo simulation of nitric oxide decomposition over Pt and Rh surfaces under lean-burn conditions

    NASA Astrophysics Data System (ADS)

    Mei, Donghai; Ge, Qingfeng; Neurock, Matthew; Kieken, Laurent; Lerou, Jan

    First-principles-based kinetic Monte Carlo simulation was used to track the elementary surface transformations involved in the catalytic decomposition of NO over Pt(100) and Rh(100) surfaces under lean-burn operating conditions. Density functional theory (DFT) calculations were carried out to establish the structure and energetics for all reactants, intermediates and products over Pt(100) and Rh(100). Lateral interactions which arise from neighbouring adsorbates were calculated by examining changes in the binding energies as a function of coverage and different coadsorbed configurations. These data were fitted to a bond order conservation (BOC) model which is subsequently used to establish the effects of coverage within the simulation. The intrinsic activation barriers for all the elementary reaction steps in the proposed mechanism of NO reduction over Pt(100) were calculated by using DFT. These values are corrected for coverage effects by using the parametrized BOC model internally within the simulation. This enables a site-explicit kinetic Monte Carlo simulation that can follow the kinetics of NO decomposition over Pt(100) and Rh(100) in the presence of excess oxygen. The simulations are used here to model various experimental protocols including temperature programmed desorption as well as batch catalytic kinetics. The simulation results for the temperature programmed desorption and decomposition of NO over Pt(100) and Rh(100) under vacuum condition were found to be in very good agreement with experimental results. NO decomposition is strongly tied to the temporal number of sites that remain vacant. Experimental results show that Pt is active in the catalytic reaction of NO into N2 and NO2 under lean-burn conditions. The simulated reaction orders for NO and O2 were found to be +0.9 and -0.4 at 723 K, respectively. The simulation also indicates that there is no activity over Rh(100) since the surface becomes poisoned by oxygen.

  19. Theoretical characterization of stable eta1-N2O-, eta2-N2O-, eta1-N2-, and eta2-N2-bound species: intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion.

    PubMed

    Olabe, José A; Estiú, Guillermina L

    2003-08-11

    The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the eta(1)- and eta(2)-linkage isomers of N(2)O and N(2), depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The eta(2)-N(2)O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the eta(1)-N(2)O isomer is followed by Fe-N(2)O dissociation. Only the eta(1)-N(2)O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N(2)O formation. eta(1)-N(2) and eta(2)-N(2) isomers are also predicted as stable species.

  20. Wood decomposition as influenced by invertebrates

    Treesearch

    Michael D. Ulyshen

    2016-01-01

    The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial...

  1. Regularization of nonlinear decomposition of spectral x-ray projection images.

    PubMed

    Ducros, Nicolas; Abascal, Juan Felipe Perez-Juste; Sixou, Bruno; Rit, Simon; Peyrin, Françoise

    2017-09-01

    Exploiting the x-ray measurements obtained in different energy bins, spectral computed tomography (CT) has the ability to recover the 3-D description of a patient in a material basis. This may be achieved solving two subproblems, namely the material decomposition and the tomographic reconstruction problems. In this work, we address the material decomposition of spectral x-ray projection images, which is a nonlinear ill-posed problem. Our main contribution is to introduce a material-dependent spatial regularization in the projection domain. The decomposition problem is solved iteratively using a Gauss-Newton algorithm that can benefit from fast linear solvers. A Matlab implementation is available online. The proposed regularized weighted least squares Gauss-Newton algorithm (RWLS-GN) is validated on numerical simulations of a thorax phantom made of up to five materials (soft tissue, bone, lung, adipose tissue, and gadolinium), which is scanned with a 120 kV source and imaged by a 4-bin photon counting detector. To evaluate the method performance of our algorithm, different scenarios are created by varying the number of incident photons, the concentration of the marker and the configuration of the phantom. The RWLS-GN method is compared to the reference maximum likelihood Nelder-Mead algorithm (ML-NM). The convergence of the proposed method and its dependence on the regularization parameter are also studied. We show that material decomposition is feasible with the proposed method and that it converges in few iterations. Material decomposition with ML-NM was very sensitive to noise, leading to decomposed images highly affected by noise, and artifacts even for the best case scenario. The proposed method was less sensitive to noise and improved contrast-to-noise ratio of the gadolinium image. Results were superior to those provided by ML-NM in terms of image quality and decomposition was 70 times faster. For the assessed experiments, material decomposition was possible

  2. Lossless and Sufficient - Invariant Decomposition of Deterministic Target

    NASA Astrophysics Data System (ADS)

    Paladini, Riccardo; Ferro Famil, Laurent; Pottier, Eric; Martorella, Marco; Berizzi, Fabrizio

    2011-03-01

    The symmetric radar scattering matrix of a reciprocal target is projected on the circular polarization basis and is decomposed into four orientation invariant parameters, relative phase and relative orientation. The physical interpretation of this results is found in the wave-particle nature of radar scattering due to the circular polarization nature of elemental packets of energy. The proposed decomposition, is based on left orthogonal to left Special Unitary basis, providing the target description in term of a unitary vector. A comparison between the proposed CTD and Cameron, Kennaugh and Krogager decompositions is also pointed out. A validation by the use of both anechoic chamber data and airborne EMISAR data of DTU is used to show the effectiveness of this decomposition for the analysis of coherent targets. In the second paper we will show the application of the rotation group U(3) for the decomposition of distributed targets into nine meaningful parameters.

  3. The Thermal Decomposition of Basic Copper(II) Sulfate.

    ERIC Educational Resources Information Center

    Tanaka, Haruhiko; Koga, Nobuyoshi

    1990-01-01

    Discussed is the preparation of synthetic brochantite from solution and a thermogravimetric-differential thermal analysis study of the thermal decomposition of this compound. Other analyses included are chemical analysis and IR spectroscopy. Experimental procedures and results are presented. (CW)

  4. Probing the Natural World, Level III, Teacher's Edition: Investigating Variation. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit focuses on diversity in human populations, measurement, and data collection. Optional excursions are described for students who wish to study a topic in greater depth. An introduction describes…

  5. Probing the Natural World, Level III, Teacher's Edition: Environmental Science. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit and its activities focuses on environmental pollution and hazards. Optional excursions are suggested for students who wish to study an area in greater depth. An introduction describes the problem…

  6. High temperature decomposition of hydrogen peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2004-01-01

    Nitric oxide (NO) is oxidized into nitrogen dioxide (NO.sub.2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

  7. High temperature decomposition of hydrogen peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2011-01-01

    Nitric oxide (NO) is oxidized into nitrogen dioxide (NO.sub.2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

  8. High temperature decomposition of hydrogen peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2005-01-01

    Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

  9. High Temperature Decomposition of Hydrogen Peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2004-01-01

    Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydropemxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

  10. Comparison of the decomposition VOC profile during winter and summer in a moist, mid-latitude (Cfb) climate.

    PubMed

    Forbes, Shari L; Perrault, Katelynn A; Stefanuto, Pierre-Hugues; Nizio, Katie D; Focant, Jean-François

    2014-01-01

    The investigation of volatile organic compounds (VOCs) associated with decomposition is an emerging field in forensic taphonomy due to their importance in locating human remains using biological detectors such as insects and canines. A consistent decomposition VOC profile has not yet been elucidated due to the intrinsic impact of the environment on the decomposition process in different climatic zones. The study of decomposition VOCs has typically occurred during the warmer months to enable chemical profiling of all decomposition stages. The present study investigated the decomposition VOC profile in air during both warmer and cooler months in a moist, mid-latitude (Cfb) climate as decomposition occurs year-round in this environment. Pig carcasses (Sus scrofa domesticus L.) were placed on a soil surface to decompose naturally and their VOC profile was monitored during the winter and summer months. Corresponding control sites were also monitored to determine the natural VOC profile of the surrounding soil and vegetation. VOC samples were collected onto sorbent tubes and analyzed using comprehensive two-dimensional gas chromatography--time-of-flight mass spectrometry (GC × GC-TOFMS). The summer months were characterized by higher temperatures and solar radiation, greater rainfall accumulation, and comparable humidity when compared to the winter months. The rate of decomposition was faster and the number and abundance of VOCs was proportionally higher in summer. However, a similar trend was observed in winter and summer demonstrating a rapid increase in VOC abundance during active decay with a second increase in abundance occurring later in the decomposition process. Sulfur-containing compounds, alcohols and ketones represented the most abundant classes of compounds in both seasons, although almost all 10 compound classes identified contributed to discriminating the stages of decomposition throughout both seasons. The advantages of GC × GC-TOFMS were demonstrated

  11. First-principles studies of phase stability and crystal structures in Li-Zn mixed-metal borohydrides

    NASA Astrophysics Data System (ADS)

    Wang, Yongli; Zhang, Yongsheng; Wolverton, C.

    2013-07-01

    We address the problem of finding mixed-metal borohydrides with favorable thermodynamics and illustrate the approach using the example of LiZn2(BH4)5. Using density functional theory (DFT), along with the grand-canonical linear programming method (GCLP), we examine the experimentally and computationally proposed crystal structures and the finite-temperature thermodynamics of dehydrogenation for the quaternary hydride LiZn2(BH4)5. We find the following: (i) For LiZn2(BH4)5, DFT calculations of the experimental crystal structures reveal that the structure from the neutron diffraction experiments of Ravnsbæk is more stable [by 24 kJ/(mol f.u.)] than that based on a previous x-ray study. (ii) Our DFT calculations show that when using the neutron-diffraction structure of LiZn2(BH4)5, the recently theoretically predicted LiZn(BH4)3 compound is unstable with respect to the decomposition into LiZn2(BH4)5+LiBH4. (iii) GCLP calculations show that even though LiZn2(BH4)5 is a combination of weakly [Zn(BH4)2] and strongly (LiBH4) bound borohydrides, its decomposition is not intermediate between the two individual borohydrides. Rather, we find that the decomposition of LiZn2(BH4)5 is divided into a weakly exothermic step [LiZn2(BH4)5→2Zn+(1)/(5)LiBH4+(2)/(5)Li2B12H12+(36)/(5)H2] and three strong endothermic steps (12LiBH4→10LiH+Li2B12H12+13H2; Zn+LiH→LiZn+(1)/(2)H2; 2Zn+Li2B12H12→2LiZn+12B+6H2). DFT-calculated ΔHZPET=0K values for the first three LiZn2(BH4)5 decomposition steps are -19, +37, +74 kJ/(mol H2), respectively. The behavior of LiZn2(BH4)5 shows that mixed-metal borohydrides formed by mixing borohydrides of high and low thermodynamics stabilities do not necessarily have an intermediate decomposition tendency. Our results suggest the correct strategy to find intermediate decomposition in mixed-metal borohydrides is to search for stable mixed-metal products such as ternary metal borides.

  12. 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.

  13. Decomposition Behavior of Curcumin during Solar Irradiation when Contact with Inorganic Particles

    NASA Astrophysics Data System (ADS)

    Nandiyanto, A. B. D.; Wiryani, A. S.; Rusli, A.; Purnamasari, A.; Abdullah, A. G.; Riza, L. S.

    2017-03-01

    Curcumin is one of materials which have been widely used in medicine, Asian cuisine, and traditional cosmetic. Therefore, understanding the stability of curcumin has been widely studied. The purpose of this study was to investigate the stability of curcumin solution against solar irradiation when making contact with inorganic material. As a model for the inorganic material, titanium dioxide (TiO2) was used. In the experimental method, the curcumin solution was irradiated using a solar irradiation. To confirm the stability of curcumin when contact with inorganic material, we added TiO2 micro particles with different concentrations. The results showed that the concentration of curcumin decreased during solar irradiation. The less concentration of curcumin affected the more decomposition rate obtained. The decomposition rate was increased greatly when TiO2 was added, in which the more TiO2 concentration added allowed the faster decomposition rate. Based on the result, we conclude that the curcumin is relatively stable as long as using higher concentration of curcumin and is no inorganic material existed. Then, the decomposition can be minimized by avoiding contact with inorganic material.

  14. Cigarette Butt Decomposition and Associated Chemical Changes Assessed by 13C CPMAS NMR

    PubMed Central

    Bonanomi, Giuliano; Incerti, Guido; Cesarano, Gaspare; Gaglione, Salvatore A.; Lanzotti, Virginia

    2015-01-01

    Cigarette butts (CBs) are the most common type of litter on earth, with an estimated 4.5 trillion discarded annually. Apart from being unsightly, CBs pose a serious threat to living organisms and ecosystem health when discarded in the environment because they are toxic to microbes, insects, fish and mammals. In spite of the CB toxic hazard, no studies have addressed the effects of environmental conditions on CB decomposition rate. In this study we investigate the interactive effects of substrate fertility and N transfer dynamics on CB decomposition rate and carbon quality changes. We carried out an experiment using smoked CBs and wood sticks, used as a slow decomposing standard organic substrate, incubated in both laboratory and field conditions for two years. CB carbon quality changes during decomposition was assessed by 13C CPMAS NMR. Our experiment confirmed the low degradation rate of CBs which, on average, lost only 37.8% of their initial mass after two years of decomposition. Although a net N transfer occurred from soil to CBs, contrary to our hypothesis, mass loss in the medium-term (two years) was unaffected by N availability in the surrounding substrate. The opposite held for wood sticks, in agreement with the model that N-rich substrates promote the decomposition of other N-poor natural organic materials with a high C/N ratio. As regards CB chemical quality, after two years of decomposition 13C NMR spectroscopy highlighted very small changes in C quality that are likely to reflect a limited microbial attack. PMID:25625643

  15. Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

    NASA Astrophysics Data System (ADS)

    Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

    2013-02-01

    Results are presented from experimental studies of decomposition of toluene (C6H5CH3) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C6H5CH3 removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N2: O2: H2O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C6H5CH3 decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C6H5CH3 is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

  16. MHD oxidant intermediate temperature ceramic heater study

    NASA Technical Reports Server (NTRS)

    Carlson, A. W.; Chait, I. L.; Saari, D. P.; Marksberry, C. L.

    1981-01-01

    The use of three types of directly fired ceramic heaters for preheating oxygen enriched air to an intermediate temperature of 1144K was investigated. The three types of ceramic heaters are: (1) a fixed bed, periodic flow ceramic brick regenerative heater; (2) a ceramic pebble regenerative heater. The heater design, performance and operating characteristics under conditions in which the particulate matter is not solidified are evaluated. A comparison and overall evaluation of the three types of ceramic heaters and temperature range determination at which the particulate matter in the MHD exhaust gas is estimated to be a dry powder are presented.

  17. Land-use legacies regulate decomposition dynamics following bioenergy crop conversion

    DOE PAGES

    Kallenbach, Cynthia M.; Stuart Grandy, A.

    2014-07-14

    Land-use conversion into bioenergy crop production can alter litter decomposition processes tightly coupled to soil carbon and nutrient dynamics. Yet, litter decomposition has been poorly described in bioenergy production systems, especially following land-use conversion. Predicting decomposition dynamics in postconversion bioenergy production systems is challenging because of the combined influence of land-use legacies with current management and litter quality. To evaluate how land-use legacies interact with current bioenergy crop management to influence litter decomposition in different litter types, we conducted a landscape-scale litterbag decomposition experiment. We proposed land-use legacies regulate decomposition, but their effects are weakened under higher quality litter andmore » when current land use intensifies ecosystem disturbance relative to prior land use. We compared sites left in historical land uses of either agriculture (AG) or Conservation Reserve Program grassland (CRP) to those that were converted to corn or switchgrass bioenergy crop production. Enzyme activities, mass loss, microbial biomass, and changes in litter chemistry were monitored in corn stover and switchgrass litter over 485 days, accompanied by similar soil measurements. Across all measured variables, legacy had the strongest effect (P < 0.05) relative to litter type and current management, where CRP sites maintained higher soil and litter enzyme activities and microbial biomass relative to AG sites. Decomposition responses to conversion depended on legacy but also current management and litter type. Within the CRP sites, conversion into corn increased litter enzymes, microbial biomass, and litter protein and lipid abundances, especially on decomposing corn litter, relative to nonconverted CRP. However, conversion into switchgrass from CRP, a moderate disturbance, often had no effect on switchgrass litter decomposition parameters. Thus, legacies shape the direction and

  18. Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

    NASA Astrophysics Data System (ADS)

    Zhu, Yan-Li; Huang, Hao; Ren, Hui; Jiao, Qing-Jie

    2014-01-01

    The method of thermogravimetry/differential scanning calorimetry-mass spectrometry-Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N2O and NO2 were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N2O and that of NO2 during the process with an iso-concentration point of N2O and NO2. The dependence of the activation energy calculated by Friedman's iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.

  19. Randomized interpolative decomposition of separated representations

    NASA Astrophysics Data System (ADS)

    Biagioni, David J.; Beylkin, Daniel; Beylkin, Gregory

    2015-01-01

    We introduce an algorithm to compute tensor interpolative decomposition (dubbed CTD-ID) for the reduction of the separation rank of Canonical Tensor Decompositions (CTDs). Tensor ID selects, for a user-defined accuracy ɛ, a near optimal subset of terms of a CTD to represent the remaining terms via a linear combination of the selected terms. CTD-ID can be used as an alternative to or in combination with the Alternating Least Squares (ALS) algorithm. We present examples of its use within a convergent iteration to compute inverse operators in high dimensions. We also briefly discuss the spectral norm as a computational alternative to the Frobenius norm in estimating approximation errors of tensor ID. We reduce the problem of finding tensor IDs to that of constructing interpolative decompositions of certain matrices. These matrices are generated via randomized projection of the terms of the given tensor. We provide cost estimates and several examples of the new approach to the reduction of separation rank.

  20. Hydroxyacetone production from C 3 Criegee intermediates

    DOE PAGES

    Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon; ...

    2016-12-21

    Hydroxyacetone (CH 3C(O)CH 2OH) is observed as a stable end product from reactions of the (CH 3) 2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerizationmore » via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.« less

  1. How does low temperature coupled with different pressures affect initiation mechanisms and subsequent decompositions in nitramine explosive HMX?

    PubMed

    Wu, Qiong; Xiong, Guolin; Zhu, Weihua; Xiao, Heming

    2015-09-21

    We have performed ab initio molecular dynamics simulations to study coupling effects of temperature (534-873 K) and pressure (1-20 GPa) on the initiation mechanisms and subsequent chemical decompositions of nitramine explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). A new initiation decomposition mechanism of HMX was found to be the unimolecular C-H bond breaking, and this mechanism was independent of the coupling effects of different temperatures and pressures. The formed hydrogen radicals could promote subsequent decompositions of HMX. Subsequent decompositions were very sensitive to the pressure at low temperatures (534 and 608 K), while the temperature became the foremost factor that affected the decomposition at a high temperature (873 K) instead of the pressure. Our study may provide a new insight into understanding the coupling effects of the temperature and pressure on the initiation decomposition mechanisms of nitramine explosives.

  2. Plants Regulate Soil Organic Matter Decomposition in Response to Sea Level Rise

    NASA Astrophysics Data System (ADS)

    Megonigal, P.; Mueller, P.; Jensen, K.

    2014-12-01

    Tidal wetlands have a large capacity for producing and storing organic matter, making their role in the global carbon budget disproportionate to their land area. Most of the organic matter stored in these systems is in soils where it contributes 2-5 times more to surface accretion than an equal mass of minerals. Soil organic matter (SOM) sequestration is the primary process by which tidal wetlands become perched high in the tidal frame, decreasing their vulnerability to accelerated sea level rise. Plant growth responses to sea level rise are well understood and represented in century-scale forecast models of soil surface elevation change. We understand far less about the response of soil organic matter decomposition to rapid sea level rise. Here we quantified the effects of sea level on SOM decomposition rates by exposing planted and unplanted tidal marsh monoliths to experimentally manipulated flood duration. The study was performed in a field-based mesocosm facility at the Smithsonian's Global Change Research Wetland. SOM decomposition rate was quantified as CO2 efflux, with plant- and SOM-derived CO2 separated with a two end-member δ13C-CO2 model. Despite the dogma that decomposition rates are inversely related to flooding, SOM mineralization was not sensitive to flood duration over a 35 cm range in soil surface elevation. However, decomposition rates were strongly and positively related to aboveground biomass (R2≥0.59, p≤0.01). We conclude that soil carbon loss through decomposition is driven by plant responses to sea level in this intensively studied tidal marsh. If this result applies more generally to tidal wetlands, it has important implications for modeling soil organic matter and surface elevation change in response to accelerated sea level rise.

  3. Primary decomposition of zero-dimensional ideals over finite fields

    NASA Astrophysics Data System (ADS)

    Gao, Shuhong; Wan, Daqing; Wang, Mingsheng

    2009-03-01

    A new algorithm is presented for computing primary decomposition of zero-dimensional ideals over finite fields. Like Berlekamp's algorithm for univariate polynomials, the new method is based on the invariant subspace of the Frobenius map acting on the quotient algebra. The dimension of the invariant subspace equals the number of primary components, and a basis of the invariant subspace yields a complete decomposition. Unlike previous approaches for decomposing multivariate polynomial systems, the new method does not need primality testing nor any generic projection, instead it reduces the general decomposition problem directly to root finding of univariate polynomials over the ground field. Also, it is shown how Groebner basis structure can be used to get partial primary decomposition without any root finding.

  4. Cyberbullying in a Rural Intermediate School: An Exploratory Study

    ERIC Educational Resources Information Center

    Bauman, Sheri

    2010-01-01

    Students (N = 221) in an intermediate school (grades 5-8) in a rural area of the Southwestern United States completed a survey regarding their familiarity with technology and their experiences with cyberbullying during the school year. Initial evidence of survey reliability is presented. In the sample, 1.5% of participants were classified as…

  5. Probing the Natural World, Level III, Teacher's Edition: Well-Being. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit focuses on hazards to the body from drug use. Activities are given that relate to the topic. Optional excursions are suggested for students who wish to study an area in greater depth. An…

  6. A New Domain Decomposition Approach for the Gust Response Problem

    NASA Technical Reports Server (NTRS)

    Scott, James R.; Atassi, Hafiz M.; Susan-Resiga, Romeo F.

    2002-01-01

    A domain decomposition method is developed for solving the aerodynamic/aeroacoustic problem of an airfoil in a vortical gust. The computational domain is divided into inner and outer regions wherein the governing equations are cast in different forms suitable for accurate computations in each region. Boundary conditions which ensure continuity of pressure and velocity are imposed along the interface separating the two regions. A numerical study is presented for reduced frequencies ranging from 0.1 to 3.0. It is seen that the domain decomposition approach in providing robust and grid independent solutions.

  7. Effect of petroleum on decomposition of shrub-grass litters in soil in Northern Shaanxi of China.

    PubMed

    Zhang, Xiaoxi; Liu, Zengwen; Yu, Qi; Luc, Nhu Trung; Bing, Yuanhao; Zhu, Bochao; Wang, Wenxuan

    2015-07-01

    The impacts of petroleum contamination on the litter decomposition of shrub-grass land would directly influence nutrient cycling, and the stability and function of ecosystem. Ten common shrub and grass species from Yujiaping oil deposits were studied. Litters from these species were placed into litterbags and buried in petroleum-contaminated soil with 3 levels of contamination (slight, moderate and serious pollution with petroleum concentrations of 15, 30 and 45 g/kg, respectively). A decomposition experiment was then conducted in the lab to investigate the impacts of petroleum contamination on litter decomposition rates. Slight pollution did not inhibit the decomposition of any litters and significantly promoted the litter decomposition of Hippophae rhamnoides, Caragana korshinskii, Amorpha fruticosa, Ziziphus jujuba var. spinosa, Periploca sepium, Medicago sativa and Bothriochloa ischaemum. Moderate pollution significantly inhibited litter decomposition of M. sativa, Coronilla varia, Artemisia vestita and Trrifolium repens and significantly promoted the litter decomposition of C. korshinskii, Z. jujuba var. spinosa and P. sepium. Serious pollution significantly inhibited the litter decomposition of H. rhamnoides, A. fruticosa, B. ischaemum and A. vestita and significantly promoted the litter decomposition of Z. jujuba var. spinosa, P. sepium and M. sativa. In addition, the impacts of petroleum contamination did not exhibit a uniform increase or decrease as petroleum concentration increased. Inhibitory effects of petroleum on litter decomposition may hinder the substance cycling and result in the degradation of plant communities in contaminated areas. Copyright © 2015. Published by Elsevier B.V.

  8. Breast tissue decomposition with spectral distortion correction: A postmortem study

    PubMed Central

    Ding, Huanjun; Zhao, Bo; Baturin, Pavlo; Behroozi, Farnaz; Molloi, Sabee

    2014-01-01

    Purpose: To investigate the feasibility of an accurate measurement of water, lipid, and protein composition of breast tissue using a photon-counting spectral computed tomography (CT) with spectral distortion corrections. Methods: Thirty-eight postmortem breasts were imaged with a cadmium-zinc-telluride-based photon-counting spectral CT system at 100 kV. The energy-resolving capability of the photon-counting detector was used to separate photons into low and high energy bins with a splitting energy of 42 keV. The estimated mean glandular dose for each breast ranged from 1.8 to 2.2 mGy. Two spectral distortion correction techniques were implemented, respectively, on the raw images to correct the nonlinear detector response due to pulse pileup and charge-sharing artifacts. Dual energy decomposition was then used to characterize each breast in terms of water, lipid, and protein content. In the meantime, the breasts were chemically decomposed into their respective water, lipid, and protein components to provide a gold standard for comparison with dual energy decomposition results. Results: The accuracy of the tissue compositional measurement with spectral CT was determined by comparing to the reference standard from chemical analysis. The averaged root-mean-square error in percentage composition was reduced from 15.5% to 2.8% after spectral distortion corrections. Conclusions: The results indicate that spectral CT can be used to quantify the water, lipid, and protein content in breast tissue. The accuracy of the compositional analysis depends on the applied spectral distortion correction technique. PMID:25281953

  9. Critical and Reflective Thinking in an Intermediate Financial Accounting Course: An Action Research Study

    ERIC Educational Resources Information Center

    Cobb, Janice Lynn

    2017-01-01

    Accounting professionals have consistently called for educators to develop curriculum designed to encourage students to develop intellectual skills. The purpose of this action research study was to develop and implement an instructional method that requires intermediate financial accounting (IFA) students to consistently practice higher order…

  10. A comparison between decomposition rates of buried and surface remains in a temperate region of South Africa.

    PubMed

    Marais-Werner, Anátulie; Myburgh, J; Becker, P J; Steyn, M

    2018-01-01

    Several studies have been conducted on decomposition patterns and rates of surface remains; however, much less are known about this process for buried remains. Understanding the process of decomposition in buried remains is extremely important and aids in criminal investigations, especially when attempting to estimate the post mortem interval (PMI). The aim of this study was to compare the rates of decomposition between buried and surface remains. For this purpose, 25 pigs (Sus scrofa; 45-80 kg) were buried and excavated at different post mortem intervals (7, 14, 33, 92, and 183 days). The observed total body scores were then compared to those of surface remains decomposing at the same location. Stages of decomposition were scored according to separate categories for different anatomical regions based on standardised methods. Variation in the degree of decomposition was considerable especially with the buried 7-day interval pigs that displayed different degrees of discolouration in the lower abdomen and trunk. At 14 and 33 days, buried pigs displayed features commonly associated with the early stages of decomposition, but with less variation. A state of advanced decomposition was reached where little change was observed in the next ±90-183 days after interment. Although the patterns of decomposition for buried and surface remains were very similar, the rates differed considerably. Based on the observations made in this study, guidelines for the estimation of PMI are proposed. This pertains to buried remains found at a depth of approximately 0.75 m in the Central Highveld of South Africa.

  11. Climate and litter quality differently modulate the effects of soil fauna on litter decomposition across biomes

    PubMed Central

    García-Palacios, Pablo; Maestre, Fernando T.; Kattge, Jens; Wall, Diana H.

    2015-01-01

    Climate and litter quality have been identified as major drivers of litter decomposition at large spatial scales. However, the role played by soil fauna remains largely unknown, despite its importance for litter fragmentation and microbial activity. We synthesized litterbag studies to quantify the effect sizes of soil fauna on litter decomposition rates at the global and biome scales, and to assess how climate, litter quality and soil fauna interact to determine such rates. Soil fauna consistently enhanced litter decomposition at both global and biome scales (average increment ~27%). However, climate and litter quality differently modulated the effects of soil fauna on decomposition rates between biomes, from climate-driven biomes to those where climate effects were mediated by changes in litter quality. Our results advocate for the inclusion of biome-specific soil fauna effects on litter decomposition as a mean to reduce the unexplained variation in large-scale decomposition models. PMID:23763716

  12. Remission of Intermediate Uveitis: Incidence and Predictive Factors.

    PubMed

    Kempen, John H; Gewaily, Dina Y; Newcomb, Craig W; Liesegang, Teresa L; Kaçmaz, R Oktay; Levy-Clarke, Grace A; Nussenblatt, Robert B; Rosenbaum, James T; Sen, H Nida; Suhler, Eric B; Thorne, Jennifer E; Foster, C Stephen; Jabs, Douglas A; Payal, Abhishek; Fitzgerald, Tonetta D

    2016-04-01

    To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Retrospective cohort study. Involved eyes of patients with primary noninfectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval [CI], 7.4-10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (hazard ratio [HR] [vs no PPV] = 2.39; 95% CI, 1.42-4.00), diagnosis of intermediate uveitis within the last year (HR [vs diagnosis >5 years ago] =3.82; 95% CI, 1.91-7.63), age ≥45 years (HR [vs age <45 years] = 1.79; 95% CI, 1.03-3.11), female sex (HR = 1.61; 95% CI, 1.04-2.49), and Hispanic race/ethnicity (HR [vs white race] = 2.81; 95% CI, 1.23-6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed patients and older, female, and Hispanic patients were more likely to remit. With regard to management, pars plana vitrectomy was associated with increased probability of remission. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Remission of Intermediate Uveitis: Incidence and Predictive Factors

    PubMed Central

    Kempen, John H.; Gewaily, Dina Y.; Newcomb, Craig W.; Liesegang, Teresa L.; Kaçmaz, R. Oktay; Levy-Clarke, Grace A.; Nussenblatt, Robert B.; Rosenbaum, James T.; Sen, H. Nida; Suhler, Eric B.; Thorne, Jennifer E.; Foster, C. Stephen; Jabs, Douglas A.; Payal, Abhishek; Fitzgerald, Tonetta D.

    2016-01-01

    Purpose To evaluate the incidence of remission among patients with intermediate uveitis; to identify factors potentially predictive of remission. Design Retrospective cohort study. Methods Involved eyes of patients with primary non-infectious intermediate uveitis at 4 academic ocular inflammation subspecialty practices, followed sufficiently long to meet the remission outcome definition, were studied retrospectively by standardized chart review data. Remission of intermediate uveitis was defined as a lack of inflammatory activity at ≥2 visits spanning ≥90 days in the absence of any corticosteroid or immunosuppressant medications. Factors potentially predictive of intermediate uveitis remission were evaluated using survival analysis. Results Among 849 eyes (of 510 patients) with intermediate uveitis followed over 1,934 eye-years, the incidence of intermediate uveitis remission was 8.6/100 eye-years (95% confidence interval (CI), 7.4–10.1). Factors predictive of disease remission included prior pars plana vitrectomy (PPV) (HR (vs. no PPV)=2.39; 95% CI, 1.42–4.00), diagnosis of intermediate uveitis within the last year (vs. diagnosis >5 years ago)=3.82; 95% CI, 1.91–7.63), age ≥45 years (HR (vs. age <45 years)=1.79; 95% CI, 1.03–3.11), female sex (HR=1.61; 95% CI, 1.04–2.49), and Hispanic race/ethnicity (HR (vs. white race)=2.81; 95% CI, 1.23–6.41). Presence/absence of a systemic inflammatory disease, laterality of uveitis, and smoking status were not associated with differential incidence. Conclusions Our results suggest that intermediate uveitis is a chronic disease with an overall low rate of remission. Recently diagnosed cases, and older, female and Hispanic cases were more likely to remit. With regards to management, pars plana vitrectomy was associated with increased probability of remission. PMID:26772874

  14. Nucleation via an unstable intermediate phase.

    PubMed

    Sear, Richard P

    2009-08-21

    The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

  15. Adsorption Behavior, Thermodynamics, and Kinetics of the Methanol Decomposition Reaction on defective graphene-supported Pt13

    NASA Astrophysics Data System (ADS)

    Gasper, Raymond; Ramasubramaniam, Ashwin

    Defective graphene has been shown experimentally to be an excellent support for transition-metal electrocatalysts in direct methanol fuel cells. Prior computational modeling has shown that the improved catalytic activity of graphene-supported metal clusters is in part due to increased resistance to catalyst sintering and CO poisoning, but the increased reaction rate for the methanol decomposition reaction (MDR) is not yet fully explained. Using DFT, we investigate the adsorption of MDR intermediates and reaction thermodynamics on defective graphene-supported Pt13 nanoclusters with realistic, low-symmetry morphologies. We find that the support-induced shifts in Pt13 electronic structure correlate well with a rigid shift in adsorption of MDR intermediates, and that adsorption energy scaling relationships perform well on the low-symmetry surface. We investigate the reaction kinetics and thermodynamics, including testing the effectiveness of scaling relationships for predicting reaction barriers on the nanoclusters. Using these fundamental data, we perform microkinetic modeling to quantify the effect of the support on the MDR, and to understand how the support influences surface coverages, CO poisoning, and the relationships between reaction pathways. Funded by U.S. Department of Energy under Award Number DE-SC0010610. Computational resources were provided by National Energy Research Scientific Computing Center.

  16. 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.

  17. Criegee intermediates in the indoor environment. New insights

    DOE PAGES

    Shallcross, D. E.; Taatjes, C. A.; Percival, C. J.

    2014-03-25

    Criegee intermediates are formed in the ozonolysis of alkenes and play an important role in indoor chemistry, notably as a source of OH radicals. Recent studies have shown that these Criegee intermediates react very quickly with NO 2, SO 2, and carbonyls, and in this study, steady-state calculations are used to inspect the potential impact of these data on indoor chemistry. It is shown that these reactions could accelerate NO 3 formation and SO 2 removal in the indoor environment significantly. In addition, reaction between Criegee intermediates and halogenated carbonyls could provide a significant loss process indoors, where currently onemore » does not exist.« less

  18. Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

    NASA Astrophysics Data System (ADS)

    Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

    2017-06-01

    The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

  19. A structural model decomposition framework for systems health management

    NASA Astrophysics Data System (ADS)

    Roychoudhury, I.; Daigle, M.; Bregon, A.; Pulido, B.

    Systems health management (SHM) is an important set of technologies aimed at increasing system safety and reliability by detecting, isolating, and identifying faults; and predicting when the system reaches end of life (EOL), so that appropriate fault mitigation and recovery actions can be taken. Model-based SHM approaches typically make use of global, monolithic system models for online analysis, which results in a loss of scalability and efficiency for large-scale systems. Improvement in scalability and efficiency can be achieved by decomposing the system model into smaller local submodels and operating on these submodels instead. In this paper, the global system model is analyzed offline and structurally decomposed into local submodels. We define a common model decomposition framework for extracting submodels from the global model. This framework is then used to develop algorithms for solving model decomposition problems for the design of three separate SHM technologies, namely, estimation (which is useful for fault detection and identification), fault isolation, and EOL prediction. We solve these model decomposition problems using a three-tank system as a case study.

  20. A Structural Model Decomposition Framework for Systems Health Management

    NASA Technical Reports Server (NTRS)

    Roychoudhury, Indranil; Daigle, Matthew J.; Bregon, Anibal; Pulido, Belamino

    2013-01-01

    Systems health management (SHM) is an important set of technologies aimed at increasing system safety and reliability by detecting, isolating, and identifying faults; and predicting when the system reaches end of life (EOL), so that appropriate fault mitigation and recovery actions can be taken. Model-based SHM approaches typically make use of global, monolithic system models for online analysis, which results in a loss of scalability and efficiency for large-scale systems. Improvement in scalability and efficiency can be achieved by decomposing the system model into smaller local submodels and operating on these submodels instead. In this paper, the global system model is analyzed offline and structurally decomposed into local submodels. We define a common model decomposition framework for extracting submodels from the global model. This framework is then used to develop algorithms for solving model decomposition problems for the design of three separate SHM technologies, namely, estimation (which is useful for fault detection and identification), fault isolation, and EOL prediction. We solve these model decomposition problems using a three-tank system as a case study.

  1. Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

    NASA Astrophysics Data System (ADS)

    Melhado, William Francis; Whitman, Jared Connor; Kong, Jessica; Anderson, Daniel Easton; Vasiliou, AnGayle (AJ)

    2016-06-01

    Combustion of organosulfur contaminants in petroleum-based fuels and biofuels produces sulfur oxides (SO_x). These pollutants are highly regulated by the EPA because they have been linked to poor respiratory health and negative environmental impacts. Therefore much effort has been made to remove sulfur compounds in petroleum-based fuels and biofuels. Currently desulfurization methods used in the fuel industry are costly and inefficient. Research of the thermal decomposition mechanisms of organosulfur species can be implemented via engineering simulations to modify existing refining technologies to design more efficient sulfur removal processes. We have used a resistively-heated SiC tubular reactor to study the thermal decomposition of ethanethiol (CH_3CH_2SH) and dimethylsulfide (CH_3SCH_3). The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. The thermal cracking products for CH_3CH_2SH are CH_2CH_2, SH, and H_2S and the thermal cracking products from CH_3SCH_3 are CH_3S, CH_2S, and CH_3.

  2. Comparative study of the dynamics of lipid membrane phase decomposition in experiment and simulation.

    PubMed

    Burger, Stefan; Fraunholz, Thomas; Leirer, Christian; Hoppe, Ronald H W; Wixforth, Achim; Peter, Malte A; Franke, Thomas

    2013-06-25

    Phase decomposition in lipid membranes has been the subject of numerous investigations by both experiment and theoretical simulation, yet quantitative comparisons of the simulated data to the experimental results are rare. In this work, we present a novel way of comparing the temporal development of liquid-ordered domains obtained from numerically solving the Cahn-Hilliard equation and by inducing a phase transition in giant unilamellar vesicles (GUVs). Quantitative comparison is done by calculating the structure factor of the domain pattern. It turns out that the decomposition takes place in three distinct regimes in both experiment and simulation. These regimes are characterized by different rates of growth of the mean domain diameter, and there is quantitative agreement between experiment and simulation as to the duration of each regime and the absolute rate of growth in each regime.

  3. Transect studies on pine litter organic matter: decomposition and chemical properties of upper soil layers in Polish forests

    Treesearch

    Alicja Breymeyer; Marek Degorski; David Reed

    1998-01-01

    The relationship between litter decomposition rate, some chemical properties of upper soil layers (iron, manganese, zinc, copper, lead, mercury, nickel, chrome in humus-mineral horizon-A), and litter (the same eight elements in needle litter fraction) in pine forests of Poland was studied. Heavy metal content in organic-mineral horizon of soils was highly correlated...

  4. Long-term experiments on log decomposition at the H.J. Andrews Experimental Forest.

    Treesearch

    M.E. Harmon

    1992-01-01

    A long-term decomposition experiment was established at the H.J. Andrews Experimental Forest, Oregon, during 1985to test the importance of substrate heterogeneity, colonization patterns, and invertebrates on the decomposition of logs. The duration of the study is anticipated to be 200 years. A total of 530 logs (50 centimeters in diameter and 5.5 meters long) were...

  5. Bond Order Conservation Strategies in Catalysis Applied to the NH 3 Decomposition Reaction

    DOE PAGES

    Yu, Liang; Abild-Pedersen, Frank

    2016-12-14

    On the basis of an extensive set of density functional theory calculations, it is shown that a simple scheme provides a fundamental understanding of variations in the transition state energies and structures of reaction intermediates on transition metal surfaces across the periodic table. The scheme is built on the bond order conservation principle and requires a limited set of input data, still achieving transition state energies as a function of simple descriptors with an error smaller than those of approaches based on linear fits to a set of calculated transition state energies. Here, we have applied this approach together withmore » linear scaling of adsorption energies to obtain the energetics of the NH 3 decomposition reaction on a series of stepped fcc(211) transition metal surfaces. Moreover, this information is used to establish a microkinetic model for the formation of N 2 and H 2, thus providing insight into the components of the reaction that determines the activity.« less

  6. TENSOR DECOMPOSITIONS AND SPARSE LOG-LINEAR MODELS

    PubMed Central

    Johndrow, James E.; Bhattacharya, Anirban; Dunson, David B.

    2017-01-01

    Contingency table analysis routinely relies on log-linear models, with latent structure analysis providing a common alternative. Latent structure models lead to a reduced rank tensor factorization of the probability mass function for multivariate categorical data, while log-linear models achieve dimensionality reduction through sparsity. Little is known about the relationship between these notions of dimensionality reduction in the two paradigms. We derive several results relating the support of a log-linear model to nonnegative ranks of the associated probability tensor. Motivated by these findings, we propose a new collapsed Tucker class of tensor decompositions, which bridge existing PARAFAC and Tucker decompositions, providing a more flexible framework for parsimoniously characterizing multivariate categorical data. Taking a Bayesian approach to inference, we illustrate empirical advantages of the new decompositions. PMID:29332971

  7. 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.

  8. 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.

  9. Bright Compact Bulges (BCBs) at intermediate redshifts

    NASA Astrophysics Data System (ADS)

    Sachdeva, Sonali; Saha, Kanak

    2018-04-01

    Studying bright (MB < -20), intermediate-redshift (0.4 < z < 1.0), disc dominated (nB < 2.5) galaxies from HST/ACS and WFC3 in Chandra Deep Field South, in rest-frame B and I-band, we found a new class of bulges which is brighter and more compact than ellipticals. We refer to them as "Bright, Compact Bulges" (BCBs) - they resemble neither classical nor pseudo-bulges and constitute ˜12% of the total bulge population at these redshifts. Examining free-bulge + disc decomposition sample and elliptical galaxy sample from Simard et al. (2011), we find that only ˜0.2% of the bulges can be classified as BCBs in the local Universe. Bulge to total ratio (B/T) of disc galaxies with BCBs is (at ˜0.4) a factor of ˜2 and ˜4 larger than for those with classical and pseudo bulges. BCBs are ˜2.5 and ˜6 times more massive than classical and pseudo bulges. Although disc galaxies with BCBs host the most massive and dominant bulge type, their specific star formation rate is 1.5-2 times higher than other disc galaxies. This is contrary to the expectations that a massive compact bulge would lead to lower star formation rates. We speculate that our BCB host disc galaxies are descendant of massive, compact and passive elliptical galaxies observed at higher redshifts. Those high redshift ellipticals lack local counterparts and possibly evolved by acquiring a compact disc around them. The overall properties of BCBs supports a picture of galaxy assembly in which younger discs are being accreted around massive pre-existing spheroids.

  10. Effect of Isomorphous Substitution on the Thermal Decomposition Mechanism of Hydrotalcites

    PubMed Central

    Crosby, Sergio; Tran, Doanh; Cocke, David; Duraia, El-Shazly M.; Beall, Gary W.

    2014-01-01

    Hydrotalcites have many important applications in catalysis, wastewater treatment, gene delivery and polymer stabilization, all depending on preparation history and treatment scenarios. In catalysis and polymer stabilization, thermal decomposition is of great importance. Hydrotalcites form easily with atmospheric carbon dioxide and often interfere with the study of other anion containing systems, particularly if formed at room temperature. The dehydroxylation and decomposition of carbonate occurs simultaneously, making it difficult to distinguish the dehydroxylation mechanisms directly. To date, the majority of work on understanding the decomposition mechanism has utilized hydrotalcite precipitated at room temperature. In this study, evolved gas analysis combined with thermal analysis has been used to show that CO2 contamination is problematic in materials being formed at RT that are poorly crystalline. This has led to some dispute as to the nature of the dehydroxylation mechanism. In this paper, data for the thermal decomposition of the chloride form of hydrotalcite are reported. In addition, carbonate-free hydrotalcites have been synthesized with different charge densities and at different growth temperatures. This combination of parameters has allowed a better understanding of the mechanism of dehydroxylation and the role that isomorphous substitution plays in these mechanisms to be delineated. In addition, the effect of anion type on thermal stability is also reported. A stepwise dehydroxylation model is proposed that is mediated by the level of aluminum substitution. PMID:28788231

  11. A contribution to the knowledge of HMX decomposition and application of results. [at atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Kraeutle, K. J.

    1980-01-01

    The decomposition of cyclotramethylenetetranitramine (HMX) in the solid and liquid phase was studied by isothermal and nonisothermal heating at atmospheric pressure. Decomposition rates of solid HMX changed with sample size and gaseous environment. Kinetic parameters were obtained from weight loss measurements in the temperature range 229 C - 269 C. These tests also yielded highly porous solid residues. Qualitative aspects of solid and liquid phase decomposition of HMX with additives were also investigated in isothermal and nonisothermal tests.

  12. Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones

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

    Jalan, Amrit; Allen, Joshua W.; Green, William H.

    Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkylmore » esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.« less

  13. Legume presence reduces the decomposition rate of non-legume roots, role of plant traits?

    NASA Astrophysics Data System (ADS)

    De Deyn, Gerlinde B.; Saar, Sirgi; Barel, Janna; Semchenko, Marina

    2016-04-01

    Plant litter traits are known to play an important role in the rate of litter decomposition and mineralization, both for aboveground and belowground litter. However also the biotic and abiotic environment in which the litter decomposes plays a significant role in the rate of decomposition. The presence of living plants may accelerate litter decomposition rates via a priming effects. The size of this effect is expected to be related to the traits of the litter. In this study we focus on root litter, given that roots and their link to ecosystem processes have received relatively little attention in trait-based research. To test the effect of a growing legume plant on root decomposition and the role of root traits in this we used dead roots of 7 different grassland species (comprising grasses, a forb and legumes), determined their C, N, P content and quantified litter mass loss after eight weeks of incubation in soil with and without white clover. We expected faster root decomposition with white clover, especially for root litter with low N content. In contrast we found slower decomposition of grass and forb roots which were poor in N (negative priming) in presence of white clover, while decomposition rates of legume roots were not affected by the presence of white clover. Overall we found that root decomposition can be slowed down in the presence of a living plant and that this effect depends on the traits of the decomposing roots, with a pronounced reduction in root litter poor in N and P, but not in the relatively nutrient-rich legume root litters. The negative priming effect of legume plants on non-legume litter decomposition may have resulted from preferential substrate utilisation by soil microbes.

  14. Thermal decomposition of high-nitrogen energetic compounds: TAGzT and GUzT

    NASA Astrophysics Data System (ADS)

    Hayden, Heather F.

    The U.S. Navy is exploring high-nitrogen compounds as burning-rate additives to meet the growing demands of future high-performance gun systems. Two high-nitrogen compounds investigated as potential burning-rate additives are bis(triaminoguanidinium) 5,5-azobitetrazolate (TAGzT) and bis(guanidinium) 5,5'-azobitetrazolate (GUzT). Small-scale tests showed that formulations containing TAGzT exhibit significant increases in the burning rates of RDX-based gun propellants. However, when GUzT, a similarly structured molecule was incorporated into the formulation, there was essentially no effect on the burning rate of the propellant. Through the use of simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and Fourier-Transform ion cyclotron resonance (FTICR) mass spectrometry methods, an investigation of the underlying chemical and physical processes that control the thermal decomposition behavior of TAGzT and GUzT alone and in the presence of RDX, was conducted. The objective was to determine why GUzT is not as good a burning-rate enhancer in RDX-based gun propellants as compared to TAGzT. The results show that TAGzT is an effective burning-rate modifier in the presence of RDX because the decomposition of TAGzT alters the initial stages of the decomposition of RDX. Hydrazine, formed in the decomposition of TAGzT, reacts faster with RDX than RDX can decompose itself. The reactions occur at temperatures below the melting point of RDX and thus the TAGzT decomposition products react with RDX in the gas phase. Although there is no hydrazine formed in the decomposition of GUzT, amines formed in the decomposition of GUzT react with aldehydes, formed in the decomposition of RDX, resulting in an increased reaction rate of RDX in the presence of GUzT. However, GUzT is not an effective burning-rate modifier because its decomposition does not alter the initial gas-phase decomposition of RDX. The decomposition of GUzT occurs at temperatures above the melting point

  15. Review on Thermal Decomposition of Ammonium Nitrate

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Shalini; Dave, Pragnesh N.

    2013-01-01

    In this review data from the literature on thermal decomposition of ammonium nitrate (AN) and the effect of additives to their thermal decomposition are summarized. The effect of additives like oxides, cations, inorganic acids, organic compounds, phase-stablized CuO, etc., is discussed. The effect of an additive mainly occurs at the exothermic peak of pure AN in a temperature range of 200°C to 140°C.

  16. Climate and litter quality differently modulate the effects of soil fauna on litter decomposition across biomes.

    PubMed

    García-Palacios, Pablo; Maestre, Fernando T; Kattge, Jens; Wall, Diana H

    2013-08-01

    Climate and litter quality have been identified as major drivers of litter decomposition at large spatial scales. However, the role played by soil fauna remains largely unknown, despite its importance for litter fragmentation and microbial activity. We synthesised litterbag studies to quantify the effect sizes of soil fauna on litter decomposition rates at the global and biome scales, and to assess how climate, litter quality and soil fauna interact to determine such rates. Soil fauna consistently enhanced litter decomposition at both global and biome scales (average increment ~ 37%). [corrected]. However, climate and litter quality differently modulated the effects of soil fauna on decomposition rates between biomes, from climate-driven biomes to those where climate effects were mediated by changes in litter quality. Our results advocate for the inclusion of biome-specific soil fauna effects on litter decomposition as a mean to reduce the unexplained variation in large-scale decomposition models. © 2013 John Wiley & Sons Ltd/CNRS.

  17. Hydrogen and carbon nanotube production via catalytic decomposition of methane

    NASA Astrophysics Data System (ADS)

    Deniz, Cansu; Karatepe, Nilgün

    2013-09-01

    The future energy demand is expected to increase significantly due to an increasing world population and demands for higher standards of living and better air quality. Hydrogen is considered as an energy carrier because of its high conversion efficiency and low pollutant emissions. It can be produced from various sources and transformed into electricity and other energy forms with a low pollution. The catalytic decomposition of hydrocarbon has been seen as a really useful method for production of pure hydrogen and for the environmental concern. The objective of this study was to assess the impact of catalyst composition and processing parameters on COx-free hydrogen production and to produce an available solid form of co-product carbon as carbon nanotubes via catalytic decomposition of methane. The optimum experimental conditions for methane decomposition have been investigated. Fe, Co and Ni are used as catalysts (nano materials) over different substrates as SiO2 and MgO to produce hydrogen at optimum temperatures.

  18. Cyclic Mario worlds — color-decomposition for one-loop QCD

    NASA Astrophysics Data System (ADS)

    Kälin, Gregor

    2018-04-01

    We present a new color decomposition for QCD amplitudes at one-loop level as a generalization of the Del Duca-Dixon-Maltoni and Johansson-Ochirov decomposition at tree level. Starting from a minimal basis of planar primitive amplitudes we write down a color decomposition that is free of linear dependencies among appearing primitive amplitudes or color factors. The conjectured decomposition applies to any number of quark flavors and is independent of the choice of gauge group and matter representation. The results also hold for higher-dimensional or supersymmetric extensions of QCD. We provide expressions for any number of external quark-antiquark pairs and gluons. [Figure not available: see fulltext.

  19. Interface conditions for domain decomposition with radical grid refinement

    NASA Technical Reports Server (NTRS)

    Scroggs, Jeffrey S.

    1991-01-01

    Interface conditions for coupling the domains in a physically motivated domain decomposition method are discussed. The domain decomposition is based on an asymptotic-induced method for the numerical solution of hyperbolic conservation laws with small viscosity. The method consists of multiple stages. The first stage is to obtain a first approximation using a first-order method, such as the Godunov scheme. Subsequent stages of the method involve solving internal-layer problem via a domain decomposition. The method is derived and justified via singular perturbation techniques.

  20. Freeze-Quench Magnetic Circular Dichroism Spectroscopic Study of the "Very Rapid" Intermediate in Xanthine Oxidase.

    PubMed

    Jones, Robert M.; Inscore, Frank E.; Hille, Russ; Kirk, Martin L.

    1999-11-01

    Freeze-quench magnetic circular dichroism spectroscopy (MCD) has been used to trap and study the excited-state electronic structure of the Mo(V) active site in a xanthine oxidase intermediate generated with substoichiometric concentrations of the slow substrate 2-hydroxy-6-methylpurine. EPR spectroscopy has shown that the intermediate observed in the MCD experiment is the "very rapid" intermediate, which lies on the main catalytic pathway. The low-energy (< approximately 30 000 cm(-1)) C-term MCD of this intermediate is remarkably similar to that of the model compound LMoO(bdt) (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; bdt = 1,2-benzenedithiolate), and the MCD bands have been assigned as dithiolate S(ip) --> Mo d(xy) and S(op) --> Mo d(xz,yz) LMCT transitions. These transitions result from a coordination geometry of the intermediate where the Mo=O bond is oriented cis to the ene-1,2-dithiolate of the pyranopterin. Since X-ray crystallography has indicated that a terminal sulfido ligand is oriented cis to the ene-1,2-dithiolate in oxidized xanthine oxidase related Desulfovibrio gigas aldehyde oxidoreductase, we have suggested that a conformational change occurs upon substrate binding. The substrate-mediated conformational change is extremely significant with respect to electron-transfer regeneration of the active site, as covalent interactions between the redox-active Mo d(xy) orbital and the S(ip) orbitals of the ene-1,2-dithiolate are maximized when the oxo ligand is oriented cis to the dithiolate plane. This underlies the importance of the ene-1,2-dithiolate portion of the pyranopterin in providing an efficient superexchange pathway for electron transfer. The results of this study indicate that electron-transfer regeneration of the active site may be gated by the orientation of the Mo=O bond relative to the ene-1,2-dithiolate chelate. Poor overlap between the Mo d(xy) orbital and the S(ip) orbitals of the dithiolate in the oxidized enzyme geometry may