CoMoS2/rGO/C3N4 ternary heterojunctions catalysts with high photocatalytic activity and stability for hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Xu, Xuejun; Si, Zhichun; Liu, Liping; Wang, Zehao; Chen, Ze; Ran, Rui; He, Yonghong; Weng, Duan

2018-03-01

Noble metal free MoS2/g-C3N4 catalyst has attracted intense attentions for visible light photocatalytic hydrogen evolution as a result of its earth abundance, low cost and unique heterojunctions stacked with two dimensional sheets. However, the low charge separation efficiency resulted from the poor conductivity of g-C3N4 and MoS2, and lack of abundant active sites from coordinative unsaturated atoms in MoS2, restricts the photocatalytic hydrogen evolution activity and stability enhancement of MoS2/C3N4 composite catalysts. Herein, CoMoS2/rGO/g-C3N4 catalysts with ternary heterojunctions are prepared by facile solvothermal method, which exhibit high visible light photocatalytic activity and stability for hydrogen evolution. The optimal hydrogen evolution rate of CoMoS2/rGO/g-C3N4 catalysts is 684 μmol g-1 h-1 when the content of CoMoS2 is 2% and the content of rGO is 0.5%. The stability of CoMoS2/rGO/C3N4 catalysts just decrease about 3% after 4 cycling runs for 16 h. The good catalytic performances of catalysts are attributed to the synergistic effect among the g-C3N4 nanosheets, rGO nanosheets and CoMoS2 nanosheets. The high conductivity of rGO nanosheets enhances the electron-hole separation and charge transfer, and Co doping increases the active sites for hydrogen evolution due to the increase of unsaturated atoms in CoMoS2 nanosheets.

Genes encoding biotin carboxylase subunit of acetyl-CoA carboxylase from Brassica napus and parental species: cloning, expression patterns, and evolution

USDA-ARS?s Scientific Manuscript database

Comparative genomics is a useful tool to investigate gene and genome evolution. Biotin carboxylase (BC), an important subunit of heteromeric ACCase that is a rate-limiting enzyme in fatty acid biosynthesis in dicots, catalyzes ATP, biotin-carboxyl-carrier protein and CO2 to form carboxybiotin-carbo...

On the rates of type Ia supernovae originating from white dwarf collisions in quadruple star systems

NASA Astrophysics Data System (ADS)

Hamers, Adrian S.

2018-04-01

We consider the evolution of stellar hierarchical quadruple systems in the 2+2 (two binaries orbiting each other's barycentre) and 3+1 (triple orbited by a fourth star) configurations. In our simulations, we take into account the effects of secular dynamical evolution, stellar evolution, tidal evolution and encounters with passing stars. We focus on type Ia supernovae (SNe Ia) driven by collisions of carbon-oxygen (CO) white dwarfs (WDs). Such collisions can arise from several channels: (1) collisions due to extremely high eccentricities induced by secular evolution, (2) collisions following a dynamical instability of the system, and (3) collisions driven by semisecular evolution. The systems considered here have initially wide inner orbits, with initial semilatus recti larger than 12 {au}, implying no interaction if the orbits were isolated. However, taking into account dynamical evolution, we find that ≈0.4 (≈0.6) of 2+2 (3+1) systems interact. In particular, Roche Lobe overflow can be triggered possibly in highly eccentric orbits, dynamical instability can ensue due to mass-loss-driven orbital expansion or secular evolution, or a semisecular regime can be entered. We compute the delay-time distributions (DTDs) of collision-induced SNe Ia, and find that they are flatter compared to the observed DTD. Moreover, our combined SNe Ia rates are (3.7± 0.7) × 10^{-6} M_⊙^{-1} and (1.3± 0.2) × 10^{-6} M_⊙^{-1} for 2+2 and 3+1 systems, respectively, three orders of magnitude lower compared to the observed rate, of order 10^{-3} M_⊙^{-1}. The low rates can be ascribed to interactions before the stars evolve to CO WDs. However, our results are lower limits given that we considered a subset of quadruple systems.

On the rates of Type Ia supernovae originating from white dwarf collisions in quadruple star systems

NASA Astrophysics Data System (ADS)

Hamers, Adrian S.

2018-07-01

We consider the evolution of stellar hierarchical quadruple systems in the 2+2 (two binaries orbiting each other's barycentre) and 3+1 (triple orbited by a fourth star) configurations. In our simulations, we take into account the effects of secular dynamical evolution, stellar evolution, tidal evolution, and encounters with passing stars. We focus on Type Ia supernovae (SNe Ia) driven by collisions of carbon-oxygen (CO) white dwarfs (WDs). Such collisions can arise from several channels: (1) collisions due to extremely high eccentricities induced by secular evolution, (2) collisions following a dynamical instability of the system, and (3) collisions driven by semisecular evolution. The systems considered here have initially wide inner orbits, with initial semilatus recti larger than 12 au, implying no interaction if the orbits were isolated. However, taking into account dynamical evolution, we find that ≈0.4 (≈0.6) of 2+2 (3+1) systems interact. In particular, Roche lobe overflow can be triggered possibly in highly eccentric orbits, dynamical instability can ensue due to mass-loss-driven orbital expansion or secular evolution, or a semisecular regime can be entered. We compute the delay-time distributions (DTDs) of collision-induced SNe Ia, and find that they are flatter compared to the observed DTD. Moreover, our combined SNe Ia rates are (3.7± 0.7) × 10^{-6} M_{⊙}^{-1} and (1.3± 0.2) × 10^{-6} M_{⊙}^{-1} for 2+2 and 3+1 systems, respectively, three orders of magnitude lower compared to the observed rate, of the order of 10^{-3} M_{⊙}^{-1}. The low rates can be ascribed to interactions before the stars evolve to CO WDs. However, our results are lower limits given that we considered a subset of quadruple systems.

Boosting the catalytic performance of MoSx cocatalysts over CdS nanoparticles for photocatalytic H2 evolution by Co doping via a facile photochemical route

NASA Astrophysics Data System (ADS)

Lei, Yonggang; Hou, Jianhua; Wang, Fang; Ma, Xiaohua; Jin, Zhiliang; Xu, Jing; Min, Shixiong

2017-10-01

Low-crystalline or amorphous molybdenum sulfides (MoSx), bearing abundant unsaturated active sites, have been identified as efficient catalysts for electrocatalytic and photocatalytic H2 evolution reactions, however, their intrinsic activity is still low and need to be further improved for large-scale applications. In this paper, we report that low-crystalline MoSx doped with Co (Co-MoSx) as efficient cocatalysts could be loaded on CdS nanoparticles through a facile and controllable photochemical reduction method and showed high performances in catalyzing H2 evolution under visible light irradiation (≥420 nm). The photochemical loading of Co-MoSx was accomplished by using an in-situ formed molecular complex precursor and photogenerated electrons on CdS as reductants under mild conditions. The optimized CdS/Co-MoSx (Co:Mo = 1:4, 2 mol% loading) photocatalyst exhibited a catalytic H2 evolution rate of 535 μmol h-1, which is 1.8 times higher than that of CdS/MoSx, and an apparent quantum efficiency (AQE) of 23.5% was achieved over CdS/Co-MoSx photocatalyst at 420 nm. Co-MoSx catalyst also shows a long-term stability without noticeable activity degradation. Notably, Co-MoSx cocatalyst was found more efficient than that of noble metals in catalyzing photocatalytic H2 evolution on CdS. The formation of CoMoS phase, the enhanced electrocatalytic activity as well as reduced electron transfer resistance due to the doping effects of Co ions, account for the enhanced catalytic activity of this Co-MoSx cocatalyst.

Net light-induced oxygen evolution in photosystem I deletion mutants of the cyanobacterium Synechocystis sp. PCC 6803.

PubMed

Wang, Qing Jun; Singh, Abhay; Li, Hong; Nedbal, Ladislav; Sherman, Louis A; Govindjee; Whitmarsh, John

2012-05-01

Oxygenic photosynthesis in cyanobacteria, algae, and plants requires photosystem II (PSII) to extract electrons from H(2)O and depends on photosystem I (PSI) to reduce NADP(+). Here we demonstrate that mixotrophically-grown mutants of the cyanobacterium Synechocystis sp. PCC 6803 that lack PSI (ΔPSI) are capable of net light-induced O(2) evolution in vivo. The net light-induced O(2) evolution requires glucose and can be sustained for more than 30 min. Utilizing electron transport inhibitors and chlorophyll a fluorescence measurements, we show that in these mutants PSII is the source of the light-induced O(2) evolution, and that the plastoquinone pool is reduced by PSII and subsequently oxidized by an unidentified electron acceptor that does not involve the plastoquinol oxidase site of the cytochrome b(6)f complex. Moreover, both O(2) evolution and chlorophyll a fluorescence kinetics of the ΔPSI mutants are highly sensitive to KCN, indicating the involvement of a KCN-sensitive enzyme(s). Experiments using (14)C-labeled bicarbonate show that the ΔPSI mutants assimilate more CO(2) in the light compared to the dark. However, the rate of the light-minus-dark CO(2) assimilation accounts for just over half of the net light-induced O(2) evolution rate, indicating the involvement of unidentified terminal electron acceptors. Based on these results we suggest that O(2) evolution in ΔPSI cells can be sustained by an alternative electron transport pathway that results in CO(2) assimilation and that includes PSII, the platoquinone pool, and a KCN-sensitive enzyme. Copyright © 2012 Elsevier B.V. All rights reserved.

Leaf Evolution: Gases, Genes and Geochemistry

PubMed Central

BEERLING, DAVID J.

2005-01-01

• Aims This Botanical Briefing reviews how the integration of palaeontology, geochemistry and developmental biology is providing a new mechanistic framework for interpreting the 40- to 50-million-year gap between the origination of vascular land plants and the advent of large (megaphyll) leaves, a long-standing puzzle in evolutionary biology. • Scope Molecular genetics indicates that the developmental mechanisms required for leaf production in vascular plants were recruited long before the advent of large megaphylls. According to theory, this morphogenetic potential was only realized as the concentration of atmospheric CO2 declined during the late Palaeozoic. Surprisingly, plants effectively policed their own evolution since the decrease in CO2 was brought about as terrestrial floras evolved accelerating the rate of silicate rock weathering and enhancing sedimentary organic carbon burial, both of which are long-term sinks for CO2. • Conclusions The recognition that plant evolution responds to and influences CO2 over millions of years reveals the existence of an intricate web of vegetation feedbacks regulating the long-term carbon cycle. Several of these feedbacks destabilized CO2 and climate during the late Palaeozoic but appear to have quickened the pace of terrestrial plant and animal evolution at that time. PMID:15965270

Leaf evolution: gases, genes and geochemistry.

PubMed

Beerling, David J

2005-09-01

This Botanical Briefing reviews how the integration of palaeontology, geochemistry and developmental biology is providing a new mechanistic framework for interpreting the 40- to 50-million-year gap between the origination of vascular land plants and the advent of large (megaphyll) leaves, a long-standing puzzle in evolutionary biology. Molecular genetics indicates that the developmental mechanisms required for leaf production in vascular plants were recruited long before the advent of large megaphylls. According to theory, this morphogenetic potential was only realized as the concentration of atmospheric CO2 declined during the late Palaeozoic. Surprisingly, plants effectively policed their own evolution since the decrease in CO2 was brought about as terrestrial floras evolved accelerating the rate of silicate rock weathering and enhancing sedimentary organic carbon burial, both of which are long-term sinks for CO2. The recognition that plant evolution responds to and influences CO(2) over millions of years reveals the existence of an intricate web of vegetation feedbacks regulating the long-term carbon cycle. Several of these feedbacks destabilized CO2 and climate during the late Palaeozoic but appear to have quickened the pace of terrestrial plant and animal evolution at that time.

The influence of meteorological variables on CO2 and CH4 trends recorded at a semi-natural station.

PubMed

Pérez, Isidro A; Sánchez, M Luisa; García, M Ángeles; Pardo, Nuria; Fernández-Duque, Beatriz

2018-03-01

CO 2 and CH 4 evolution is usually linked with sources, sinks and their changes. However, this study highlights the role of meteorological variables. It aims to quantify their contribution to the trend of these greenhouse gases and to determine which contribute most. Six years of measurements at a semi-natural site in northern Spain were considered. Three sections are established: the first focuses on monthly deciles, the second explores the relationship between pairs of meteorological variables, and the third investigates the relationship between meteorological variables and changes in CO 2 and CH 4 . In the first section, monthly outliers were more marked for CO 2 than for CH 4 . The evolution of monthly deciles was fitted to three simple expressions, linear, quadratic and exponential. The linear and exponential are similar, whereas the quadratic evolution is the most flexible since it provided a variable rate of concentration change and a better fit. With this last evolution, a decrease in the change rate was observed for low CO 2 deciles, whereas an increasing change rate prevailed for the rest and was more accentuated for CH 4 . In the second section, meteorological variables were provided by a trajectory model. Backward trajectories from 1-day prior to reaching the measurement site were used to calculate distance and direction averages as well as the recirculation factor. Terciles of these variables were determined in order to establish three intervals with low, medium and high values. These intervals were used to classify the variables following their interval widths and skewnesses. The best correlation between pairs of meteorological variables was observed for the average distance, in particular with horizontal wind speed. Sinusoidal relationships with the average direction were obtained for average distance and for vertical wind speed. Finally, in the third section, the quadratic evolution was considered in each interval of all the meteorological variables. As regards the main result, the greatest increases were obtained for high potential temperature for both gases followed by low and medium boundary layer height for CO 2 and CH 4 , respectively. Combining both meteorological variables provided increases of 22 ± 9 and 0.070 ± 0.019 ppm for CO 2 and CH 4 , respectively, although the number of observations affected is small, around 7%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nitrate-Dependent O2 Evolution in Intact Leaves 1

PubMed Central

de la Torre, Angel; Delgado, Begoña; Lara, Catalina

1991-01-01

Evolution of O2 by illuminated intact detached leaves from barley (Hordeum vulgare L. cv Athos) and pea (Pisum sativum L. cv Lincoln) in a CO2-saturating atmosphere was enhanced when KNO3 (1-2.5 millimolar) had been previously supplied through the transpiration stream. The extra O2 evolution observed after feeding KNO3 increased with the light intensity, being maximal at near saturating photon flux densities and resulting in no changes in the initial slope of the O2 versus light-intensity curve. No stimulation of O2 evolution was otherwise observed after feeding KCl or NH4Cl. The data indicate that nitrate assimilation uses photosynthetically generated reductant and stimulates the rate of non-cyclic electron flow by acting as a second electron-accepting assimilatory process in addition to CO2 fixation. PMID:16668272

Development and Evaluation of an Online CO2 Evolution Test and a Multicomponent Biodegradation Test System

PubMed Central

Strotmann, Uwe; Reuschenbach, Peter; Schwarz, Helmut; Pagga, Udo

2004-01-01

Well-established biodegradation tests use biogenously evolved carbon dioxide (CO2) as an analytical parameter to determine the ultimate biodegradability of substances. A newly developed analytical technique based on the continuous online measurement of conductivity showed its suitability over other techniques. It could be demonstrated that the method met all criteria of established biodegradation tests, gave continuous biodegradation curves, and was more reliable than other tests. In parallel experiments, only small variations in the biodegradation pattern occurred. When comparing the new online CO2 method with existing CO2 evolution tests, growth rates and lag periods were similar and only the final degree of biodegradation of aniline was slightly lower. A further test development was the unification and parallel measurement of all three important summary parameters for biodegradation—i.e., CO2 evolution, determination of the biochemical oxygen demand (BOD), and removal of dissolved organic carbon (DOC)—in a multicomponent biodegradation test system (MCBTS). The practicability of this test method was demonstrated with aniline. This test system had advantages for poorly water-soluble and highly volatile compounds and allowed the determination of the carbon fraction integrated into biomass (heterotrophic yield). The integrated online measurements of CO2 and BOD systems produced continuous degradation curves, which better met the stringent criteria of ready biodegradability (60% biodegradation in a 10-day window). Furthermore the data could be used to calculate maximal growth rates for the modeling of biodegradation processes. PMID:15294794

Adaptation of the autotrophic acetogen Sporomusa ovata to methanol accelerates the conversion of CO2 to organic products.

PubMed

Tremblay, Pier-Luc; Höglund, Daniel; Koza, Anna; Bonde, Ida; Zhang, Tian

2015-11-04

Acetogens are efficient microbial catalysts for bioprocesses converting C1 compounds into organic products. Here, an adaptive laboratory evolution approach was implemented to adapt Sporomusa ovata for faster autotrophic metabolism and CO2 conversion to organic chemicals. S. ovata was first adapted to grow quicker autotrophically with methanol, a toxic C1 compound, as the sole substrate. Better growth on different concentrations of methanol and with H2-CO2 indicated the adapted strain had a more efficient autotrophic metabolism and a higher tolerance to solvent. The growth rate on methanol was increased 5-fold. Furthermore, acetate production rate from CO2 with an electrode serving as the electron donor was increased 6.5-fold confirming that the acceleration of the autotrophic metabolism of the adapted strain is independent of the electron donor provided. Whole-genome sequencing, transcriptomic, and biochemical studies revealed that the molecular mechanisms responsible for the novel characteristics of the adapted strain were associated with the methanol oxidation pathway and the Wood-Ljungdahl pathway of acetogens along with biosynthetic pathways, cell wall components, and protein chaperones. The results demonstrate that an efficient strategy to increase rates of CO2 conversion in bioprocesses like microbial electrosynthesis is to evolve the microbial catalyst by adaptive laboratory evolution to optimize its autotrophic metabolism.

Carbon and hydrogen metabolism of green algae in light and dark

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

Not Available

1990-01-01

After adaptation to a hydrogen metabolism, Chlamydomonas reinhardtii can photoanaerobically metabolize acetate with the evolution of H{sub 2} and CO{sub 2}. An enzyme profile of the chloroplastic, cytoplasmic, and mitochondrial fractions were obtained with a cellular fractionation procedure that incorporated cell wall removal by autolysine, digestion of the plasmalemma with digitonin and fractionation by differential centrifugation on a Percoll step gradient. The sequence of events leading to the photo-evolution of H{sub 2} from acetate includes the conversion of acetate into succinate via the extraplastidic glyoxylate cycle, the oxidation of succinate to fumarate by chloroplastic succinic dehydrogenase and the oxidation ofmore » malate to oxaloacetate in the chloroplast by NAD dependent malate dehydrogenase. The level of potential activity of the enzymes was sufficient to accommodate the observed rate of gas evolution. The isolated darkened chloroplast evolves aerobically CO{sub 2} from glucose indicating a chloroplastic respiratory pathway. Evolution of CO{sub 2} is blocked by mitochondrial inhibitors.« less

Assessing the biodegradability of microparticles disposed down the drain.

PubMed

McDonough, Kathleen; Itrich, Nina; Casteel, Kenneth; Menzies, Jennifer; Williams, Tom; Krivos, Kady; Price, Jason

2017-05-01

Microparticles made from naturally occurring materials or biodegradable plastics such as poly(3-hydroxy butyrate)-co-(3-hydroxy valerate), PHBV, are being evaluated as alternatives to microplastics in personal care product applications but limited data is available on their ultimate biodegradability (mineralization) in down the drain environmental compartments. An OECD 301B Ready Biodegradation Test was used to quantify ultimate biodegradability of microparticles made of PHBV foam, jojoba wax, beeswax, rice bran wax, stearyl stearate, blueberry seeds and walnut shells. PHBV polymer was ready biodegradable reaching 65.4 ± 4.1% evolved CO 2 in 5 d and 90.5 ± 3.1% evolved CO 2 in 80 d. PHBV foam microparticles (125-500 μm) were mineralized extensively with >66% CO 2 evolution in 28 d and >82% CO 2 evolution in 80 d. PHBV foam microparticles were mineralized at a similar rate and extent as microparticles made of jojoba wax, beeswax, rice bran wax, and stearyl stearate which reached 84.8  ± 4.8, 84.9  ± 2.2, 82.7  ± 4.7, and 86.4 ± 3.2% CO 2 evolution respectively in 80 d. Blueberry seeds and walnut shells mineralized more slowly only reaching 39.3  ± 6.9 and 5.1 ± 2.8% CO 2 evolution in 80 d respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

A spongy nickel-organic CO2 reduction photocatalyst for nearly 100% selective CO production

PubMed Central

Niu, Kaiyang; Xu, You; Wang, Haicheng; Ye, Rong; Xin, Huolin L.; Lin, Feng; Tian, Chixia; Lum, Yanwei; Bustillo, Karen C.; Doeff, Marca M.; Koper, Marc T. M.; Ager, Joel; Xu, Rong; Zheng, Haimei

2017-01-01

Solar-driven photocatalytic conversion of CO2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H2 evolution during photocatalytic CO2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO2 to CO, with a production rate of ~1.6 × 104 μmol hour−1 g−1. No measurable H2 is generated during the reaction, leading to nearly 100% selective CO production over H2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO2 reduction reactions generate formic acid and acetic acid. Achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy. PMID:28782031

In situ photodeposition of amorphous CoSx on the TiO2 towards hydrogen evolution

NASA Astrophysics Data System (ADS)

Chen, Feng; Luo, Wei; Mo, Yanping; Yu, Huogen; Cheng, Bei

2018-02-01

Cocatalyst modification of photocatalysts is an important strategy to enhance the photocatalytic performance by promoting effective separation of photoinduced electron-hole pairs and providing abundant active sites. In this study, a facile in situ photodeposition method was developed to prepare amorphous CoSx-modified TiO2 photocatalysts. It was found that amorphous CoSx nanoparticles were solidly loaded on the TiO2 surface, resulting in a greatly improved photocatalytic H2-evolution performance. When the amount of amorphous CoSx was 10 wt%, the hydrogen evolution rate of the CoSx/TiO2 reached 119.7 μmol h-1, which was almost 16.7 times that of the pure TiO2. According to the above experimental results, a reasonable mechanism of improved photocatalytic performance is proposed for the CoSx/TiO2 photocatalysts, namely, the photogenerated electrons of TiO2 can rapidly transfer to amorphous CoSx nanoparticles due to the solid contact between them, and then amorphous CoSx can provide plenty of sulfur active sites to rapidly adsorb protons from solution to produce hydrogen by the photogenerated electrons. Considering the facile synthesis method, the present cheap and highly efficient amorphous CoSx-modified TiO2 photocatalysts would have great potential for practical use in photocatalytic H2 production.

Experimental study of linear and nonlinear regimes of density-driven instabilities induced by CO{sub 2} dissolution in water

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

Outeda, R.; D'Onofrio, A.; El Hasi, C.

Density driven instabilities produced by CO{sub 2} (gas) dissolution in water containing a color indicator were studied in a Hele Shaw cell. The images were analyzed and instability patterns were characterized by mixing zone temporal evolution, dispersion curves, and the growth rate for different CO{sub 2} pressures and different color indicator concentrations. The results obtained from an exhaustive analysis of experimental data show that this system has a different behaviour in the linear regime of the instabilities (when the growth rate has a linear dependence with time), from the nonlinear regime at longer times. At short times using a colormore » indicator to see the evolution of the pattern, the images show that the effects of both the color indicator and CO{sub 2} pressure are of the same order of magnitude: The growth rates are similar and the wave numbers are in the same range (0–30 cm{sup −1}) when the system is unstable. Although in the linear regime the dynamics is affected similarly by the presence of the indicator and CO{sub 2} pressure, in the nonlinear regime, the influence of the latter is clearly more pronounced than the effects of the color indicator.« less

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

USGS Publications Warehouse

Lorah, Michelle M.; Herman, Janet S.

1988-01-01

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO2outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO2, outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO2 along the entire 5.2-km flow path. Outgassing of CO2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO2. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Growth and photosynthetic responses of wheat plants grown in space

NASA Technical Reports Server (NTRS)

Tripathy, B. C.; Brown, C. S.; Levine, H. G.; Krikorian, A. D.

1996-01-01

Growth and photosynthesis of wheat (Triticum aestivum L. cv Super Dwarf) plants grown onboard the space shuttle Discovery for 10 d were examined. Compared to ground control plants, the shoot fresh weight of space-grown seedlings decreased by 25%. Postflight measurements of the O2 evolution/photosynthetic photon flux density response curves of leaf samples revealed that the CO2-saturated photosynthetic rate at saturating light intensities in space-grown plants declined 25% relative to the rate in ground control plants. The relative quantum yield of CO2-saturated photosynthetic O2 evolution measured at limiting light intensities was not significantly affected. In space-grown plants, the light compensation point of the leaves increased by 33%, which likely was due to an increase (27%) in leaf dark-respiration rates. Related experiments with thylakoids isolated from space-grown plants showed that the light-saturated photosynthetic electron transport rate from H2O through photosystems II and I was reduced by 28%. These results demonstrate that photosynthetic functions are affected by the microgravity environment.

Adaptation of the autotrophic acetogen Sporomusa ovata to methanol accelerates the conversion of CO2 to organic products

PubMed Central

Tremblay, Pier-Luc; Höglund, Daniel; Koza, Anna; Bonde, Ida; Zhang, Tian

2015-01-01

Acetogens are efficient microbial catalysts for bioprocesses converting C1 compounds into organic products. Here, an adaptive laboratory evolution approach was implemented to adapt Sporomusa ovata for faster autotrophic metabolism and CO2 conversion to organic chemicals. S. ovata was first adapted to grow quicker autotrophically with methanol, a toxic C1 compound, as the sole substrate. Better growth on different concentrations of methanol and with H2-CO2 indicated the adapted strain had a more efficient autotrophic metabolism and a higher tolerance to solvent. The growth rate on methanol was increased 5-fold. Furthermore, acetate production rate from CO2 with an electrode serving as the electron donor was increased 6.5-fold confirming that the acceleration of the autotrophic metabolism of the adapted strain is independent of the electron donor provided. Whole-genome sequencing, transcriptomic, and biochemical studies revealed that the molecular mechanisms responsible for the novel characteristics of the adapted strain were associated with the methanol oxidation pathway and the Wood-Ljungdahl pathway of acetogens along with biosynthetic pathways, cell wall components, and protein chaperones. The results demonstrate that an efficient strategy to increase rates of CO2 conversion in bioprocesses like microbial electrosynthesis is to evolve the microbial catalyst by adaptive laboratory evolution to optimize its autotrophic metabolism. PMID:26530351

A spongy nickel-organic CO 2 reduction photocatalyst for nearly 100% selective CO production

DOE PAGES

Niu, Kaiyang; Xu, You; Wang, Haicheng; ...

2017-07-28

Solar-driven photocatalytic conversion of CO 2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO 2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H 2 evolution during photocatalytic CO 2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO 2 to CO, with a production rate of ~1.6 × 10 4 μmolmore » hour –1 g –1. No measurable H 2 is generated during the reaction, leading to nearly 100% selective CO production over H 2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO 2 reduction reactions generate formic acid and acetic acid. As a result, achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy.« less

A spongy nickel-organic CO 2 reduction photocatalyst for nearly 100% selective CO production

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

Niu, Kaiyang; Xu, You; Wang, Haicheng

Solar-driven photocatalytic conversion of CO 2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO 2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H 2 evolution during photocatalytic CO 2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO 2 to CO, with a production rate of ~1.6 × 10 4 μmolmore » hour –1 g –1. No measurable H 2 is generated during the reaction, leading to nearly 100% selective CO production over H 2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO 2 reduction reactions generate formic acid and acetic acid. As a result, achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy.« less

Evolution of C4 plants: a new hypothesis for an interaction of CO2 and water relations mediated by plant hydraulics

PubMed Central

Osborne, Colin P.; Sack, Lawren

2012-01-01

C4 photosynthesis has evolved more than 60 times as a carbon-concentrating mechanism to augment the ancestral C3 photosynthetic pathway. The rate and the efficiency of photosynthesis are greater in the C4 than C3 type under atmospheric CO2 depletion, high light and temperature, suggesting these factors as important selective agents. This hypothesis is consistent with comparative analyses of grasses, which indicate repeated evolutionary transitions from shaded forest to open habitats. However, such environmental transitions also impact strongly on plant–water relations. We hypothesize that excessive demand for water transport associated with low CO2, high light and temperature would have selected for C4 photosynthesis not only to increase the efficiency and rate of photosynthesis, but also as a water-conserving mechanism. Our proposal is supported by evidence from the literature and physiological models. The C4 pathway allows high rates of photosynthesis at low stomatal conductance, even given low atmospheric CO2. The resultant decrease in transpiration protects the hydraulic system, allowing stomata to remain open and photosynthesis to be sustained for longer under drying atmospheric and soil conditions. The evolution of C4 photosynthesis therefore simultaneously improved plant carbon and water relations, conferring strong benefits as atmospheric CO2 declined and ecological demand for water rose. PMID:22232769

Evolution of C4 plants: a new hypothesis for an interaction of CO2 and water relations mediated by plant hydraulics.

PubMed

Osborne, Colin P; Sack, Lawren

2012-02-19

C(4) photosynthesis has evolved more than 60 times as a carbon-concentrating mechanism to augment the ancestral C(3) photosynthetic pathway. The rate and the efficiency of photosynthesis are greater in the C(4) than C(3) type under atmospheric CO(2) depletion, high light and temperature, suggesting these factors as important selective agents. This hypothesis is consistent with comparative analyses of grasses, which indicate repeated evolutionary transitions from shaded forest to open habitats. However, such environmental transitions also impact strongly on plant-water relations. We hypothesize that excessive demand for water transport associated with low CO(2), high light and temperature would have selected for C(4) photosynthesis not only to increase the efficiency and rate of photosynthesis, but also as a water-conserving mechanism. Our proposal is supported by evidence from the literature and physiological models. The C(4) pathway allows high rates of photosynthesis at low stomatal conductance, even given low atmospheric CO(2). The resultant decrease in transpiration protects the hydraulic system, allowing stomata to remain open and photosynthesis to be sustained for longer under drying atmospheric and soil conditions. The evolution of C(4) photosynthesis therefore simultaneously improved plant carbon and water relations, conferring strong benefits as atmospheric CO(2) declined and ecological demand for water rose.

Fundamental Study on the Dynamics of Heterogeneity-Enhanced CO2 Gas Evolution in the Shallow Subsurface During Possible Leakage from Deep Geologic Storage Sites

NASA Astrophysics Data System (ADS)

Plampin, M. R.; Lassen, R. N.; Sakaki, T.; Pawar, R.; Jensen, K.; Illangasekare, T. H.

2013-12-01

A concern for geologic carbon sequestration is the potential for CO2 stored in deep geologic formations to leak upward into shallow freshwater aquifers where it can have potentially detrimental impacts to the environment and human health. Understanding the mechanisms of CO2 exsolution, migration and accumulation (collectively referred to as 'gas evolution') in the shallow subsurface is critical to predict and mitigate the environmental impacts. During leakage, CO2 can move either as free-phase or as a dissolved component of formation brine. CO2 dissolved in brine may travel upward into shallow freshwater systems, and the gas may be released from solution. In the shallow aquifer, the exsolved gas may accumulate near interfaces between soil types, and/or create flow paths that allow the gas to escape through the vadose zone to the atmosphere. The process of gas evolution in the shallow subsurface is controlled by various factors, including temperature, dissolved CO2 concentration, water pressure, background water flow rate, and geologic heterogeneity. However, the conditions under which heterogeneity controls gas phase evolution have not yet been precisely defined and can therefore not yet be incorporated into models used for environmental risk assessment. The primary goal of this study is to conduct controlled laboratory experiments to help fill this knowledge gap. With this as a goal, a series of intermediate-scale laboratory experiments were conducted to observe CO2 gas evolution in porous media at multiple scales. Deionized water was saturated with dissolved CO2 gas under a specified pressure (the saturation pressure) before being injected at a constant volumetric flow rate into the bottom of a 1.7 meter-tall by 5.7 centimeter-diameter column or a 2.4 meter-tall by 40 centimeter-wide column that were both filled with sand in various heterogeneous packing configurations. Both test systems were initially saturated with fresh water and instrumented with soil moisture sensors to monitor the evolution of gas phase through time by measuring the average water content in small sampling volumes of soil. Tensiometers allowed for observation of water pressure through space and time in the test systems, and a computer-interfaced electronic scale continuously monitored the outflow of water from the top of the two test columns. Several packing configurations with five different types of sands were used in order to test the effects of various pore size contrasts and interface shapes on the evolution of the gas phase near soil texture transitions in the heterogeneous packings. Results indicate that: (1) heterogeneity affects gas phase evolution patterns within a predictable range of conditions quantified by the newly introduced term 'oversaturation,' (2) soil transition interfaces where less permeable material overlies more permeable material have a much more pronounced effect on gas evolution than interfaces with opposite orientations, and (3) anticlines (or stratigraphic traps) cause significantly greater gas accumulation than horizontal interfaces. Further work is underway to apply these findings to more realistic, two-dimensional scenarios, and to assess how well existing numerical models can capture these processes.

Irreversibly increased nitrogen fixation in Trichodesmium experimentally adapted to elevated carbon dioxide

PubMed Central

Hutchins, David A.; Walworth, Nathan G.; Webb, Eric A.; Saito, Mak A.; Moran, Dawn; McIlvin, Matthew R.; Gale, Jasmine; Fu, Fei-Xue

2015-01-01

Nitrogen fixation rates of the globally distributed, biogeochemically important marine cyanobacterium Trichodesmium increase under high carbon dioxide (CO2) levels in short-term studies due to physiological plasticity. However, its long-term adaptive responses to ongoing anthropogenic CO2 increases are unknown. Here we show that experimental evolution under extended selection at projected future elevated CO2 levels results in irreversible, large increases in nitrogen fixation and growth rates, even after being moved back to lower present day CO2 levels for hundreds of generations. This represents an unprecedented microbial evolutionary response, as reproductive fitness increases acquired in the selection environment are maintained after returning to the ancestral environment. Constitutive rate increases are accompanied by irreversible shifts in diel nitrogen fixation patterns, and increased activity of a potentially regulatory DNA methyltransferase enzyme. High CO2-selected cell lines also exhibit increased phosphorus-limited growth rates, suggesting a potential advantage for this keystone organism in a more nutrient-limited, acidified future ocean. PMID:26327191

Irreversibly increased nitrogen fixation in Trichodesmium experimentally adapted to elevated carbon dioxide

NASA Astrophysics Data System (ADS)

Hutchins, David A.; Walworth, Nathan G.; Webb, Eric A.; Saito, Mak A.; Moran, Dawn; McIlvin, Matthew R.; Gale, Jasmine; Fu, Fei-Xue

2015-09-01

Nitrogen fixation rates of the globally distributed, biogeochemically important marine cyanobacterium Trichodesmium increase under high carbon dioxide (CO2) levels in short-term studies due to physiological plasticity. However, its long-term adaptive responses to ongoing anthropogenic CO2 increases are unknown. Here we show that experimental evolution under extended selection at projected future elevated CO2 levels results in irreversible, large increases in nitrogen fixation and growth rates, even after being moved back to lower present day CO2 levels for hundreds of generations. This represents an unprecedented microbial evolutionary response, as reproductive fitness increases acquired in the selection environment are maintained after returning to the ancestral environment. Constitutive rate increases are accompanied by irreversible shifts in diel nitrogen fixation patterns, and increased activity of a potentially regulatory DNA methyltransferase enzyme. High CO2-selected cell lines also exhibit increased phosphorus-limited growth rates, suggesting a potential advantage for this keystone organism in a more nutrient-limited, acidified future ocean.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2018-03-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (Δ F/ F' m ), photosynthetic efficiency ( α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCOˉ 3 via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae)

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2017-06-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (ΔF/F' m ), photosynthetic efficiency (α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCO3 - via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Deep Drawing Behavior of CoCrFeMnNi High-Entropy Alloys

NASA Astrophysics Data System (ADS)

Bae, Jae Wung; Moon, Jongun; Jang, Min Ji; Ahn, Dong-Hyun; Joo, Soo-Hyun; Jung, Jaimyun; Yim, Dami; Kim, Hyoung Seop

2017-09-01

Herein, the deep drawability and deep drawing behavior of an equiatomic CoCrFeMnNi HEA and its microstructure and texture evolution are first studied for future applications. The CoCrFeMnNi HEA is successfully drawn to a limit drawing ratio (LDR) of 2.14, while the planar anisotropy of the drawn cup specimen is negligible. The moderate combination of strain hardening exponent and strain rate sensitivity and the formation of deformation twins in the edge region play important roles in successful deep drawing. In the meanwhile, the texture evolution of CoCrFeMnNi HEA has similarities with conventional fcc metals.

Long-term dynamics of adaptive evolution in a globally important phytoplankton species to ocean acidification

PubMed Central

Schlüter, Lothar; Lohbeck, Kai T.; Gröger, Joachim P.; Riebesell, Ulf; Reusch, Thorsten B. H.

2016-01-01

Marine phytoplankton may adapt to ocean change, such as acidification or warming, because of their large population sizes and short generation times. Long-term adaptation to novel environments is a dynamic process, and phenotypic change can take place thousands of generations after exposure to novel conditions. We conducted a long-term evolution experiment (4 years = 2100 generations), starting with a single clone of the abundant and widespread coccolithophore Emiliania huxleyi exposed to three different CO2 levels simulating ocean acidification (OA). Growth rates as a proxy for Darwinian fitness increased only moderately under both levels of OA [+3.4% and +4.8%, respectively, at 1100 and 2200 μatm partial pressure of CO2 (Pco2)] relative to control treatments (ambient CO2, 400 μatm). Long-term adaptation to OA was complex, and initial phenotypic responses of ecologically important traits were later reverted. The biogeochemically important trait of calcification, in particular, that had initially been restored within the first year of evolution was later reduced to levels lower than the performance of nonadapted populations under OA. Calcification was not constitutively lost but returned to control treatment levels when high CO2–adapted isolates were transferred back to present-day control CO2 conditions. Selection under elevated CO2 exacerbated a general decrease of cell sizes under long-term laboratory evolution. Our results show that phytoplankton may evolve complex phenotypic plasticity that can affect biogeochemically important traits, such as calcification. Adaptive evolution may play out over longer time scales (>1 year) in an unforeseen way under future ocean conditions that cannot be predicted from initial adaptation responses. PMID:27419227

Highly Rechargeable Lithium-CO2 Batteries with a Boron- and Nitrogen-Codoped Holey-Graphene Cathode.

PubMed

Qie, Long; Lin, Yi; Connell, John W; Xu, Jiantie; Dai, Liming

2017-06-06

Metal-air batteries, especially Li-air batteries, have attracted significant research attention in the past decade. However, the electrochemical reactions between CO 2 (0.04 % in ambient air) with Li anode may lead to the irreversible formation of insulating Li 2 CO 3 , making the battery less rechargeable. To make the Li-CO 2 batteries usable under ambient conditions, it is critical to develop highly efficient catalysts for the CO 2 reduction and evolution reactions and investigate the electrochemical behavior of Li-CO 2 batteries. Here, we demonstrate a rechargeable Li-CO 2 battery with a high reversibility by using B,N-codoped holey graphene as a highly efficient catalyst for CO 2 reduction and evolution reactions. Benefiting from the unique porous holey nanostructure and high catalytic activity of the cathode, the as-prepared Li-CO 2 batteries exhibit high reversibility, low polarization, excellent rate performance, and superior long-term cycling stability over 200 cycles at a high current density of 1.0 A g -1 . Our results open up new possibilities for the development of long-term Li-air batteries reusable under ambient conditions, and the utilization and storage of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Evolution of CO2 on Mars

NASA Technical Reports Server (NTRS)

Kahn, R.

1985-01-01

The consequences of the hypothesis that the evolution of CO2 is directly linked to the occurrence of at least transitory pockets of moisture were exposed. The current conditions preclude the existence of open bodies of liquid water and the formation of moisture in disequilibrium is not excluded by any known constraints. The water evaporation rate is inversely proportional to PCO2, and the existence of a limiting value (P*) for which liquid water can form in the Mars environment is postulated. The evolution of PCO2 is controlled largely by relatively rapid aqueous chemistry forming carbon-containing sedimentary rocks, perhaps during early history in open water, but more recently in transitory pockets of moisture in the soil. Once the total atmospheric pressure is reduced to near P*, the occurrence of transitory moisture is inhibited, and atmospheric CO2 is no longer depleted by an efficient mechanism. The role of the carbonate reservoir in the current overall carbon budget on Mars, according to this scheme, is illustrated.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

ALMA Spectroscopic Survey in the Hubble Ultra Deep Field: CO Luminosity Functions and the Evolution of the Cosmic Density of Molecular Gas

NASA Astrophysics Data System (ADS)

Decarli, Roberto; Walter, Fabian; Aravena, Manuel; Carilli, Chris; Bouwens, Rychard; da Cunha, Elisabete; Daddi, Emanuele; Ivison, R. J.; Popping, Gergö; Riechers, Dominik; Smail, Ian R.; Swinbank, Mark; Weiss, Axel; Anguita, Timo; Assef, Roberto J.; Bauer, Franz E.; Bell, Eric F.; Bertoldi, Frank; Chapman, Scott; Colina, Luis; Cortes, Paulo C.; Cox, Pierre; Dickinson, Mark; Elbaz, David; Gónzalez-López, Jorge; Ibar, Edo; Infante, Leopoldo; Hodge, Jacqueline; Karim, Alex; Le Fevre, Olivier; Magnelli, Benjamin; Neri, Roberto; Oesch, Pascal; Ota, Kazuaki; Rix, Hans-Walter; Sargent, Mark; Sheth, Kartik; van der Wel, Arjen; van der Werf, Paul; Wagg, Jeff

2016-12-01

In this paper we use ASPECS, the ALMA Spectroscopic Survey in the Hubble Ultra Deep Field in band 3 and band 6, to place blind constraints on the CO luminosity function and the evolution of the cosmic molecular gas density as a function of redshift up to z ˜ 4.5. This study is based on galaxies that have been selected solely through their CO emission and not through any other property. In all of the redshift bins the ASPECS measurements reach the predicted “knee” of the CO luminosity function (around 5 × 109 K km s-1 pc2). We find clear evidence of an evolution in the CO luminosity function with respect to z ˜ 0, with more CO-luminous galaxies present at z ˜ 2. The observed galaxies at z ˜ 2 also appear more gas-rich than predicted by recent semi-analytical models. The comoving cosmic molecular gas density within galaxies as a function of redshift shows a drop by a factor of 3-10 from z ˜ 2 to z ˜ 0 (with significant error bars), and possibly a decline at z > 3. This trend is similar to the observed evolution of the cosmic star formation rate density. The latter therefore appears to be at least partly driven by the increased availability of molecular gas reservoirs at the peak of cosmic star formation (z ˜ 2).

Leaf fossil record suggests limited influence of atmospheric CO2 on terrestrial productivity prior to angiosperm evolution

PubMed Central

Boyce, C. Kevin; Zwieniecki, Maciej A.

2012-01-01

Declining CO2 over the Cretaceous has been suggested as an evolutionary driver of the high leaf vein densities (7–28 mm mm−2) that are unique to the angiosperms throughout all of Earth history. Photosynthetic modeling indicated the link between high vein density and productivity documented in the modern low-CO2 regime would be lost as CO2 concentrations increased but also implied that plants with very low vein densities (less than 3 mm mm−2) should experience substantial disadvantages with high CO2. Thus, the hypothesized relationship between CO2 and plant evolution can be tested through analysis of the concurrent histories of alternative lineages, because an extrinsic driver like atmospheric CO2 should affect all plants and not just the flowering plants. No such relationship is seen. Regardless of CO2 concentrations, low vein densities are equally common among nonangiosperms throughout history and common enough to include forest canopies and not just obligate shade species that will always be of limited productivity. Modeling results can be reconciled with the fossil record if maximum assimilation rates of nonflowering plants are capped well below those of flowering plants, capturing biochemical and physiological differences that would be consistent with extant plants but previously unrecognized in the fossil record. Although previous photosynthetic modeling suggested that productivity would double or triple with each Phanerozoic transition from low to high CO2, productivity changes are likely to have been limited before a substantial increase accompanying the evolution of flowering plants. PMID:22689947

The Interactive Effects of Elevated CO2 and Ammonium Enrichment on the Physiological Performances of Saccharina japonica (Laminariales, Phaeophyta)

NASA Astrophysics Data System (ADS)

Kang, Jin Woo; Chung, Ik Kyo

2018-04-01

Environmental challenges such as ocean acidification and eutrophication influence the physiology of kelp species. We investigated their interactive effects on Saccharina japonica (Laminariales, Phaeophyta) under two pH conditions [Low, 7.50; High (control), 8.10] and three NH4 +concentrations (Low, 4; Medium, 60; High, 120 μM). The degree of variation of pH values in the culture medium and inhibition rate of photosynthetic oxygen evolution by acetazolamide were affected by pH treatments. Relative growth rates, carbon, nitrogen, and the C:N ratio in tissue samples were influenced by higher concentrations of NH4 + . Rates of photosynthetic oxygen evolution were enhanced under elevated CO2 or NH4 +conditions, independently, but these two factors did not show an interactive effect. However, rates of NH4 +uptake were influenced by the interactive effect of increased CO2 under elevated NH4 +treatment. Although ocean acidification and eutrophication states had an impact on physiological performance, chlorophyll fluorescence was not affected by those conditions. Our results indicated that the physiological reactions by this alga were influenced to some extent by a rise in the levels of CO2 and NH4 + . Therefore, we expect that the biomass accumulation of S. japonica may well increase under future scenarios of ocean acidification and eutrophication.

Evolution of Abnormally Low Pressure at Bravo Dome and its Implications for Carbon Capture and Storage (CCS)

NASA Astrophysics Data System (ADS)

Akhbari, D.; Hesse, M. A.

2015-12-01

Carbon capture and storage allows reductions of the rapidly rising CO2 from fossil fuel-based power generation, if large storage rates and capacities can be achieved. The injection of large fluid volumes at high rates leads to a build-up of pore-pressure in the storage formation that may induce seismicity and compromise the storage security. Many natural CO2 fields in midcontinent US, in contrast, are under-pressured rather than over-pressured suggesting that natural processes reduce initial over-pressures and generate significant under-pressures. The question is therefore to understand the sequence of process(es) that allow the initial over-pressure to be eliminated and the under-pressure to be maintained over geological periods of time. We therefore look into pressure evolution in Bravo Dome, one of the largest natural CO2 accumulations in North America, which stores 1.3 Gt of CO2. Bravo Dome is only 580-900 m deep and is divided into several compartments with near gas-static pressure (see Figure). The pre-production gas pressures in the two main compartments that account for 70% of the mass of CO2 stored at Bravo Dome are more than 6 MPa below hydrostatic pressure. Here we show that the under-pressure in the Bravo Dome CO2 reservoir is maintained by hydrological compartmentalization over millennial timescales and generated by a combination of processes including cooling, erosional unloading, limited leakage into overlying formations, and CO2 dissolution into brine. Herein, we introduce CO2 dissolution into brine as a new process that reduce gas pressure in a compartmentalized reservoir and our results suggest that it may contribute significantly to reduce the initial pressure build-up due to injection. Bravo Dome is the first documented case of pressure drop due to CO2 dissolution. To have an accurate prediction of pressure evolution in Bravo Dome, our models must include geomechanics and thermodynamics for the reservoir while they account for the pressure changes due to the CO2 dissolution.

Co-evolution of SNF spliceosomal proteins with their RNA targets in trans-splicing nematodes.

PubMed

Strange, Rex Meade; Russelburg, L Peyton; Delaney, Kimberly J

2016-08-01

Although the mechanism of pre-mRNA splicing has been well characterized, the evolution of spliceosomal proteins is poorly understood. The U1A/U2B″/SNF family (hereafter referred to as the SNF family) of RNA binding spliceosomal proteins participates in both the U1 and U2 small interacting nuclear ribonucleoproteins (snRNPs). The highly constrained nature of this system has inhibited an analysis of co-evolutionary trends between the proteins and their RNA binding targets. Here we report accelerated sequence evolution in the SNF protein family in Phylum Nematoda, which has allowed an analysis of protein:RNA co-evolution. In a comparison of SNF genes from ecdysozoan species, we found a correlation between trans-splicing species (nematodes) and increased phylogenetic branch lengths of the SNF protein family, with respect to their sister clade Arthropoda. In particular, we found that nematodes (~70-80 % of pre-mRNAs are trans-spliced) have experienced higher rates of SNF sequence evolution than arthropods (predominantly cis-spliced) at both the nucleotide and amino acid levels. Interestingly, this increased evolutionary rate correlates with the reliance on trans-splicing by nematodes, which would alter the role of the SNF family of spliceosomal proteins. We mapped amino acid substitutions to functionally important regions of the SNF protein, specifically to sites that are predicted to disrupt protein:RNA and protein:protein interactions. Finally, we investigated SNF's RNA targets: the U1 and U2 snRNAs. Both are more divergent in nematodes than arthropods, suggesting the RNAs have co-evolved with SNF in order to maintain the necessarily high affinity interaction that has been characterized in other species.

Algal evolution in relation to atmospheric CO2: carboxylases, carbon-concentrating mechanisms and carbon oxidation cycles

PubMed Central

Raven, John A.; Giordano, Mario; Beardall, John; Maberly, Stephen C.

2012-01-01

Oxygenic photosynthesis evolved at least 2.4 Ga; all oxygenic organisms use the ribulose bisphosphate carboxylase-oxygenase (Rubisco)–photosynthetic carbon reduction cycle (PCRC) rather than one of the five other known pathways of autotrophic CO2 assimilation. The high CO2 and (initially) O2-free conditions permitted the use of a Rubisco with a high maximum specific reaction rate. As CO2 decreased and O2 increased, Rubisco oxygenase activity increased and 2-phosphoglycolate was produced, with the evolution of pathways recycling this inhibitory product to sugar phosphates. Changed atmospheric composition also selected for Rubiscos with higher CO2 affinity and CO2/O2 selectivity correlated with decreased CO2-saturated catalytic capacity and/or for CO2-concentrating mechanisms (CCMs). These changes increase the energy, nitrogen, phosphorus, iron, zinc and manganese cost of producing and operating Rubisco–PCRC, while biosphere oxygenation decreased the availability of nitrogen, phosphorus and iron. The majority of algae today have CCMs; the timing of their origins is unclear. If CCMs evolved in a low-CO2 episode followed by one or more lengthy high-CO2 episodes, CCM retention could involve a combination of environmental factors known to favour CCM retention in extant organisms that also occur in a warmer high-CO2 ocean. More investigations, including studies of genetic adaptation, are needed. PMID:22232762

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand.

PubMed

Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D; Lowry, Gregory V

2017-01-15

The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW=12K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7×10 -4 Lhr -1 m -2 ) and hydrogen evolution rate constant (1.4 nanomolLhr -1 m -2 ) were independent of nZVI concentration above 10g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H 2 evolution was explained by differences in pH and E h at each nZVI mass loading; PCE reactivity increased when solution E h decreased, and the H 2 evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime. Copyright © 2016 Elsevier B.V. All rights reserved.

Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

2014-11-01

We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

Biochemical characterization of predicted Precambrian RuBisCO

PubMed Central

Shih, Patrick M.; Occhialini, Alessandro; Cameron, Jeffrey C.; Andralojc, P John; Parry, Martin A. J.; Kerfeld, Cheryl A.

2016-01-01

The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism. PMID:26790750

Biochemical characterization of predicted Precambrian RuBisCO.

PubMed

Shih, Patrick M; Occhialini, Alessandro; Cameron, Jeffrey C; Andralojc, P John; Parry, Martin A J; Kerfeld, Cheryl A

2016-01-21

The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism.

Intra-puff CO and CO 2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

NASA Astrophysics Data System (ADS)

Crawford, Danielle R.; Parrish, Milton E.; Gee, Diane L.; Harward, Charles N.

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO 2 as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1 s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO 2 intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO 2 deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy.

PubMed

Crawford, Danielle R; Parrish, Milton E; Gee, Diane L; Harward, Charles N

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Evolution of CO2 in lakes Monoun and Nyos, Cameroon, before and during controlled degassing

USGS Publications Warehouse

Kusakabe, M.; Ohba, T.; Issa,; Yoshida, Y.; Satake, H.; Ohizumi, T.; Evans, William C.; Tanyileke, G.; Kling, G.W.

2008-01-01

Evolution of CO2 in Lakes Monoun and Nyos (Cameroon) before and during controlled degassing is described using results of regular monitoring obtained during the last 21 years. The CO2(aq) profiles soon after the limnic eruptions were estimated for Lakes Monoun and Nyos using the CTD data obtained in October and November 1986, respectively. Based on the CO2(aq) profiles through time, the CO2 Content and its change over time were calculated for both lakes. The CO2 accumulation rate calculated from the pre-degassing data, was constant after the limnic eruption at Lake Nyos (1986-2001), whereas the rate appeared initially high (1986-1996) but later slowed down (1996-2003) at Lake Monoun. The CO2 concentration at 58 m depth in Lake Monoun in January 2003 was very close to saturation due to the CO2 accumulation. This situation is suggestive of a mechanism for the limnic eruption, because it may take place spontaneously without receiving an external trigger. The CO2 content of the lakes decreased significantly after controlled degassing started in March 2001 at Lake Nyos and in February 2003 at Lake Monoun. The current content is lower than the content estimated soon after the limnic eruption at both lakes. At Monoun the degassing rate increased greatly after February 2006 due to an increase of the number of degassing pipes and deepening of the pipe intake depth. The current CO2 content is ???40% of the maximum content attained just before the degassing started. At current degassing rates the lower chemocline will subside to the degassing pipe intake depth of 93 m in about one year. After this depth is reached, the gas removal rate will progressively decline because water of lower CO2(aq) concentration will be tapped by the pipes. To keep the CO2 content of Lake Monoun as small as possible, it is recommended to set up a new, simple device that sends deep water to the surface since natural recharge of CO2 will continue. Controlled degassing at Lake Nyos since 2001 has also reduced the CO2 content. It is currently slightly below the level estimated after the limnic eruption in 1986. However, the current CO2 content still amounts to 80% of the maximum level of 14.8 giga moles observed in January 2001. The depth of the lower chemocline may reach the pipe intake depth of 203 m within a few years. After this situation is reached the degassing rate with the current system will progressively decline, and it would take decades to remove the majority of dissolved gases even if the degassing system keeps working continuously. Additional degassing pipes must be installed to speed up gas removal from Lake Nyos in order to make the area safer for local populations. Copyright ?? 2008 by The Geochemical Society of Japan.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

PubMed Central

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-01-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions. PMID:26355955

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co(2+) Solution: Interactional Performance and Mechanism.

PubMed

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-10

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co(2+) solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co(2+) reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the "structural influence" crucial for the full and dynamical understanding of nZVI reactions.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions.

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

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

Chen, Li; Wang, Mengyi; Kang, Qinjun

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

DOE PAGES

Chen, Li; Wang, Mengyi; Kang, Qinjun; ...

2018-04-26

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

Environmentally driven evolution of Rubisco and improved photosynthesis and growth within the C3 genus Limonium (Plumbaginaceae).

PubMed

Galmés, Jeroni; Andralojc, P John; Kapralov, Maxim V; Flexas, Jaume; Keys, Alfred J; Molins, Arántzazu; Parry, Martin A J; Conesa, Miquel À

2014-08-01

Carbon assimilation by most ecosystems requires ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco). Its kinetic parameters are likely to have evolved in parallel with intracellular CO2 availability, with the result that faster forms of Rubisco occur in species with CO2 -concentrating mechanisms. The Rubisco catalytic properties were determined and evaluated in relation to growth and carbon assimilation capacity in Mediterranean Limonium species, inhabiting severe stress environments. Significant kinetic differences between closely related species depended on two amino acid substitutions at functionally important residues 309 and 328 within the Rubisco large subunit. The Rubisco of species facing the largest CO2 restrictions during drought had relatively high affinity for CO2 (low Michaelis-Menten constant for CO2 Kc) but low maximum rates of carboxylation (kcatc), while the opposite was found for species that maintained higher CO2 concentrations under similar conditions. Rubisco kinetic characteristics were correlated with photosynthetic rate in both well-watered and drought-stressed plants. Moreover, the drought-mediated decrease in plant biomass accumulation was consistently lower in species with higher Rubisco carboxylase catalytic efficiency (kcatc/Kc). The present study is the first demonstration of Rubisco adaptation during species diversification within closely related C3 plants, revealing a direct relationship between Rubisco molecular evolution and the biomass accumulation of closely related species subjected to unfavourable conditions. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Pore scale study of multiphase multicomponent reactive transport during CO2 dissolution trapping

NASA Astrophysics Data System (ADS)

Chen, Li; Wang, Mengyi; Kang, Qinjun; Tao, Wenquan

2018-06-01

Solubility trapping is crucial for permanent CO2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO2-water two-phase flow, multicomponent (CO2(aq), H+, HCO3-, CO32- and OH-) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO2(aq) concentration, scCO2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is required by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Finally, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

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

Li, Hui; Li, Qi; Wen, Peng

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

DOE PAGES

Li, Hui; Li, Qi; Wen, Peng; ...

2018-01-15

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

2 years with comet 67P/Churyumov-Gerasimenko: H2O, CO2, CO as seen by ROSINA RTOF

NASA Astrophysics Data System (ADS)

Hoang, M.; Garnier, P.; Lasue, J.; Reme, H.; Altwegg, K.; Balsiger, H. R.; Bieler, A. M.; Calmonte, U.; Capria, M. T.; Combi, M. R.; De Keyser, J. M.; Fiethe, B.; Fougere, N.; Fuselier, S. A.; Galli, A.; Gasc, S.; Gombosi, T. I.; Hansen, K. C.; Jäckel, A.; Korth, A.; Mall, U.; Migliorini, A.; Rubin, M.; Sémon, T.; Tzou, C. Y.; Waite, J. H., Jr.; Wurz, P.

2017-12-01

The Rosetta space mission investigated comet 67P/Churyumov-Gerasimenko (67P) over two years from August 2014 to September 2016. Onboard the spacecraft, the ROSINA experiment included two mass spectrometers to derive the composition of neutrals and ions, and a COmet Pressure Sensor (COPS) to monitor the density and velocity of the neutrals in the coma. We will here analyse and discuss data from the Reflectron-type Time-Of-Flight instrument during the comet escort phase. The RTOF mass spectrometer possessed a wide mass range and a high temporal resolution (Balsiger et al., 2007). The analysis of 67P/C-G's coma major molecules over the mission showed strong variability of the comet coma's main volatiles concentrations (H2O, CO2, CO) and their relative abundances. The 2 years long Rosetta mission allowed us to observe the seasonal evolution in the atmosphere of 67P, in particular the change occurring during the equinoxes and at perihelion. In this work, we analyze the asymmetry in the outgassing rate before and after the perihelion (13/08/2015), the evolution of abundance ratios through the whole mission, and in particular the behavior of the very volatile CO molecules. Density maps projected on the surface of 67P demonstrate the evolution of the three main coma species after the outbound equinox. We will present first results of our comet nucleus thermal modelling used to simulate the internal structure and temperature evolution of 67P at characteristic surface areas. These results will be compared with the coma composition measurements obtained by ROSINA.

N2-fixing tropical legume evolution: a contributor to enhanced weathering through the Cenozoic?

PubMed Central

Hedin, Lars O.; Leake, Jonathan R.

2017-01-01

Fossil and phylogenetic evidence indicates legume-rich modern tropical forests replaced Late Cretaceous palm-dominated tropical forests across four continents during the early Cenozoic (58–42 Ma). Tropical legume trees can transform ecosystems via their ability to fix dinitrogen (N2) and higher leaf N compared with non-legumes (35–65%), but it is unclear how their evolutionary rise contributed to silicate weathering, the long-term sink for atmospheric carbon dioxide (CO2). Here we hypothesize that the increasing abundance of N2-fixing legumes in tropical forests amplified silicate weathering rates by increased input of fixed nitrogen (N) to terrestrial ecosystems via interrelated mechanisms including increasing microbial respiration and soil acidification, and stimulating forest net primary productivity. We suggest the high CO2 early Cenozoic atmosphere further amplified legume weathering. Evolution of legumes with high weathering rates was probably driven by their high demand for phosphorus and micronutrients required for N2-fixation and nodule formation. PMID:28814651

N2-fixing tropical legume evolution: a contributor to enhanced weathering through the Cenozoic?

PubMed

Epihov, Dimitar Z; Batterman, Sarah A; Hedin, Lars O; Leake, Jonathan R; Smith, Lisa M; Beerling, David J

2017-08-16

Fossil and phylogenetic evidence indicates legume-rich modern tropical forests replaced Late Cretaceous palm-dominated tropical forests across four continents during the early Cenozoic (58-42 Ma). Tropical legume trees can transform ecosystems via their ability to fix dinitrogen (N 2 ) and higher leaf N compared with non-legumes (35-65%), but it is unclear how their evolutionary rise contributed to silicate weathering, the long-term sink for atmospheric carbon dioxide (CO 2 ). Here we hypothesize that the increasing abundance of N 2 -fixing legumes in tropical forests amplified silicate weathering rates by increased input of fixed nitrogen (N) to terrestrial ecosystems via interrelated mechanisms including increasing microbial respiration and soil acidification, and stimulating forest net primary productivity. We suggest the high CO 2 early Cenozoic atmosphere further amplified legume weathering. Evolution of legumes with high weathering rates was probably driven by their high demand for phosphorus and micronutrients required for N 2 -fixation and nodule formation. © 2017 The Author(s).

CO 2 Leakage Into Shallow Aquifers: Modeling CO 2 Gas Evolution and Accumulation at Interfaces of Heterogeneity

DOE PAGES

Porter, Mark L.; Plampin, Michael; Pawar, Rajesh; ...

2014-12-31

The physicochemical processes associated with CO 2 leakage into shallow aquifer systems are complex and span multiple spatial and time scales. Continuum-scale numerical models that faithfully represent the underlying pore-scale physics are required to predict the long-term behavior and aid in risk analysis regarding regulatory and management decisions. This study focuses on benchmarking the numerical simulator, FEHM, with intermediate-scale column experiments of CO 2 gas evolution in homogeneous and heterogeneous sand configurations. Inverse modeling was conducted to calibrate model parameters and determine model sensitivity to the observed steady-state saturation profiles. It is shown that FEHM is a powerful tool thatmore » is capable of capturing the experimentally observed out ow rates and saturation profiles. Moreover, FEHM captures the transition from single- to multi-phase flow and CO 2 gas accumulation at interfaces separating sands. We also derive a simple expression, based on Darcy's law, for the pressure at which CO 2 free phase gas is observed and show that it reliably predicts the location at which single-phase flow transitions to multi-phase flow.« less

Chemical evolution in spiral and irregular galaxies

NASA Technical Reports Server (NTRS)

Torres-Peimbert, S.

1986-01-01

A brief review of models of chemical evolution of the interstellar medium in our galaxy and other galaxies is presented. These models predict the time variation and radial dependence of chemical composition in the gas as function of the input parameters; initial mass function, stellar birth rate, chemical composition of mass lost by stars during their evolution (yields), and the existence of large scale mass flows, like infall from the halo, outflow to the intergalactic medium or radial flows within a galaxy. At present there is a considerable wealth of observational data on the composition of HII regions in spiral and irregular galaxies to constrain the models. Comparisons are made between theory and the observed physical conditions. In particular, studies of helium, carbon, nitrogen and oxygen abundances are reviewed. In many molecular clouds the information we have on the amount of H2 is derived from the observed CO column density, and a standard CO/H2 ratio derived for the solar neighborhood. Chemical evolution models and the observed variations in O/H and N/O values, point out the need to include these results in a CO/H2 relation that should be, at least, a function of the O/H ratio. This aspect is also discussed.

Biodegradation of biodiesel fuels

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

Zhang, X.; Haws, R.; Wright, B.

1995-12-31

Biodiesel fuel test substances Rape Ethyl Ester (REE), Rape Methyl Ester (RME), Neat Rape Oil (NR), Say Methyl Ester (SME), Soy Ethyl Ester (SEE), Neat Soy Oil (NS), and proportionate combinations of RME/diesel and REE/diesel were studied to test the biodegradability of the test substances in an aerobic aquatic environment using the EPA 560/6-82-003 Shake Flask Test Method. A concurrent analysis of Phillips D-2 Reference Diesel was also performed for comparison with a conventional fuel. The highest rates of percent CO{sub 2} evolution were seen in the esterified fuels, although no significant difference was noted between them. Ranges of percentmore » CO{sub 2} evolution for esterified fuels were from 77% to 91%. The neat rape and neat soy oils exhibited 70% to 78% CO{sub 2} evolution. These rates were all significantly higher than those of the Phillips D-2 reference fuel which evolved from 7% to 26% of the organic carbon to CO{sub 2}. The test substances were examined for BOD{sub 5} and COD values as a relative measure of biodegradability. Water Accommodated Fraction (WAF) was experimentally derived and BOD{sub 5} and COD analyses were carried out with a diluted concentration at or below the WAF. The results of analysis at WAF were then converted to pure substance values. The pure substance BOD{sub 5} and COD values for test substances were then compared to a control substance, Phillips D-2 Reference fuel. No significant difference was noted for COD values between test substances and the control fuel. (p > 0.20). The D-2 control substance was significantly lower than all test substances for BCD, values at p << 0.01. RME was also significantly lower than REE (p < 0.05) and MS (p < 0.01) for BOD{sub 5} value.« less

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

ALMA SPECTROSCOPIC SURVEY IN THE HUBBLE ULTRA DEEP FIELD: CO LUMINOSITY FUNCTIONS AND THE EVOLUTION OF THE COSMIC DENSITY OF MOLECULAR GAS

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

Decarli, Roberto; Walter, Fabian; Aravena, Manuel

2016-12-10

In this paper we use ASPECS, the ALMA Spectroscopic Survey in the Hubble Ultra Deep Field in band 3 and band 6, to place blind constraints on the CO luminosity function and the evolution of the cosmic molecular gas density as a function of redshift up to z  ∼ 4.5. This study is based on galaxies that have been selected solely through their CO emission and not through any other property. In all of the redshift bins the ASPECS measurements reach the predicted “knee” of the CO luminosity function (around 5 × 10{sup 9} K km s{sup −1} pc{sup 2}). We find clear evidence ofmore » an evolution in the CO luminosity function with respect to z  ∼ 0, with more CO-luminous galaxies present at z  ∼ 2. The observed galaxies at z  ∼ 2 also appear more gas-rich than predicted by recent semi-analytical models. The comoving cosmic molecular gas density within galaxies as a function of redshift shows a drop by a factor of 3–10 from z  ∼ 2 to z  ∼ 0 (with significant error bars), and possibly a decline at z  > 3. This trend is similar to the observed evolution of the cosmic star formation rate density. The latter therefore appears to be at least partly driven by the increased availability of molecular gas reservoirs at the peak of cosmic star formation ( z  ∼ 2).« less

Two Back Stress Hardening Models in Rate Independent Rigid Plastic Deformation

NASA Astrophysics Data System (ADS)

Yun, Su-Jin

In the present work, the constitutive relations based on the combination of two back stresses are developed using the Armstrong-Frederick, Phillips and Ziegler’s type hardening rules. Various evolutions of the kinematic hardening parameter can be obtained by means of a simple combination of back stress rate using the rule of mixtures. Thus, a wide range of plastic deformation behavior can be depicted depending on the dominant back stress evolution. The ultimate back stress is also determined for the present combined kinematic hardening models. Since a kinematic hardening rule is assumed in the finite deformation regime, the stress rate is co-rotated with respect to the spin of substructure obtained by incorporating the plastic spin concept. A comparison of the various co-rotational rates is also included. Assuming rigid plasticity, the continuum body consists of the elastic deformation zone and the plastic deformation zone to form a hybrid finite element formulation. Then, the plastic deformation behavior is investigated under various loading conditions with an assumption of the J2 deformation theory. The plastic deformation localization turns out to be strongly dependent on the description of back stress evolution and its associated hardening parameters. The analysis for the shear deformation with fixed boundaries is carried out to examine the deformation localization behavior and the evolution of state variables.

Solar radiation and landscape evolution: co-evolution of topography, vegetation, and erosion rates in a semi-arid ecosystem

NASA Astrophysics Data System (ADS)

Istanbulluoglu, Erkan; Yetemen, Omer

2016-04-01

In this study CHILD landscape evolution model (LEM) is used to study the role of solar radiation on the co-evolution of landscape morphology, vegetation patterns, and erosion rates in a central New Mexico catchment. In the study site north facing slopes (NFS) are characterized by steep diffusion-dominated planar hillslopes covered by co-exiting juniper pine and grass vegetation. South facing slopes (SFS) are characterized by shallow slopes and covered by sparse shrub vegetation. Measured short-term and Holocene-averaged erosion rates show higher soil loss on SFS than NFS. In this study CHILD LEM is first confirmed with ecohydrologic field data and used to systematically examine the co-evolution of topography, vegetation pattern, and erosion rates. Aspect- and network-control are identified as the two main topographic drivers of soil moisture and vegetation organization on the landscape. Landscape-scale and long-term implications of solar radiation driven ecohdrologic patterns emerged in modeled landscape: NFS supported denser vegetation cover and became steeper and planar, while on SFS vegetation grew sparser and slopes declined with more fluvial activity. At the landscape scale, these differential erosion processes led to asymmetric development of catchment forms, consistent with regional observations. While the general patterns of vegetation and topography were reproduced by the model using a stationary representation of the current climate, the observed differential Holocene erosion rates were captured by the model only when cyclic climate is used. This suggests sensitivity of Holocene erosion rates to long-term climate fluctuations.

Diverse strategies of O2 usage for preventing photo-oxidative damage under CO2 limitation during algal photosynthesis.

PubMed

Shimakawa, Ginga; Matsuda, Yusuke; Nakajima, Kensuke; Tamoi, Masahiro; Shigeoka, Shigeru; Miyake, Chikahiro

2017-01-20

Photosynthesis produces chemical energy from photon energy in the photosynthetic electron transport and assimilates CO 2 using the chemical energy. Thus, CO 2 limitation causes an accumulation of excess energy, resulting in reactive oxygen species (ROS) which can cause oxidative damage to cells. O 2 can be used as an alternative energy sink when oxygenic phototrophs are exposed to high light. Here, we examined the responses to CO 2 limitation and O 2 dependency of two secondary algae, Euglena gracilis and Phaeodactylum tricornutum. In E. gracilis, approximately half of the relative electron transport rate (ETR) of CO 2 -saturated photosynthesis was maintained and was uncoupled from photosynthesis under CO 2 limitation. The ETR showed biphasic dependencies on O 2 at high and low O 2 concentrations. Conversely, in P. tricornutum, most relative ETR decreased in parallel with the photosynthetic O 2 evolution rate in response to CO 2 limitation. Instead, non-photochemical quenching was strongly activated under CO 2 limitation in P. tricornutum. The results indicate that these secondary algae adopt different strategies to acclimatize to CO 2 limitation, and that both strategies differ from those utilized by cyanobacteria and green algae. We summarize the diversity of strategies for prevention of photo-oxidative damage under CO 2 limitation in cyanobacterial and algal photosynthesis.

What determines catalyst functionality in molecular water oxidation? Dependence on ligands and metal nuclearity in cobalt clusters.

PubMed

Smith, Paul F; Kaplan, Christopher; Sheats, John E; Robinson, David M; McCool, Nicholas S; Mezle, Nicholas; Dismukes, G Charles

2014-02-17

The metal-oxo M4O4 "cubane" topology is of special significance to the field of water oxidation as it represents the merging of bioinspired structural principles derived from natural photosynthesis with successful artificial catalysts known to date. Herein, we directly compare the rates of water oxidation/O2 evolution catalyzed by six cobalt-oxo clusters including the Co4O4 cubanes, Co4O4(OAc)4(py)4 and [Co4O4(OAc)2(bpy)4](2+), using the common Ru(bpy)3(2+)/S2O8(2-) photo-oxidant assay. At pH 8, the first-order rate constants for these cubanes differ by 2-fold, 0.030 and 0.015 s(-1), respectively, reflecting the number of labile carboxylate sites that allow substrate water binding in a pre-equilibrium step before O2 release. Kinetic results reveal a deprotonation step occurs on this pathway and that two electrons are removed before O2 evolution occurs. The Co4O4 cubane core is shown to be the smallest catalytic unit for the intramolecular water oxidation pathway, as neither "incomplete cubane" trimers [Co3O(OH)3(OAc)2(bpy)3](2+) and [Co3O(OH)2(OAc)3(py)5](2+) nor "half cubane" dimers [Co2(OH)2(OAc)3(bpy)2](+) and [Co2(OH)2(OAc)3(py)4](+) were found capable of evolving O2, despite having the same ligand sets as their cubane counterparts. Electrochemical studies reveal that oxidation of both cubanes to formally Co4(3III,IV) (0.7 V vs Ag/AgCl) occurs readily, while neither dimers nor trimers are oxidized below 1.5 V, pointing to appreciably greater charge delocalization in the [Co4O4](5+) core. The origin of catalytic activity by Co4O4 cubanes illustrates three key features for water oxidation: (1) four one-electron redox metals, (2) efficient charge delocalization of the first oxidation step across the Co4O4 cluster, allowing for stabilization of higher oxidizing equivalents, and (3) terminal coordination site for substrate aquo/oxo formation.

Short- versus long-term responses to changing CO2 in a coastal dinoflagellate bloom: implications for interspecific competitive interactions and community structure.

PubMed

Tatters, Avery O; Schnetzer, Astrid; Fu, Feixue; Lie, Alle Y A; Caron, David A; Hutchins, David A

2013-07-01

Increasing pCO2 (partial pressure of CO2 ) in an "acidified" ocean will affect phytoplankton community structure, but manipulation experiments with assemblages briefly acclimated to simulated future conditions may not accurately predict the long-term evolutionary shifts that could affect inter-specific competitive success. We assessed community structure changes in a natural mixed dinoflagellate bloom incubated at three pCO2 levels (230, 433, and 765 ppm) in a short-term experiment (2 weeks). The four dominant species were then isolated from each treatment into clonal cultures, and maintained at all three pCO2 levels for approximately 1 year. Periodically (4, 8, and 12 months), these pCO2 -conditioned clones were recombined into artificial communities, and allowed to compete at their conditioning pCO2 level or at higher and lower levels. The dominant species in these artificial communities of CO2 -conditioned clones differed from those in the original short-term experiment, but individual species relative abundance trends across pCO2 treatments were often similar. Specific growth rates showed no strong evidence for fitness increases attributable to conditioning pCO2 level. Although pCO2 significantly structured our experimental communities, conditioning time and biotic interactions like mixotrophy also had major roles in determining competitive outcomes. New methods of carrying out extended mixed species experiments are needed to accurately predict future long-term phytoplankton community responses to changing pCO2 . © 2013 The Author(s). Evolution © 2013 The Society for the Study of Evolution.

Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

PubMed

Zhang, Yun-Xiao; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

2018-09-15

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS 2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS 2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS 2 /CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS 2 /CNTs/CN catalyst exhibits high performance for H 2 evolution and the optimized rate is 309.9 μmol·h -1 ·g -1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost. Copyright © 2018 Elsevier Inc. All rights reserved.

Documenting a significant relationship between macroevolutionary origination rates and Phanerozoic pCO2 levels.

PubMed

Cornette, James L; Lieberman, Bruce S; Goldstein, Robert H

2002-06-11

We show that the rates of diversification of the marine fauna and the levels of atmospheric CO(2) have been closely correlated for the past 545 million years. These results, using two of the fundamental databases of the Earth's biota and the Earth's atmospheric composition, respectively, are highly statistically significant (P < 0.001). The strength of the correlation suggests that one or more environmental variables controlling CO(2) levels have had a profound impact on evolution throughout the history of metazoan life. Comparing our work with highly significant correlations described by D. H. Rothman [Rothman, D. H. (2001) Proc. Natl. Acad. Sci. USA 98, 4305-4310] between total biological diversity and a measure of stable carbon isotope fractionation, we find that the rates of diversification rather than total diversification correlate with environmental variables, and that the rate of diversification follows the record of CO(2) projected by R. A. Berner and Z. Kothavala [Berner, R. A. & Kothavala, Z. (2001) Am. J. Sci. 301, 182-204] more closely than that predicted by Rothman.

Carbon dioxide exchange in compact and semi-open sorghum inflorescences

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

Eastin, J.D.; Sullivan, C.Y.

Carbon dioxide exchange rates were monitored in light and dark in compact and semi-open heads of sorghum (Sorghum bicolor (L.) Moench). Developmental stages ranged from bottom to hard dough in the grain. Highest CO/sub 2/ uptake in both head types occurred at the bloom stage when net uptake rates for semi-open and compact type heads were 3.9 and 1.2 mg CO/sub 2/ g dry wt/sup -1/ hr/sup -1/, respectively. Beginning at the milk stage, a net CO/sub 2/ evolution on the order of 1 to 1.4 mg g dry wt/sup -1/ hr/sup -1/ occurred in compact heads in the light.more » The semi-open head type continued a small net CO/sub 2/ uptake in the light through the milk and soft dough stages. Both head types evolved CO/sub 2/ at hard dough stage. Dark respiration was similar in both head types and decreased from about 4 to 1 mg CO/sub 2/ g dry wt/sup -1/ hr/sup -1/ from bloom to hard dough. 16 references, 1 figure.« less

Microbial oxidation of lithospheric organic carbon in rapidly eroding tropical mountain soils

NASA Astrophysics Data System (ADS)

Hemingway, Jordon D.; Hilton, Robert G.; Hovius, Niels; Eglinton, Timothy I.; Haghipour, Negar; Wacker, Lukas; Chen, Meng-Chiang; Galy, Valier V.

2018-04-01

Lithospheric organic carbon (“petrogenic”; OCpetro) is oxidized during exhumation and subsequent erosion of mountain ranges. This process is a considerable source of carbon dioxide (CO2) to the atmosphere over geologic time scales, but the mechanisms that govern oxidation rates in mountain landscapes are poorly constrained. We demonstrate that, on average, 67 ± 11% of the OCpetro initially present in bedrock exhumed from the tropical, rapidly eroding Central Range of Taiwan is oxidized in soils, leading to CO2 emissions of 6.1 to 18.6 metric tons of carbon per square kilometer per year. The molecular and isotopic evolution of bulk OC and lipid biomarkers during soil formation reveals that OCpetro remineralization is microbially mediated. Rapid oxidation in mountain soils drives CO2 emission fluxes that increase with erosion rate, thereby counteracting CO2 drawdown by silicate weathering and biospheric OC burial.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

In situ Visualization of State-of-Charge Heterogeneity within a LiCoO 2 Particle that Evolves upon Cycling at Different Rates

DOE PAGES

Xu, Yahong; Hu, Enyuan; Zhang, Kai; ...

2017-05-05

For designing new battery systems with higher energy density and longer cycle life, it is important to understand the degradation mechanism of the electrode material, especially at the individual particle level. Using in situ transmission X-ray microscopy (TXM) coupled to a pouch cell setup, the inhomogeneous Li distribution as well as the formation, population, and evolution of inactive domains in a single LiCoO 2 particle were visualized in this paper as it was cycled for many times. It is found that the percentage of the particle that fully recovered to the pristine state is strongly related to the cycling rate.more » Interestingly, we also observed the evolution of the inactive region within the particle during long-term cycling. The relationship between morphological degradation and chemical inhomogeneity, including the formation of unanticipated Co metal phase, is also observed. Finally, our work highlights the capability of in situ TXM for studying the degradation mechanism of materials in LIBs.« less

Preparation of NiS/ZnIn2S4 as a superior photocatalyst for hydrogen evolution under visible light irradiation

PubMed Central

Wei, Liang; Chen, Yongjuan; Zhao, Jialin

2013-01-01

Summary In this study, NiS/ZnIn2S4 nanocomposites were successfully prepared via a facile two-step hydrothermal process. The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). Their photocatalytic performance for hydrogen evolution under visible light irradiation was also investigated. It was found that the photocatalytic hydrogen evolution activity over hexagonal ZnIn2S4 can be significantly increased by loading NiS as a co-catalyst. The formation of a good junction between ZnIn2S4 and NiS via the two step hydrothermal processes is beneficial for the directional migration of the photo-excited electrons from ZnIn2S4 to NiS. The highest photocatalytic hydrogen evolution rate (104.7 μmol/h), which is even higher than that over Pt/ZnIn2S4 nanocomposite (77.8 μmol/h), was observed over an optimum NiS loading amount of 0.5 wt %. This work demonstrates a high potential of the developing of environmental friendly, cheap noble-metal-free co-catalyst for semiconductor-based photocatalytic hydrogen evolution. PMID:24455453

Testing of some assumptions about biodegradability in soil as measured by carbon dioxide evolution

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

El-Din Sharabi, N.; Bartha, R.

1993-04-01

The Toxic Substance Control Act calls for a premanufacturing review of novel chemical substances including their biodegradability. Carbon dioxide evolution, using non-labeled carbon or [sup 14]C, is a common method of testing. This study examines assumptions of carbon dioxide evolution testing. Test substances used included: glucose, adipic acid, benzoic acid, and n-hexadecane. Chemical composition other than carbon content appears to influence minimally the percentages conversion to CO[sub 2]. However, that although CO[sub 2] evolution seemed proportional to the carbon content and concentration of the test substance, at least one-half of the evolved net CO[sub 2] did not come directly frommore » the test substance. Conversion to CO[sub 2] in the soil appeared to depend on carbon content only. In experiments of 1 month or longer, the net CO[sub 2] evolution in response to substrate may be above 100% of the added substrate carbon. Whether this applies to all substrate additions remains to be studied. The authors conclude that net CO[sub 2] and [sup 14]CO[sub 2] evolution measurements are useful as a first-tier tests for assessing biodegradability in soil. 11 refs., 6 figs.« less

Peroxisomal Malate Dehydrogenase Is Not Essential for Photorespiration in Arabidopsis But Its Absence Causes an Increase in the Stoichiometry of Photorespiratory CO2 Release1[W][OA

PubMed Central

Cousins, Asaph B.; Pracharoenwattana, Itsara; Zhou, Wenxu; Smith, Steven M.; Badger, Murray R.

2008-01-01

Peroxisomes are important for recycling carbon and nitrogen that would otherwise be lost during photorespiration. The reduction of hydroxypyruvate to glycerate catalyzed by hydroxypyruvate reductase (HPR) in the peroxisomes is thought to be facilitated by the production of NADH by peroxisomal malate dehydrogenase (PMDH). PMDH, which is encoded by two genes in Arabidopsis (Arabidopsis thaliana), reduces NAD+ to NADH via the oxidation of malate supplied from the cytoplasm to oxaloacetate. A double mutant lacking the expression of both PMDH genes was viable in air and had rates of photosynthesis only slightly lower than in the wild type. This is in contrast to other photorespiratory mutants, which have severely reduced rates of photosynthesis and require high CO2 to grow. The pmdh mutant had a higher O2-dependent CO2 compensation point than the wild type, implying that either Rubisco specificity had changed or that the rate of CO2 released per Rubisco oxygenation was increased in the pmdh plants. Rates of gross O2 evolution and uptake were similar in the pmdh and wild-type plants, indicating that chloroplast linear electron transport and photorespiratory O2 uptake were similar between genotypes. The CO2 postillumination burst and the rate of CO2 released during photorespiration were both greater in the pmdh mutant compared with the wild type, suggesting that the ratio of photorespiratory CO2 release to Rubisco oxygenation was altered in the pmdh mutant. Without PMDH in the peroxisome, the CO2 released per Rubisco oxygenation reaction can be increased by over 50%. In summary, PMDH is essential for maintaining optimal rates of photorespiration in air; however, in its absence, significant rates of photorespiration are still possible, indicating that there are additional mechanisms for supplying reductant to the peroxisomal HPR reaction or that the HPR reaction is altogether circumvented. PMID:18685043

Simulation of permeability evolution of leakage pathway in carbonate-rich caprocks in carbon sequestration

NASA Astrophysics Data System (ADS)

Guo, B.; Fitts, J. P.; Dobossy, M. E.; Peters, C. A.

2013-12-01

Geologic carbon sequestration in deep saline aquifers is a promising strategy for mitigating climate change. A major concern is the possibility of brine and CO2 migration through the caprock such as through fractures and faults. In this work, we examine the extent to which mineral dissolution will substantially alter the porosity and permeability of caprock leakage pathways as CO2-acidified brine flows through them. Three models were developed. Firstly, a reactive transport model, Permeability Evolution of Leakage pathway (PEL), was developed to simulate permeability evolution of a leakage pathway during the injection period, and assumes calcite is the only reactive mineral. The system domain is a 100 m long by 0.2 m diameter cylindrical flow path with fixed boundaries containing a rock matrix with an initial porosity of 30% and initial permeability of 1×10-13 m2. One example result is for an initial calcite volume fraction (CVF) of 0.20, in which all the calcite is dissolved after 50 years and the permeability reaches 3.2×10-13 m2. For smaller values of CVF, the permeability reaches its final value earlier but the increase in permeability is minimal. For a large value of CVF such as 0.50, the permeability could eventually reach 1×10-12 m2, but the large amount of dissolved calcium buffers the solution and slows the reaction. After 50 years the permeability change is negligible. Thus, there is a non-monotonic relationship between the amount of calcite in the rock and the resulting permeability change because of the competing dynamics of calcite dissolution and alkalinity build-up. In the second model, PEL was coupled to an existing basin-scale multiphase flow model, Princeton's Estimating Leakage Semi-Analytical (ELSA) model. The new model, ELSA-PEL, estimates the brine and CO2 leakage rates during the injection period under conditions of permeability evolution. The scenario considered in this work is for 50 years of CO2 injection into the Mt. Simon formation in the Michigan basin at an injection rate of 1 Mt/y. As an example, for a CVF value of 5%, the brine leakage rate after fifty years for a leakage pathway 1,000 m distance from the injection well is 0.88 kg/s, which is 2.4% larger than if there were no geochemical evolution of the permeability. In a sensitivity analysis with regard to the distance between the leakage pathway and the injection well, it was found that the cumulative leakage first increases with the distance and the relationship reverses after a certain distance. When the leakage pathway is farther away, the pressure increment drops leading to less acid brine flow; meanwhile, the time before the CO2 plume reaches the pathway is longer and this lengthens the reaction time with brine. Thirdly, we explored the role that SO2 would play if it were present as a co-injectant in carbon sequestration. The reaction considered is SO2 hydrolysis to form sulfurous acid. We expect the sulfurous acid will erode the calcite faster than carbonic acid because it is a stronger acid. Contrary to intuition, the simulation results showed a decrease in permeability due to CaSO3 precipitation in replacement of CaCO3, as CaSO3 has a larger molar volume.

Light-enhanced dark respiration in leaves, isolated cells and protoplasts of various types of C4 plants.

PubMed

Parys, Eugeniusz; Jastrzebski, Hubert

2006-04-01

The rate of respiratory CO2 evolution from the leaves of Zea mays, Panicum miliaceum, and Panicum maximum, representing NADP-ME, NAD-ME, and PEP-CK types of C4 plants, respectively, was increased by approximately two to four times after a period of photosynthesis. This light-enhanced dark respiration (LEDR) was a function of net photosynthetic rate specific to plant species, and was depressed by 1% O2. When malate, aspartate, oxaloacetate or glycine solution at 50 mM concentration was introduced into the leaves instead of water, the rate of LEDR was enhanced, far less in Z. mays (by 10-25%) than in P. miliaceum (by 25-35%) or P. maximum (by 40-75%). The enhancement of LEDR under glycine was relatively stable over a period of 1 h, whereas the remaining metabolites caused its decrease following a transient increase. The metabolites reduced the net photosynthesis rate in the two Panicum species, but not in Z. mays, where this process was stimulated by glycine. The bundle sheath cells from P. miliaceum exhibited a higher rate of LEDR than those of Z. mays and P. maximum. Glycine had no effect on the respiration rate of the cells, but malate increased in cells of Z. mays and P. miliaceum by about 50% and 30%, respectively. With the exception of aspartate, which stimulated both the O2 evolution and O2 uptake in P. maximum, the remaining metabolites reduced photosynthetic O2 evolution from bundle sheath cells in Panicun species. The net O2 exchange in illuminated cells of Z. mays did not respond to CO2 or metabolites. Leaf mesophyll protoplasts of Z. mays and P. miliaceum, and bundle sheath protoplasts of Z. mays, which are unable to fix CO2 photosynthetically, also produced LEDR, but the mesophyll protoplasts, compared with bundle sheath protoplasts, required twice the time of illumination to obtain the maximal rate. The results suggest that the substrates for LEDR in C4 plants are generated during a period of illumination not only via the Calvin cycle reactions, but also by the conversion of endogenous compounds present in leaf cells. The stimulation of LEDR under glycine is discussed in relation to its direct or indirect effect on mitochondrial respiration.

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

Star Formation in the Central Regions of Galaxies

NASA Astrophysics Data System (ADS)

Tsai, Mengchun

2015-08-01

The galactic central region connects the galactic nucleus to the host galaxy. If the central black hole co-evolved with the host galaxies, there should be some evidence left in the central region. We use the environmental properties in the central regions such as star-forming activity, stellar population and molecular abundance to figure out a possible scenario of the evolution of galaxies. In this thesis at first we investigated the properties of the central regions in the host galaxies of active and normal galaxies. We used radio emission around the nuclei of the host galaxies to represent activity of active galactic nuclei (AGNs), and used infrared ray (IR) emission to represent the star-forming activity and stellar population of the host galaxies. We determined that active galaxies have higher stellar masses (SMs) within the central kiloparsec radius than normal galaxies do independent of the Hubble types of the host galaxies; but both active and normal galaxies exhibit similar specific star formation rates (SSFRs). We also discovered that certain AGNs exhibit substantial inner stellar structures in the IR images; most of the AGNs with inner structures are Seyferts, whereas only a few LINERs exhibit inner structures. We note that the AGNs with inner structures show a positive correlation between the radio activity of the AGNs and the SFRs of the host galaxies, but the sources without inner structures show a negative correlation between the radio power and the SFRs. These results might be explained with a scenario of starburst-AGN evolution. In this scenario, AGN activities are triggered following a nuclear starburst; during the evolution, AGN activities are accompanied by SF activity in the inner regions of the host galaxies; at the final stage of the evolution, the AGNs might transform into LINERs, exhibiting weak SF activity in the central regions of the host galaxies. For further investigation about the inner structure, we choose the most nearby and luminous Seyfert galaxy with inner structure as an example. In this thesis, we present CO(3-2) interferometric observations of the central region of the Seyfert 2 galaxy NGC1068 using the Submillimeter Array, together with CO(1-0) data taken with the Owens Valley Radio Observatory Millimeter Array. Both the CO(3-2) and CO(1-0) emission lines are mainly distributed within ~5 arcsec of the nucleus and along the spiral arms, but the intensity distributions show differences; the CO(3-2) map peaks in the nucleus, while the CO(1-0) emission is mainly located along the spiral arms. The CO(3-2)/CO(1-0) ratio is about 3.1 in the nucleus, which is four times as large as the average line ratio in the spiral arms, suggesting that the molecular gas there must be affected by the radiation arising from the AGN. On the other hand, the line ratios in the spiral arms vary over a wide range from 0.24 to 2.34 with a average value around 0.75, which is similar to the line ratios of star-formation regions, indicating that the molecular gas is affected by star formation. Besides, we see a tight correlation between CO(3-2)/(1-0) ratios in the spiral arms and star formation rate surface densities derived from Spitzer 8 micron dust flux densities. We also compare the CO(3-2)/(1-0) ratio and the star formation rate at different positions within the spiral arms; both are found to decrease as the radius from the nucleus increases.

Fast stochastic algorithm for simulating evolutionary population dynamics

NASA Astrophysics Data System (ADS)

Tsimring, Lev; Hasty, Jeff; Mather, William

2012-02-01

Evolution and co-evolution of ecological communities are stochastic processes often characterized by vastly different rates of reproduction and mutation and a coexistence of very large and very small sub-populations of co-evolving species. This creates serious difficulties for accurate statistical modeling of evolutionary dynamics. In this talk, we introduce a new exact algorithm for fast fully stochastic simulations of birth/death/mutation processes. It produces a significant speedup compared to the direct stochastic simulation algorithm in a typical case when the total population size is large and the mutation rates are much smaller than birth/death rates. We illustrate the performance of the algorithm on several representative examples: evolution on a smooth fitness landscape, NK model, and stochastic predator-prey system.

Use of scanning calorimetry and microrespiration to determine effects of Bt toxin doses on Pandemis leafroller (Lepidoptera: Tortricidae) metabolism

USDA-ARS?s Scientific Manuscript database

Differential scanning calorimetry and microrespiration were used to determine the effects of the biopesticide, Bt toxin, on the metabolism of infected Pandemis leafroller, Pandemis purusana (Kearfott). The metabolic heat rate, CO2 evolution, O2 consumption of 2nd and 3rd instars following a 2 h expo...

Preliminary evidences of CCM operation and its down regulation in relation to increasing CO2 levels in natural phytoplankton assemblages from the coastal waters of Bay of Bengal

NASA Astrophysics Data System (ADS)

Biswas, Haimanti; Rahman Shaik, Aziz Ur; Bandyopadhyay, Debasmita

2014-05-01

Bay of Bengal (BoB), a low productive part of the North Indian Ocean, often possesses low CO2 levels in its surface water and diatoms dominate the phytoplankton communities. Virtually no studies are available from this area reporting how this diatom dominated phytoplankton community would respond any increase in dissolved CO2 levels either naturally or anthopogenically. In most of the marine phytoplankton, the inefficiency of the sole carbon fixing enzyme Rubisco necessitates the need of concentrating dissolved inorganic carbon (DIC) (mostly as HCO3) inside the cell in excess of the ambient water concentrations in order to maintain high rate of photosynthesis under low CO2 levels through an energy consuming carbon concentration mechanisms (CCMs). The ubiquitous enzyme carbonic anhydrase (CA) plays a vital role in CCMs by converting HCO3- to CO2 and usually utilizes the trace metal zinc (Zn) as a cofactor. However, it is evident in many marine phytoplankton species that with increasing external CO2 levels, CCMs can be down-regulated leading to energetic savings which can be reallocated to growth; although exceptions occur. Hence, in order to predict their responses to the projected changes, it is imperative to understand their carbon metabolism patterns. We have conducted a series of incubation experiments in microcosms with natural phytoplankton communities from the coastal waters of BoB under different CO2 levels. Our results revealed that the rate of net photosynthetic oxygen evolution and biomass build-up increased in response to increasing CO2 levels. The depletion in δ13CPOM values were more in the high CO2 treatments relative to the low CO2 treated cells (control), indicating that dissolved CO2 uptake was higher when CO2 levels were increased. When additional Zn was added to the low CO2 treated cells, net photosynthetic oxygen evolution rate was increased significantly than that of the untreated control. It is likely that upon the supply of Zn under low CO2 levels, CA activity was enhanced and accelerated DIC transport and photosynthetic rate. Moreover, δ13CPOM values of low CO2 samples (both Zn treated and untreated) were almost identical, though the rate of photosynthesis was higher in response to Zn addition. This could be because of the fact that under low CO2 levels, DIC was possibly transported as HCO3- and an active HCO3- transport can contribute to low discrimination of 13C compared to diffusive CO2uptake leading to unaltered values of δ13CPOM. Furthermore, under low CO2 treatments, the need of nitrogen resource can be higher to maintain an active CCM (to build-up required proteins, Rubisco and CCM components) and our results showed higher values of δ15NPOMunder low CO2 levels relative to the high CO2treatments suggesting higher nitrogen utilization efficiency in the former case. These observations strengthen the possibility of operating an active CCM under low CO2 levels. HPLC pigment analysis revealed the occurrences of diatoxanthin (DT) [indicator of non-photo-chemical quenching (NPQ)] and high values of photoprotective carotenoid to light harvesting carotenoid ratios (PPC/LHC) in the low CO2 treated cells indicating light stress. This is likely that, when CO2, the only substrate for Rubisco, is low, absorbed light energy within the cell can be surplus leading to photo-damage and to protect the cell from potential damage, DT was produced by energy dissipation via NPQ and PPC were synthesized in excess of LHC. Conversely, in Zn and high CO2 treated cells, the absence of DT and reduced values of PPC/LHC indirectly indicates reduced light stress which was possibly because of enhanced supply of Rubisco substrate either via active bicarbonate transport or diffusive CO2 supply. Thus, we infer that the diatom dominated phytoplankton communities from the study area perform CCMs under low CO2 conditions and the same can be down regulated upon the increasing levels of CO2 and the community may benefit from the increasing CO2 levels followed by increased rate of carbon fixation. These can have large biogeochemical significance.

Temporal evolution of the anthropogenic CO2 and acidification of the northwestern Mediterranean Sea, from the mid-1990s to the mid-2000s

NASA Astrophysics Data System (ADS)

Savy, J.-P.; Yao, K. M.; Touratier, F.; Goyet, C.

2012-04-01

Since the beginning of the industrial era, humankind consumption of fossil fuels at increasing rates has led to increases in atmospheric CO2 concentrations by approximately 105 ppm. In the same time, the Mediterranean coastal regions experienced a brutal population growth, from 94 million habitants in 1950 to 274 million in 2000, generating a strong anthropogenic pressure on the Mediterranean marine ecosystems. To follow the man-induced changes on the Mediterranean carbonate system properties (pH; total alkalinity, AT; total inorganic carbon CT, and CO2 partial pressure, pCO2), an entire body-research has recently emerged in order to quantify both the present and future penetration of anthropogenic carbon (CANT) in the Mediterranean Sea and the inferred acidification of its waters. From monthly observations accumulated over more than a decade (from 1993 to 2005) at DYFAMED time-series station (DYnamique des Flux Atmosphériques en MEDiterranée) located in the central part of the Ligurian Sea, Touratier and Goyet (2009) have estimated the temporal evolution of CANT of the western Mediterranean Sea. This study highlights that concentrations of anthropogenic CO2 are much higher at DYFAMED site (> 50 mol.kg-1) than those found in the Atlantic Ocean. Our study, conducted with measurements performed at 10 meters depth from 1995 to 2011 at the same location, allowed us to investigate the temporal evolution of CANT into the upper seawater layer. Our results indicate an averaged annual CANT increase of 3 µmol.kg-1 and a linked pH drop of 0.0032 per year confirming the ongoing acidification of the Mediterranean water masses. These results suggest the vulnerability and the endangerment of the Mediterranean ecosystems by the massive human-induced CO2 emissions. Touratier F. and C. Goyet (2009). Decadal evolution of anthropogenic CO2 in the north western Mediterranean Sea (at the Dyfamed site) from the mid-1990's to the mid-2000's. Deep Sea Research Part I, 56, 1708-1716

Co-evolutionary constraints of globular proteins correlate with their folding rates.

PubMed

Mallik, Saurav; Kundu, Sudip

2015-08-04

Folding rates (lnkf) of globular proteins correlate with their biophysical properties, but relationship between lnkf and patterns of sequence evolution remains elusive. We introduce 'relative co-evolution order' (rCEO) as length-normalized average primary chain separation of co-evolving pairs (CEPs), which negatively correlates with lnkf. In addition to pairs in native 3D contact, indirectly connected and structurally remote CEPs probably also play critical roles in protein folding. Correlation between rCEO and lnkf is stronger in multi-state proteins than two-state proteins, contrasting the case of contact order (co), where stronger correlation is found in two-state proteins. Finally, rCEO, co and lnkf are fitted into a 3D linear correlation. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Photoelectrocatalytic reduction of CO2 to methanol over a photosystem II-enhanced Cu foam/Si-nanowire system.

PubMed

Lian, Zichao; Pan, Donglai; Wang, Wenchao; Zhang, Dieqing; Li, Guisheng; Li, Hexing

2017-10-01

A solar-light double illumination photoelectrocatalytic cell (SLDIPEC) was fabricated for autonomous CO 2 reduction and O 2 evolution with the aid of photosystem II (PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires (Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO 2 conversion to methanol, with a high evolution rate (41.94mmol/hr), owing to fast electron transfer from PS-II to Cu foam. Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage (0.5V), and a suitable conduction band potential of Si (-0.6eV) allowed CO 2 to be easily reduced to CH 3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO 2 (8.03mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy. Copyright © 2017. Published by Elsevier B.V.

Adaptive Molecular Evolution for 13,000 Phage Generations

PubMed Central

Wichman, Holly A.; Millstein, Jack; Bull, J. J.

2005-01-01

Bacteriophage φX174 was evolved on a continuous supply of sensitive hosts for 180 days (∼13,000 phage generations). The average rate of nucleotide substitution was nearly 0.2% (11 substitutions)/20 days, and, surprisingly, substitutions accumulated in a clock-like manner throughout the study, except for a low rate during the first 20 days. Rates of silent and missense substitutions varied over time and among genes. Approximately 40% of the 71 missense changes and 25% of the 58 silent changes have been observed in previous adaptations; the rate of parallel substitution was highest in the early phase of the evolution, but 7% of the later changes had evolved in previous studies of much shorter duration. Several lines of evidence suggest that most of the changes were adaptive, even many of the silent substitutions. The sustained, high rate of adaptive evolution for 180 days defies a model of adaptation to a constant environment. We instead suggest that continuing molecular evolution reflects a potentially indefinite arms race, stemming from high levels of co-infection and the resulting conflict among genomes competing within the same cell. PMID:15687276

Photocatalytic water oxidation by a pyrochlore oxide upon irradiation with visible light: rhodium substitution into yttrium titanate.

PubMed

Kiss, Borbala; Didier, Christophe; Johnson, Timothy; Manning, Troy D; Dyer, Matthew S; Cowan, Alexander J; Claridge, John B; Darwent, James R; Rosseinsky, Matthew J

2014-12-22

A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2 Ti2 O7 is demonstrated by monitoring Vegard's law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2 Ti1.94 Rh0.06 O7 an excellent candidate for use in a Z-scheme water-splitting system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of complex carbon addition to soil CO2 efflux and isotopic composition to soils near dead and live piñon pine trees

NASA Astrophysics Data System (ADS)

Powers, H.; McDowell, N.; Breecker, D. O.

2010-12-01

We test the hypothesis that soils collected near dead and living pinus edulous (piñon pine) trees should show a difference in their capacities to decompose complex carbon compounds. Since soils near dead trees have a large amount of cellulose and other complex carbon, the soil microbial community should be selected to metabolize cellulose. We collected soils from both live and dead piñon trees, added cellulose to half of the replicates, and placed them in microcosms for incubation. The microcosms were periodically sampled by a trace gas analyzer (TGA100, Campbell Scientific, USA) for CO2 concentration and δ13C and δ18O analysis. We found that CO2 evolution rates from live soils were significantly higher than rates from dead soils (1.1 and 0.6 ug CO2 g-1 soil s-1 respectively); soils with added cellulose displayed higher rates (1.1 and 0.8 and ug CO2 g-1 soil s-1). We did not see any significant differences in δ13C values between treatments, but there was a difference in δ18O between soils treated with cellulose and soils with no cellulose. Soils from both dead and live trees showed an increase in CO2 efflux when cellulose was added; however there was no distinguishable difference in efflux rate between live and dead soils in the cellulose added treatments.

Microbial oxidation of lithospheric organic carbon in rapidly eroding tropical mountain soils.

PubMed

Hemingway, Jordon D; Hilton, Robert G; Hovius, Niels; Eglinton, Timothy I; Haghipour, Negar; Wacker, Lukas; Chen, Meng-Chiang; Galy, Valier V

2018-04-13

Lithospheric organic carbon ("petrogenic"; OC petro ) is oxidized during exhumation and subsequent erosion of mountain ranges. This process is a considerable source of carbon dioxide (CO 2 ) to the atmosphere over geologic time scales, but the mechanisms that govern oxidation rates in mountain landscapes are poorly constrained. We demonstrate that, on average, 67 ± 11% of the OC petro initially present in bedrock exhumed from the tropical, rapidly eroding Central Range of Taiwan is oxidized in soils, leading to CO 2 emissions of 6.1 to 18.6 metric tons of carbon per square kilometer per year. The molecular and isotopic evolution of bulk OC and lipid biomarkers during soil formation reveals that OC petro remineralization is microbially mediated. Rapid oxidation in mountain soils drives CO 2 emission fluxes that increase with erosion rate, thereby counteracting CO 2 drawdown by silicate weathering and biospheric OC burial. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Physiological response of a red tide alga (Skeletonema costatum) to nitrate enrichment, with special reference to inorganic carbon acquisition.

PubMed

Gao, Guang; Xia, Jianrong; Yu, Jinlan; Zeng, Xiaopeng

2018-02-01

A classical red tide alga Skeletonema costatum was cultured under various nitrate levels to investigate its physiological response to nitrate enrichment combined with CO 2 limitation. The higher nitrate levels increased content of photosynthetic pigments (Chl a and Chl c), electron transport rate in photosystem II, photosynthetic O 2 evolution, and thus growth rate in S. costatum. On the other hand, the lower CO 2 levels (3.5-4.4 μmol kg -1 seawater) and higher pH (8.56-8.63) values in seawater were observed under higher nitrate conditions. Redox activity of plasma membrane and carbonic anhydrase in S. costatum was enhanced to address the reduced CO 2 level at higher nitrate levels. In addition, the pH compensation point was enhanced and direct HCO 3 - use was induced at higher nitrate levels. These findings indicate that nitrate enrichment would stimulate the breakout of S. costatum dominated red tides via enhancing its photosynthetic performances, and maintain a quick growth rate under CO 2 limitation conditions through improving its inorganic carbon acquisition capability. Our study sheds light on the mechanisms of S. costatum defeating CO 2 limitation during algal bloom. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

PubMed

Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

2018-08-15

In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

The water-water cycle in leaves is not a major alternative electron sink for dissipation of excess excitation energy when CO(2) assimilation is restricted.

PubMed

Driever, Steven M; Baker, Neil R

2011-05-01

Electron flux from water via photosystem II (PSII) and PSI to oxygen (water-water cycle) may provide a mechanism for dissipation of excess excitation energy in leaves when CO(2) assimilation is restricted. Mass spectrometry was used to measure O(2) uptake and evolution together with CO(2) uptake in leaves of French bean and maize at CO(2) concentrations saturating for photosynthesis and the CO(2) compensation point. In French bean at high CO(2) and low O(2) concentrations no significant water-water cycle activity was observed. At the CO(2) compensation point and 3% O(2) a low rate of water-water cycle activity was observed, which accounted for 30% of the linear electron flux from water. In maize leaves negligible water-water cycle activity was detected at the compensation point. During induction of photosynthesis in maize linear electron flux was considerably greater than CO(2) assimilation, but no significant water-water cycle activity was detected. Miscanthus × giganteus grown at chilling temperature also exhibited rates of linear electron transport considerably in excess of CO(2) assimilation; however, no significant water-water cycle activity was detected. Clearly the water-water cycle can operate in leaves under some conditions, but it does not act as a major sink for excess excitation energy when CO(2) assimilation is restricted. © 2011 Blackwell Publishing Ltd.

Vibrational energy transfer in OH X 2Pi(i), v = 2 and 1

NASA Technical Reports Server (NTRS)

Raiche, George A.; Jeffries, Jay B.; Rensberger, Karen J.; Crosley, David R.

1990-01-01

Using an IR-pump/UV-probe method in a flow discharge cell, vibrational energy transfer in OH X 2Pi(i) has been studied. OH is prepared in v = 2 by overtone excitation, and the time evolution of population in v = 2 and 1 monitored by laser-induced fluorescence. Rate constants for vibrational relaxation by the colliders H2O, NH3, CO2, and CH4 were measured. Ratios of rate constants for removal from the two states, k2/k1, range from two to five.

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

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Effects of elevated CO sub 2 concentrations on glycolysis in intact Bartlett pear fruit. [Pyrus communis L

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

Kerbel, E.L.; Kader, A.A.; Romani, R.J.

1988-04-01

Mature intact Bartlett pear fruit (Pyrus communis L.) were stored under a continuous flow of air or air + 10% CO{sub 2} for 4 days at 20{degree}C. Fruit kept under elevated CO{sub 2} concentrations exhibited reduced respiration (O{sub 2} consumption) and ethylene evolution rates, and remained firmer and greener than fruit stored in air. Protein content, fructose 1,6-bisphosphate levels, and ATP:phosphofructokinase and PPi:phosphofructokinase activities declined, while levels of fructose 6-phosphate and fructose 2,6-bisphosphate increased in fruit exposed to air + 10% CO{sub 2}. These results are discussed in light of a possible inhibitory effect of CO{sub 2} at the sitemore » of action of both phosphofructokinases in the glycolytic pathway, which could account, at least in part, for the observed reduction in respiration.« less

Influence of Suprathermal Atoms on the Escape and Evolution of Mars' CO2 Atmosphere

NASA Astrophysics Data System (ADS)

Lichtenegger, H.; Amerstorfer, U. V.; Gröller, H.; Tian, F.; Lammer, H.; Noack, L.; Johnstone, C.; Tu, L.

2017-09-01

Suprathermal oxygen and carbon atoms are produced by photochemical processes in the upper atmosphere of Mars. Due to their relatively high energies, these particle form an extended corona around Mars and can be picked up by the solar wind and emoved from the planet. The influence of an increased EUV flux, as it prevailed in the past, on the formation of the corona is studied and the corresponding loss rates are estimated. It is shown that the atmospheric loss due to the various processes varies with time and that most of the initial CO2 atmosphere is removed within the first few hundred million years after the formation of the planet. These results are important in order to better understand the atmosphere evolution of terrestrial planets.

Formation of crystalline phase in the glass matrix of Zr-Co-Al glass-matrix composites and its effect on their mechanical properties

NASA Astrophysics Data System (ADS)

Kim, Woo Chul; Kim, Kang Chul; Na, Min Young; Jeong, Seok Hoan; Kim, Won Tae; Kim, Do Hyang

2017-11-01

The microstructural evolution and mechanical properties of Zr-Co-Al alloys, with compositions of (Zr50Co50)x (Zr56Co26Al18)1-x (x = 1/6, 2/6, 3/6, 4/6, 5/6, 1) and Zr54Co35Al11, (referred to as Z1, Z2, Z3, Z4, Z5, Z6, and Z4.5), were investigated. Alloys Z1-Z3 consisted of crystalline phases, while alloys Z4 and Z4.5 consisted of crystalline phase particles ( 3 vol% and 35 vol%, respectively) embedded within the glassy matrix. Alloys Z5 and Z6 consisted of a monolithic glass phase. The crystalline phase of alloys Z1-Z4.5 consisted of primary B2-ZrCo dendrite and an interdendritic B2-ZrCo/Zr6CoAl2 eutectic phase. The B2-ZrCo dendritic phase exhibited a high work-hardening rate, which originated from the deformation-induced B2-to-B33 martensitic transformation. However, when the brittle interdendritic B2-ZrCo/Zr6CoAl2 eutectic phase fraction increased, the work-hardening rate significantly decreased. The ductility of the glass-matrix composites was significantly impaired by the presence of the interdendritic eutectic phase in the crystalline phase. The results indicate that the design of the crystalline particle microstructure is important with regard to enhancing the plasticity of glass-matrix composites.

Crassulacean acid metabolism in the shade. Studies on an epiphytic fern, Pyrrosia longifolia, and other rainforest species from Australia.

PubMed

Winter, K; Osmond, C B; Hubick, K T

1986-01-01

Crassulacean acid metabolism (CAM) was studied in a tropical epiphytic fern, Pyrrosia longifolia, from a fully sun-exposed and from a very shaded site in Northern Queensland, Australia. Measurements of instantaneous net CO 2 exchange showed carbon gain via CO 2 dark fixation with some net CO 2 uptake also occuring during late afternoon, in both sun and shade fronds. Maximum rates of net CO 2 uptake and the nocturnal increase in titratable acidity were lower in shade than in sun fronds. δ 13 C values of sun and shade fronds were not significantly different, and ranged between-14 and-15‰ suggesting that, in the long term, carbon gain was mainly via CO 2 dark fixation. Sun fronds had a higher light compensation point of photosynthesis than shade fronds but the same quantum yield. Yet there was no acclimation of photosynthetic O 2 evolution, (measured at 5% CO 2 ) in sun and shade fronds and photosynthesis saturated at between 200 and 400 μmol quanta m -2 s -1 . Use of higher light intensities for photosynthesis of sun fronds was probably precluded by low nutrient availability. Total nitrogen was less than 1% of dry weight in fully expanded sun and shade fronds. Exposure of shade fronds to full sunlight for 6 h led to a 60% decline in the quantum yield of photosynthesis and to a decline in variable fluorescence measured at room temperature. Photoinhibition by high light was also observed in Hoya nicholsoniae, a rainforest climber growing in deep shade. This species also exhibited CAM as demonstrated by nocturnal net CO 2 uptake, nocturnal acidification and a δ 13 C value of-14‰. Photosynthetic O 2 evolution in this species was saturated at 2.5% of full sunlight. Two species of Dendrobium (Orchidaceae) from sun-exposed sites, one species exhibiting CAM and the other one exhibiting net CO 2 uptake exclusively during daytime via conventional C 3 photosynthesis, showed similar light response curves and the same quantum yield for photosynthetic O 2 evolution.

Effects of overexpressing photosynthetic carbon flux control enzymes in the cyanobacterium Synechocystis PCC 6803.

PubMed

Liang, Feiyan; Lindblad, Peter

2016-11-01

Synechocystis PCC 6803 is a model unicellular cyanobacterium used in e.g. photosynthesis and CO 2 assimilation research. In the present study we examined the effects of overexpressing Ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), sedoheptulose 1,7-biphosphatase (SBPase), fructose-bisphosphate aldolase (FBA) and transketolase (TK), confirmed carbon flux control enzymes of the Calvin-Bassham-Benson (CBB) cycle in higher plants, in Synechocystis PCC 6803. Overexpressing RuBisCO, SBPase and FBA resulted in increased in vivo oxygen evolution (maximal 115%), growth rate and biomass accumulation (maximal 52%) under 100μmolphotonsm -2 s -1 light condition. Cells overexpressing TK showed a chlorotic phenotype but increased biomass by approximately 42% under 100μmolphotonsm -2 s -1 light condition. Under 15μmolphotonsm -2 s -1 light condition, cells overexpressing TK showed enhanced in vivo oxygen evolution. This study demonstrates increased growth and biomass accumulation when overexpressing selected enzymes of the CBB cycle. RuBisCO, SBPase, FBA and TK are identified as four potential targets to improve growth and subsequently also yield of valuable products from Synechocystis PCC 6803. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

On-line estimation of O2 production, CO2 uptake, and growth kinetics of microalgal cultures in a gas-tight photobioreactor

PubMed Central

Riisgård, Frederik Kier; Gunther, William Stuart; Lønsmann Iversen, Jens Jørgen

2006-01-01

Growth of the green algae Chlamydomonas reinhardtii and Chlorella sp. in batch cultures was investigated in a novel gas-tight photobioreactor, in which CO2, H2, and N2 were titrated into the gas phase to control medium pH, dissolved oxygen partial pressure, and headspace pressure, respectively. The exit gas from the reactor was circulated through a loop of tubing and re-introduced into the culture. CO2 uptake was estimated from the addition of CO2 as acidic titrant and O2 evolution was estimated from titration by H2, which was used to reduce O2 over a Pd catalyst. The photosynthetic quotient, PQ, was estimated as the ratio between O2 evolution and CO2 up-take rates. NH4+, NO2−, or NO3− was the final cell density limiting nutrient. Cultures of both algae were, in general, characterised by a nitrogen sufficient growth phase followed by a nitrogen depleted phase in which starch was the major product. The estimated PQ values were dependent on the level of oxidation of the nitrogen source. The PQ was 1 with NH4+ as the nitrogen source and 1.3 when NO3− was the nitrogen source. In cultures grown on all nitrogen sources, the PQ value approached 1 when the nitrogen source was depleted and starch synthesis became dominant, to further increase towards 1.3 over a period of 3–4 days. This latter increase in PQ, which was indicative of production of reduced compounds like lipids, correlated with a simultaneous increase in the degree of reduction of the biomass. When using the titrations of CO2 and H2 into the reactor headspace to estimate the up-take of CO2, the production of O2, and the PQ, the rate of biomass production could be followed, the stoichiometrical composition of the produced algal biomass could be estimated, and different growth phases could be identified. PMID:19396354

Opposing effects of folding and assembly chaperones on evolvability of Rubisco.

PubMed

Durão, Paulo; Aigner, Harald; Nagy, Péter; Mueller-Cajar, Oliver; Hartl, F Ulrich; Hayer-Hartl, Manajit

2015-02-01

Ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) catalyzes the fixation of CO2 in photosynthesis. Despite its pivotal role, Rubisco is an inefficient enzyme and thus is a key target for directed evolution. Rubisco biogenesis depends on auxiliary factors, including the GroEL/ES-type chaperonin for folding and the chaperone RbcX for assembly. Here we performed directed evolution of cyanobacterial form I Rubisco using a Rubisco-dependent Escherichia coli strain. Overexpression of GroEL/ES enhanced Rubisco solubility and tended to expand the range of permissible mutations. In contrast, the specific assembly chaperone RbcX had a negative effect on evolvability by preventing a subset of mutants from forming holoenzyme. Mutation F140I in the large Rubisco subunit, isolated in the absence of RbcX, increased carboxylation efficiency approximately threefold without reducing CO2 specificity. The F140I mutant resulted in a ∼55% improved photosynthesis rate in Synechocystis PCC6803. The requirement of specific biogenesis factors downstream of chaperonin may have retarded the natural evolution of Rubisco.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CoCoNuT: General relativistic hydrodynamics code with dynamical space-time evolution

NASA Astrophysics Data System (ADS)

Dimmelmeier, Harald; Novak, Jérôme; Cerdá-Durán, Pablo

2012-02-01

CoCoNuT is a general relativistic hydrodynamics code with dynamical space-time evolution. The main aim of this numerical code is the study of several astrophysical scenarios in which general relativity can play an important role, namely the collapse of rapidly rotating stellar cores and the evolution of isolated neutron stars. The code has two flavors: CoCoA, the axisymmetric (2D) magnetized version, and CoCoNuT, the 3D non-magnetized version.

Kinetic characteristics and modeling of microalgae Chlorella vulgaris growth and CO2 biofixation considering the coupled effects of light intensity and dissolved inorganic carbon.

PubMed

Chang, Hai-Xing; Huang, Yun; Fu, Qian; Liao, Qiang; Zhu, Xun

2016-04-01

Understanding and optimizing the microalgae growth process is an essential prerequisite for effective CO2 capture using microalgae in photobioreactors. In this study, the kinetic characteristics of microalgae Chlorella vulgaris growth in response to light intensity and dissolved inorganic carbon (DIC) concentration were investigated. The greatest values of maximum biomass concentration (Xmax) and maximum specific growth rate (μmax) were obtained as 2.303 g L(-1) and 0.078 h(-1), respectively, at a light intensity of 120 μmol m(-2) s(-1) and DIC concentration of 17 mM. Based on the results, mathematical models describing the coupled effects of light intensity and DIC concentration on microalgae growth and CO2 biofixation are proposed. The models are able to predict the temporal evolution of C. vulgaris growth and CO2 biofixation rates from lag to stationary phases. Verification experiments confirmed that the model predictions agreed well with the experimental results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dynamic analysis of CO₂ labeling and cell respiration using membrane-inlet mass spectrometry.

PubMed

Yang, Tae Hoon

2014-01-01

Here, we introduce a mass spectrometry-based analytical method and relevant technical details for dynamic cell respiration and CO2 labeling analysis. Such measurements can be utilized as additional information and constraints for model-based (13)C metabolic flux analysis. Dissolved dynamics of oxygen consumption and CO2 mass isotopomer evolution from (13)C-labeled tracer substrates through different cellular processes can be precisely measured on-line using a miniaturized reactor system equipped with a membrane-inlet mass spectrometer. The corresponding specific rates of physiologically relevant gases and CO2 mass isotopomers can be quantified within a short-term range based on the liquid-phase dynamics of dissolved fermentation gases.

Recovery of photosynthesis in 1-year-old needles of unfertilized and fertilized Norway spruce (Picea abies (L.) Karst.) during spring.

PubMed

Strand, M; Lundmark, T

1995-03-01

Photosynthetic O(2) evolution and chlorophyll a fluorescence were measured in 1-year-old needles of unfertilized and fertilized trees of Norway spruce (Picea abies (L.) Karst.) during recovery of photosynthesis from winter inhibition in northern Sweden. Measurements were made under laboratory conditions at 20 degrees C. In general, the CO(2)-saturated rate of O(2) evolution was higher in needles of fertilized trees than in needles of unfertilized trees over a wide range of incident photon flux densities. Furthermore, the maximum photochemical efficiency of photosystem (PS) II, as indicated by the ratio of variable to maximum fluorescence (F(V)/F(M)) was higher in needles of fertilized trees than in needles of unfertilized trees. The largest differences in F(V)/F(M) between the two treatments occurred before the main recovery of photosynthesis from winter inhibition in late May. The rate of O(2) evolution was higher in needles of north-facing branches than in needles of south-facing branches in the middle of May. Simultaneous measurements of O(2) exchange and chlorophyll fluorescence indicated that differences in the rate of O(2) evolution between the two treatments were paralleled by differences in the rate of PS II electron transport determined by chlorophyll fluorescence. We suggest that, during recovery of photosynthesis from winter inhibition, the balance between carbon assimilation and PS II electron transport was maintained largely by adjustments in the nonphotochemical dissipation of excitation energy within PS II.

Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

PubMed

Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

2016-05-23

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conditions for oceans on Earth-like planets orbiting within the habitable zone: importance of volcanic CO{sub 2} degassing

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

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@astrobio.k.u-tokyo.ac.jp

2014-08-01

Earth-like planets in the habitable zone (HZ) have been considered to have warm climates and liquid water on their surfaces if the carbonate-silicate geochemical cycle is working as on Earth. However, it is known that even the present Earth may be globally ice-covered when the rate of CO{sub 2} degassing via volcanism becomes low. Here we discuss the climates of Earth-like planets in which the carbonate-silicate geochemical cycle is working, with focusing particularly on insolation and the CO{sub 2} degassing rate. The climate of Earth-like planets within the HZ can be classified into three climate modes (hot, warm, and snowballmore » climate modes). We found that the conditions for the existence of liquid water should be largely restricted even when the planet is orbiting within the HZ and the carbonate-silicate geochemical cycle is working. We show that these conditions should depend strongly on the rate of CO{sub 2} degassing via volcanism. It is, therefore, suggested that thermal evolution of the planetary interiors will be a controlling factor for Earth-like planets to have liquid water on their surface.« less

Izu-Oshima volcano, Japan: ten years of geochemical monitoring by means of CO2 soil diffuse degassing

NASA Astrophysics Data System (ADS)

Hernandez Perez, P. A.; Mori, T.; Notsu, K.; Morita, M.; Padron, E.; Onizawa, S.; Melián, G.; Sumino, H.; Asensio-Ramos, M.; Nogami, K.; Yamane, K.; Perez, N. M.

2016-12-01

Izu-Oshima is an active volcanic island located around 100 km SSW of Tokyo. The centre of the island is occupied by a caldera complex with a diameter of 3 km. A large post-caldera cone known as Mt. Mihara is located at the south-western quadrant of the caldera. Izu-Oshima has erupted 74 times, consisting mainly in fissure eruptions, both inside and outside of the caldera. The last eruption of Izu-Oshima occurred in 1986. Since 2007, eight soil gas surveys have been carried out to investigate the spatial and temporal evolution of diffuse CO2 emission from this volcanic system and to identify those structures controlling the degassing process. Diffuse CO2 emission surveys were always carried out following the accumulation chamber method. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. The location of the CO2 anomalies has always shown a close relationship with the structural characteristics of Miharayama, with most of the gas discharged from the rim of the summit crater. Temporal evolution of diffuse CO2 emission rate from Mt. Miharayama has shown a good temporal correlation with the main two peaks of seismic activity occur when highest CO diffuse emissions were computed, March 2007, August 2010 and July 2011, may be associated with fluid pressure fluctuations in the volcanic system due stress changes at depth. In order to strength the contribution of deep seated gases, we performed carbon isotopic analysis of soil gas samples at selected sites during 2010, 2013, 2015 and 2016 surveys. At isotopic compositions lighter than - 6‰, the soil CO2 effluxes were always low, while at heavier isotopic compositions an increasing number of points are characterized by relatively high soil CO efflux. Soil CO2 efflux peak values (xB) showed also a good correlation with the observed seismicity, with the largest value computed on June 2013. This parameter is a geochemical expression of the magnitude of the anomalous degassing, and the observed change in the trend may indicate an increase of the seismic-volcanic activity in the next future. Therefore, performing regularly soil CO2 efflux surveys seems to be an effective geochemical surveillance tool Izu-Oshima volcano in order to detect a change in the tendency of the CO2 emission rate in case of future episodes of volcanic unrest.

Lipid degradation and sensory characteristics of ripened sausages packed in modified atmosphere at different carbon dioxide concentrations.

PubMed

Summo, Carmine; Pasqualone, Antonella; Paradiso, Vito Michele; Centomani, Isabella; Centoducati, Gerardo; Caponio, Francesco

2016-01-15

Conflicting results about the effect of modified atmosphere packaging (MAP) rich in CO2 on the quality of different kinds of meat products are present in the literature. In this study, the degree of lipid degradation and the sensory characteristics of ripened sausages packed in modified atmosphere at three different carbon dioxide (CO2) concentrations were evaluated during 5 months of storage. The degree of hydrolytic degradation of the lipid fraction was found to decrease with increasing CO2 concentration. Similarly, oxidative phenomena occurred at a lower rate when the CO2 concentration increased. The variations in CO2 concentration influenced the perception of rancid flavor in the examined sausages. An increase in CO2 concentration in MAP slowed down the evolution of lipid oxidation owing to the minor extent of hydrolytic degradation, whose products have pro-oxidant activity. This effect was more evident in the first 2 months of storage. © 2015 Society of Chemical Industry.

No way out? The double-bind in seeking global prosperity along with mitigated climate change

NASA Astrophysics Data System (ADS)

Garrett, T. J.

2011-04-01

In a prior study (Garrett, 2011), I introduced a simple thermodynamics-based economic growth model. By treating civilization as a whole, it was found that the global economy's current rate of energy consumption can be tied through a constant to its current accumulation of wealth. The value of the constant is λ = 9.7 ± 0.3 milliwatts per 1990 US dollar. Here, this model is coupled to a linear formulation for the evolution of atmospheric CO2 concentrations. Despite the model's extreme simplicity, multi-decadal hindcasts of trajectories in gross world product (GWP) and CO2 agree closely with recent observations. Extending the model to the future, the model implies that the well-known IPCC SRES scenarios substantially underestimate how much CO2 levels will rise for a given level of future economic prosperity. Instead, what is shown is that, like a long-term natural disaster, future greenhouse warming should be expected to retard the real growth of wealth through inflationary pressures. Because wealth is tied to rates of energy consumption through the constant λ, it follows that dangerous climate change should be a negative feedback on CO2 emission rates, and therefore the ultimate extent of greenhouse warming. Nonetheless, if atmospheric CO2 concentrations are to remain below a "dangerous" level of 450 ppmv (Hansen et al., 2007), there will have to be some combination of an unrealistically rapid rate of energy decarbonization and a near immediate collapse of civilization wealth. Effectively, civilization is in a double-bind. If civilization does not collapse quickly this century, then CO2 levels will likely end up exceeding 1000 ppmv; but, if CO2 levels rise by this much, then the danger is that civilization will gradually tend towards collapse.

Catalyst mixtures

DOEpatents

Masel, Richard I.; Rosen, Brian A.

2017-02-14

Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

The co-evolution of microstructure features in self-ion irradiated HT9 at very high damage levels

NASA Astrophysics Data System (ADS)

Getto, Elizabeth Margaret

The objective of this study was to understand the co-evolution of microstructure features in self-ion irradiated HT9 at very high damage levels. HT9 (heat 84425) was pre-implanted with 10 atom parts per million helium and then irradiated with 5 MeV Fe++ in the temperature range of 440-480°C to 188 dpa. A damage dependence study from 75 to 650 dpa was performed at the peak swelling temperature of 460°C. The swelling, dislocation and precipitate evolution was determined using Analytic Electron Microscopes in both Conventional Transmission electron microscopy (CTEM) and Scanning Transmission Electron Microscopy (STEM) modes. Void swelling reached a nominally linear rate of 0.03%/dpa from 188 to 650 dpa at 460°C. G phase precipitates were observed by 75 dpa and grew linearly up to 650 dpa. M 2X was observed by 250 dpa and peaked in volume fraction at 450 dpa. Dislocation loop evolution was observed up to 650 dpa including a step change in diameter between 375 and 450 dpa; which correlated with nucleation and growth of M2X. The experimental results were interpreted using a rate theory model, the Radiation Induced Microstructure Evolution (RIME), in the damage range from 188 to 650 dpa. A simple system of voids and dislocations was modeled in which the dislocations measured from experiment were used as input, or the dislocations were allowed to evolve dynamically, resulting in swelling that was overestimated by 63% relative to that observed experimentally. G phase had limited effect on the void or dislocation behavior. The behavior of M2X within the microstructure was characterized as a direct effect as a coherent sink, and as an indirect effect in consuming carbon from the matrix, which had the largest impact on both void and dislocation behavior. A slowly monotonically increasing swelling rate was observed both experimentally and computationally, with swelling rates of ˜0.025%/dpa and ˜0.036%/dpa before and after 450 dpa. The agreement in void behavior between experiment and model when all effects (loops, network, G phase, M2X formation and growth, and removal of carbon) are accounted for demonstrates the importance of characterizing the evolution of the full microstructure over a large dpa range.

Sink- or Source-driven Phanerozoic carbon cycle?

NASA Astrophysics Data System (ADS)

Godderis, Y.; Donnadieu, Y.; Maffre, P.; Carretier, S.

2017-12-01

The Phanerozoic evolution of the atmospheric CO2 level is controlled by the fluxes entering or leaving the exospheric system. Those fluxes (including continental weathering, magmatic degassing, organic carbon burial, oxidation of sedimentary organic carbon) are intertwined, and their relative importance in driving the global carbon cycle evolution may have fluctuated through time. Deciphering the causes of the Phanerozoic climate evolution thus requires a holistic and quantitative approach. Here we focus on the role played by the paleogeographic configuration on the efficiency of the CO2 sink by continental silicate weathering, and on the impact of the magmatic degassing of CO2. We use the spatially resolved numerical model GEOCLIM (geoclimmodel.worpress.com) to compute the response of the silicate weathering and atmospheric CO2 to continental drift for 22 time slices of the Phanerozoic. Regarding the CO2 released by the magmatic activity, we reconstruct several Phanerozoic histories of this flux, based on published indexes. We calculate the CO2 evolution for each degassing scenario, and accounting for the paleogeographic setting. We show that the paleogeographic setting is a main driver of the climate from 540 Ma to about the beginning of the Jurassic. Regarding the role of the magmatic degassing, the various reconstructions do not converge towards a single signal, and thus introduce large uncertainties in the calculated CO2 level over time. Nevertheless, the continental dispersion, which prevails since the Jurassic, promotes the CO2 consumption by weathering and forces atmospheric CO2 to stay low. Warm climates of the "middle" Cretaceous and early Cenozoic require enhanced CO2 degassing by magmatic activity. In summary, the Phanerozoic climate evolution can be hardly assigned to a single process, but is the result of complex and intertwined processes.

Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

2016-09-01

The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

Direct Simulation Monte Carlo modelling of the major species in the coma of comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Fougere, Nicolas; Altwegg, K.; Berthelier, J.-J.; Bieler, A.; Bockelée-Morvan, D.; Calmonte, U.; Capaccioni, F.; Combi, M. R.; De Keyser, J.; Debout, V.; Erard, S.; Fiethe, B.; Filacchione, G.; Fink, U.; Fuselier, S. A.; Gombosi, T. I.; Hansen, K. C.; Hässig, M.; Huang, Z.; Le Roy, L.; Leyrat, C.; Migliorini, A.; Piccioni, G.; Rinaldi, G.; Rubin, M.; Shou, Y.; Tenishev, V.; Toth, G.; Tzou, C.-Y.

2016-11-01

We analyse the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) - the Double Focusing Mass Spectrometer data between 2014 August and 2016 February to examine the effect of seasonal variations on the four major species within the coma of 67P/Churyumov-Gerasimenko (H2O, CO2, CO, and O2), resulting from the tilt in the orientation of the comet's spin axis. Using a numerical data inversion, we derive the non-uniform activity distribution at the surface of the nucleus for these species, suggesting that the activity distribution at the surface of the nucleus has not significantly been changed and that the differences observed in the coma are solely due to the variations in illumination conditions. A three-dimensional Direct Simulation Monte Carlo model is applied where the boundary conditions are computed with a coupling of the surface activity distributions and the local illumination. The model is able to reproduce the evolution of the densities observed by ROSINA including the changes happening at equinox. While O2 stays correlated with H2O as it was before equinox, CO2 and CO, which had a poor correlation with respect to H2O pre-equinox, also became well correlated with H2O post-equinox. The integration of the densities from the model along the line of sight results in column densities directly comparable to the VIRTIS-H observations. Also, the evolution of the volatiles' production rates is derived from the coma model showing a steepening in the production rate curves after equinox. The model/data comparison suggests that the seasonal effects result in the Northern hemisphere of 67P's nucleus being more processed with a layered structure while the Southern hemisphere constantly exposes new material.

Sequence Comparisons of Odorant Receptors among Tortricid Moths Reveal Different Rates of Molecular Evolution among Family Members

PubMed Central

Carraher, Colm; Authier, Astrid; Steinwender, Bernd; Newcomb, Richard D.

2012-01-01

In insects, odorant receptors detect volatile cues involved in behaviours such as mate recognition, food location and oviposition. We have investigated the evolution of three odorant receptors from five species within the moth genera Ctenopseustis and Planotrotrix, family Tortricidae, which fall into distinct clades within the odorant receptor multigene family. One receptor is the orthologue of the co-receptor Or83b, now known as Orco (OR2), and encodes the obligate ion channel subunit of the receptor complex. In comparison, the other two receptors, OR1 and OR3, are ligand-binding receptor subunits, activated by volatile compounds produced by plants - methyl salicylate and citral, respectively. Rates of sequence evolution at non-synonymous sites were significantly higher in OR1 compared with OR2 and OR3. Within the dataset OR1 contains 109 variable amino acid positions that are distributed evenly across the entire protein including transmembrane helices, loop regions and termini, while OR2 and OR3 contain 18 and 16 variable sites, respectively. OR2 shows a high level of amino acid conservation as expected due to its essential role in odour detection; however we found unexpected differences in the rate of evolution between two ligand-binding odorant receptors, OR1 and OR3. OR3 shows high sequence conservation suggestive of a conserved role in odour reception, whereas the higher rate of evolution observed in OR1, particularly at non-synonymous sites, may be suggestive of relaxed constraint, perhaps associated with the loss of an ancestral role in sex pheromone reception. PMID:22701634

Simulation of CO2 Sequestration at Rock Spring Uplift, Wyoming: Heterogeneity and Uncertainties in Storage Capacity, Injectivity and Leakage

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

Deng, Hailin; Dai, Zhenxue; Jiao, Zunsheng

2011-01-01

Many geological, geochemical, geomechanical and hydrogeological factors control CO{sub 2} storage in subsurface. Among them heterogeneity in saline aquifer can seriously influence design of injection wells, CO{sub 2} injection rate, CO{sub 2} plume migration, storage capacity, and potential leakage and risk assessment. This study applies indicator geostatistics, transition probability and Markov chain model at the Rock Springs Uplift, Wyoming generating facies-based heterogeneous fields for porosity and permeability in target saline aquifer (Pennsylvanian Weber sandstone) and surrounding rocks (Phosphoria, Madison and cap-rock Chugwater). A multiphase flow simulator FEHM is then used to model injection of CO{sub 2} into the target salinemore » aquifer involving field-scale heterogeneity. The results reveal that (1) CO{sub 2} injection rates in different injection wells significantly change with local permeability distributions; (2) brine production rates in different pumping wells are also significantly impacted by the spatial heterogeneity in permeability; (3) liquid pressure evolution during and after CO{sub 2} injection in saline aquifer varies greatly for different realizations of random permeability fields, and this has potential important effects on hydraulic fracturing of the reservoir rock, reactivation of pre-existing faults and the integrity of the cap-rock; (4) CO{sub 2} storage capacity estimate for Rock Springs Uplift is 6614 {+-} 256 Mt at 95% confidence interval, which is about 36% of previous estimate based on homogeneous and isotropic storage formation; (5) density profiles show that the density of injected CO{sub 2} below 3 km is close to that of the ambient brine with given geothermal gradient and brine concentration, which indicates CO{sub 2} plume can sink to the deep before reaching thermal equilibrium with brine. Finally, we present uncertainty analysis of CO{sub 2} leakage into overlying formations due to heterogeneity in both the target saline aquifer and surrounding formations. This uncertainty in leakage will be used to feed into risk assessment modeling.« less

Stability of a Cu0.7Co2.3O4 electrode during the oxygen evolution reaction for alkaline anion-exchange membrane water electrolysis

NASA Astrophysics Data System (ADS)

Kang, Kyoung Eun; Kim, Chi Ho; Lee, Myung Sup; Jung, Chang Wook; Kim, Yang Do; Lee, Jae Ho

2018-01-01

The electrode materials for oxygen evolution, especially non-platinum group metal oxides, have attracted increasing attention. Among the spinel-type transition metal oxides, Cu0.7Co2.3O4 powders were evaluated as a potential replacement for expensive dimensionally stabilized anode materials. Cu0.7Co2.3O4 powder for use as an electrode material for oxygen evolution in an alkaline anion-exchange membrane water electrolyzer was prepared using a thermal decomposition method. The Cu0.7Co2.3O4 powders heat-treated at 250 °C exhibited the same X-ray diffraction patterns without any secondary phases as the Co3O4 spinel structure did. The Cu0.7Co2.3O4 powders heat-treated at 250 °C for 30 minutes showed the smallest mean particle size of approximately 376 nm with the powders having a homogeneous shape and size distribution. The fine powders with a relatively homogeneous size distribution showed a higher current density during the oxygen evolution reaction. The lifetime of the Cu0.7Co2.3O4 electrode was relatively long at a low current density, but was quickly shortened due to physical detachment of the Cu0.7Co2.3O4 powders as the current density was increased. This study showed that the efficiency and the stability of Cu0.7Co2.3O4 powders during the oxygen evolution reaction were related directly to the active electrode area.

Efficient whole cell biocatalyst for formate-based hydrogen production.

PubMed

Kottenhahn, Patrick; Schuchmann, Kai; Müller, Volker

2018-01-01

Molecular hydrogen (H 2 ) is an attractive future energy carrier to replace fossil fuels. Biologically and sustainably produced H 2 could contribute significantly to the future energy mix. However, biological H 2 production methods are faced with multiple barriers including substrate cost, low production rates, and low yields. The C1 compound formate is a promising substrate for biological H 2 production, as it can be produced itself from various sources including electrochemical reduction of CO 2 or from synthesis gas. Many microbes that can produce H 2 from formate have been isolated; however, in most cases H 2 production rates cannot compete with other H 2 production methods. We established a formate-based H 2 production method utilizing the acetogenic bacterium Acetobacterium woodii . This organism can use formate as sole energy and carbon source and possesses a novel enzyme complex, the hydrogen-dependent CO 2 reductase that catalyzes oxidation of formate to H 2 and CO 2 . Cell suspensions reached specific formate-dependent H 2 production rates of 71 mmol g protein -1 h -1 (30.5 mmol g CDW -1 h -1 ) and maximum volumetric H 2 evolution rates of 79 mmol L -1 h -1 . Using growing cells in a two-step closed batch fermentation, specific H 2 production rates reached 66 mmol g CDW -1 h -1 with a volumetric H 2 evolution rate of 7.9 mmol L -1  h -1 . Acetate was the major side product that decreased the H 2 yield. We demonstrate that inhibition of the energy metabolism by addition of a sodium ionophore is suitable to completely abolish acetate formation. Under these conditions, yields up to 1 mol H 2 per mol formate were achieved. The same ionophore can be used in cultures utilizing formate as specific switch from a growing phase to a H 2 production phase. Acetobacterium woodii reached one of the highest formate-dependent specific H 2 productivity rates at ambient temperatures reported so far for an organism without genetic modification and converted the substrate exclusively to H 2 . This makes this organism a very promising candidate for sustainable H 2 production and, because of the reversibility of the A. woodii enzyme, also a candidate for reversible H 2 storage.

Meteoric Metal Chemistry in the Martian Atmosphere

NASA Astrophysics Data System (ADS)

Plane, J. M. C.; Carrillo-Sanchez, J. D.; Mangan, T. P.; Crismani, M. M. J.; Schneider, N. M.; Määttänen, A.

2018-03-01

Recent measurements by the Imaging Ultraviolet Spectrograph (IUVS) instrument on NASA's Mars Atmosphere and Volatile EvolutioN mission show that a persistent layer of Mg+ ions occurs around 90 km in the Martian atmosphere but that neutral Mg atoms are not detectable. These observations can be satisfactorily modeled with a global meteoric ablation rate of 0.06 t sol-1, out of a cosmic dust input of 2.7 ± 1.6 t sol-1. The absence of detectable Mg at 90 km requires that at least 50% of the ablating Mg atoms ionize through hyperthermal collisions with CO2 molecules. Dissociative recombination of MgO+.(CO2)n cluster ions with electrons to produce MgCO3 directly, rather than MgO, also avoids a buildup of Mg to detectable levels. The meteoric injection rate of Mg, Fe, and other metals—constrained by the IUVS measurements—enables the production rate of metal carbonate molecules (principally MgCO3 and FeCO3) to be determined. These molecules have very large electric dipole moments (11.6 and 9.2 Debye, respectively) and thus form clusters with up to six H2O molecules at temperatures below 150 K. These clusters should then coagulate efficiently, building up metal carbonate-rich ice particles which can act as nucleating particles for the formation of CO2-ice clouds. Observable mesospheric clouds are predicted to occur between 65 and 80 km at temperatures below 95 K and above 85 km at temperatures about 5 K colder.

High-temperature characteristics of advanced Ni-MH batteries using nickel electrodes containing CaF 2

NASA Astrophysics Data System (ADS)

Zhang, Xuezeng; Gong, Zhixin; Zhao, Shumei; Geng, Mingming; Wang, Yan; Northwood, Derek O.

The high-temperature charge acceptance of Ni-MH batteries has been improved through the addition of calcium fluoride to the pasted nickel hydroxide electrode made using spherical Co(OH) 2-coated nickel hydroxide powder. The charge acceptance of the Ni-MH battery at 60 °C is over 95% at 1 C charge/discharge rates. The charge acceptance at 60 °C remains at over 90% through 10 cycles. The use of Co(OH) 2-coated Ni(OH) 2 plus a CaF 2 addition to the positive electrode also significantly improved the high-temperature stability in terms of reduced gas evolution.

Co-variation between seed dormancy, growth rate and flowering time changes with latitude in Arabidopsis thaliana.

PubMed

Debieu, Marilyne; Tang, Chunlao; Stich, Benjamin; Sikosek, Tobias; Effgen, Sigi; Josephs, Emily; Schmitt, Johanna; Nordborg, Magnus; Koornneef, Maarten; de Meaux, Juliette

2013-01-01

Life-history traits controlling the duration and timing of developmental phases in the life cycle jointly determine fitness. Therefore, life-history traits studied in isolation provide an incomplete view on the relevance of life-cycle variation for adaptation. In this study, we examine genetic variation in traits covering the major life history events of the annual species Arabidopsis thaliana: seed dormancy, vegetative growth rate and flowering time. In a sample of 112 genotypes collected throughout the European range of the species, both seed dormancy and flowering time follow a latitudinal gradient independent of the major population structure gradient. This finding confirms previous studies reporting the adaptive evolution of these two traits. Here, however, we further analyze patterns of co-variation among traits. We observe that co-variation between primary dormancy, vegetative growth rate and flowering time also follows a latitudinal cline. At higher latitudes, vegetative growth rate is positively correlated with primary dormancy and negatively with flowering time. In the South, this trend disappears. Patterns of trait co-variation change, presumably because major environmental gradients shift with latitude. This pattern appears unrelated to population structure, suggesting that changes in the coordinated evolution of major life history traits is adaptive. Our data suggest that A. thaliana provides a good model for the evolution of trade-offs and their genetic basis.

In situ measurements of the photochemical formation rates and optical properties of organic aerosols in CH4/CO2 mixtures.

NASA Astrophysics Data System (ADS)

Adamkovics, M.; Boering, K. A.

2003-12-01

The presence of photochemically-generated hazes has a significant impact on radiative transfer in planetary atmospheres. While the rates of particle formation have been inferred from photochemical or microphysical models constrained to match observations, these rates have not been determined experimentally. Thus, the fundamental kinetics of particle formation are not known and remain highly parameterized in planetary atmospheric models. We have developed instrumentation for measuring the formation rates and optical properties of organic aerosols produced by irradiating mixtures of precursor gases via in situ optical (633nm) scattering and online quadrupole mass spectrometry (1-200 amu). Results for the generation of particulate hydrocarbons from the irradiation of pure, gas-phase CH4 as well as CH4/CO2 mixtures with vacuum ultraviolet (120-160nm) light, along with simultaneous measurements of the evolution of higher gas-phase hydrocarbons will be presented.

Long-term evolution of biodegradation and volatilization rates in a crude oil-contaminated aquifer

USGS Publications Warehouse

Chaplin, B.P.; Delin, G.N.; Baker, R.J.; Lahvis, M.A.

2002-01-01

Volatilization and subsequent biodegradation near the water Table make up a coupled natural attenuation pathway that results in significant mass loss of hydrocarbons. Rates of biodegradation and volatilization were documented twice 12 years apart at a crude-oil spill site near Bemidji, Minnesota. Biodegradation rates were determined by calibrating a gas transport model to O2, CO2, and CH4 gas-concentration data in the unsaturated zone. Reaction stoichiometry was assumed in converting O2 and CO2 gas-flux estimates to rates of aerobic biodegradation and CH4 gas-flux estimates to rates of methanogenesis. Model results indicate that the coupled pathway has resulted in significant hydrocarbon mass loss at the site, and it was estimated that approximately 10.52 kg/day were lost in 1985 and 1.99 kg/day in 1997. In 1985 3% of total volatile hydrocarbons diffusing from the floating oil were biodegraded in the lower 1 m of the unsaturated zone and increased to 52% by 1997. Rates of hydrocarbon biodegradation above the center of the floating oil were relatively stable from 1985 to 1997, as the primary metabolic pathway shifted from aerobic to methanogenic biodegradation. Model results indicate that in 1997 biodegradation under methanogenenic conditions represented approximately one-half of total hydrocarbon biodegradation in the lower 1 m of the unsaturated zone. Further downgradient, where substrate concentrations have greatly increased, total biodegradation rates increased by greater than an order of magnitude from 0.04 to 0.43 g/m2-day. It appears that volatilization is the primary mechanism for attenuation in early stages of plume evolution, while biodegradation dominates in later stages.

Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: An efficient electrocatalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei

2018-02-01

The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.

Effect of CO2-induced seawater acidification on growth, photosynthesis and inorganic carbon acquisition of the harmful bloom-forming marine microalga, Karenia mikimotoi.

PubMed

Hu, Shunxin; Zhou, Bin; Wang, You; Wang, Ying; Zhang, Xinxin; Zhao, Yan; Zhao, Xinyu; Tang, Xuexi

2017-01-01

Karenia mikimotoi is a widespread, toxic and non-calcifying dinoflagellate, which can release and produce ichthyotoxins and hemolytic toxins affecting the food web within the area of its bloom. Shifts in the physiological characteristics of K. mikimotoi due to CO2-induced seawater acidification could alter the occurrence, severity and impacts of harmful algal blooms (HABs). Here, we investigated the effects of elevated pCO2 on the physiology of K. mikimotoi. Using semi-continuous cultures under controlled laboratory conditions, growth, photosynthesis and inorganic carbon acquisition were determined over 4-6 week incubations at ambient (390ppmv) and elevated pCO2 levels (1000 ppmv and 2000 ppmv). pH-drift and inhibitor-experiments suggested that K. mikimotoi was capable of acquiring HCO3-, and that the utilization of HCO3- was predominantly mediated by anion-exchange proteins, but that HCO3- dehydration catalyzed by external carbonic anhydrase (CAext) only played a minor role in K. mikimotoi. Even though down-regulated CO2 concentrating mechanisms (CCMs) and enhanced gross photosynthetic O2 evolution were observed under 1000 ppmv CO2 conditions, the saved energy did not stimulate growth of K. mikimotoi under 1000 ppmv CO2, probably due to the increased dark respiration. However, significantly higher growth and photosynthesis [in terms of photosynthetic oxygen evolution, effective quantum Yield (Yield), photosynthetic efficiency (α), light saturation point (Ek) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity] were observed under 2000 ppmv CO2 conditions. Furthermore, elevated pCO2 increased the photo-inhibition rate of photosystem II (β) and non-photochemical quenching (NPQ) at high light. We suggest that the energy saved through the down-regulation of CCMs might lead to the additional light stress and photo-damage. Therefore, the response of this species to elevated CO2 conditions will be determined by more than regulation and efficiency of CCMs.

Disintegration of Meatball Electrodes for LiNi x Mn y Co z O 2 Cathode Materials

DOE PAGES

Xu, R.; de Vasconcelos, L. S.; Shi, J.; ...

2017-05-12

Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on themore » charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.« less

Modelling (18)O2 and (16)O2 unidirectional fluxes in plants. III: fitting of experimental data by a simple model.

PubMed

André, Marcel J

2013-08-01

Photosynthetic assimilation of CO2 in plants results in the balance between the photochemical energy developed by light in chloroplasts, and the consumption of that energy by the oxygenation processes, mainly the photorespiration in C3 plants. The analysis of classical biological models shows the difficulties to bring to fore the oxygenation rate due to the photorespiration pathway. As for other parameters, the most important key point is the estimation of the electron transport rate (ETR or J), i.e. the flux of biochemical energy, which is shared between the reductive and oxidative cycles of carbon. The only reliable method to quantify the linear electron flux responsible for the production of reductive energy is to directly measure the O2 evolution by (18)O2 labelling and mass spectrometry. The hypothesis that the respective rates of reductive and oxidative cycles of carbon are only determined by the kinetic parameters of Rubisco, the respective concentrations of CO2 and O2 at the Rubisco site and the available electron transport rate, ultimately leads to propose new expressions of biochemical model equations. The modelling of (18)O2 and (16)O2 unidirectional fluxes in plants shows that a simple model can fit the photosynthetic and photorespiration exchanges for a wide range of environmental conditions. Its originality is to express the carboxylation and the oxygenation as a function of external gas concentrations, by the definition of a plant specificity factor Sp that mimics the internal reactions of Rubisco in plants. The difference between the specificity factors of plant (Sp) and of Rubisco (Sr) is directly related to the conductance values to CO2 transfer between the atmosphere and the Rubisco site. This clearly illustrates that the values and the variation of conductance are much more important, in higher C3 plants, than the small variations of the Rubisco specificity factor. The simple model systematically expresses the reciprocal variations of carboxylation and oxygenation exchanges illustrated by a "mirror effect". It explains the protective sink effect of photorespiration, e.g. during water stress. The importance of the CO2 compensation point, in classical models, is reduced at the benefit of the crossing points Cx and Ox, concentration values where carboxylation and oxygenation are equal or where the gross O2 uptake is half of the gross O2 evolution. This concept is useful to illustrate the feedback effects of photorespiration in the atmosphere regulation. The constancy of Sp and of Cx for a great variation of P under several irradiance levels shows that the regulation of the conductance maintains constant the internal CO2 and the ratio of photorespiration to photosynthesis (PR/P). The maintenance of the ratio PR/P, in conditions of which PR could be reduced and the carboxylation increased, reinforces the hypothesis of a positive role of photorespiration and its involvement in the plant-atmosphere co-evolution. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Regulation of valine and. alpha. -ketoisocaproate metabolism in rat kidney mitochondria

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

Miller, R.H.; Harper, A.E.

1988-10-01

Activities of branched-chain amino acid (BCAA) aminotransferase (BCAT) and {alpha}-keto acid dehydrogenase (BCKD) were assayed in mitochondria isolated from kidneys of rats. Rates of transamination of valine and oxidation of keto acids {alpha}-ketoisocaproate (KIC) or {alpha}-ketoisovalerate (KIV) were estimated using radioactive tracers of the appropriate substrate from amounts of {sup 14}C-labeled products formed. Because of the high mitochondrial BCAT activity, an amino acceptor for BCAT, {alpha}-ketoglutarate ({alpha}-KG) or KIC, was added to the assay medium when valine was the substrate. Rates of valine transamination and subsequent oxidation of the KIV formed were determined with 0.5 mM {alpha}-KG as the aminomore » acceptor; these rates were 5- to 50-fold those without added {alpha}-KG. Rates of CO{sub 2} evolution from valine also increased when KIC was present; however, with KIC concentrations above 0.2 mM, rates of CO{sub 2} evolution from valine declined although rates of transamination continued to rise. When 0.05 mM KIC was added to the assay medium, oxidation of KIC was suppressed by inclusion of valine or glutamate in the medium. When valine was present KIC was not oxidized preferentially, presumably because it was also serving as an amino acceptor for BCAT. These results indicate that as the supply of amino acceptor, {alpha}-KG or KIC, is increased in mitochondria not only is the rate of valine transamination stimulated but also the rate of oxidation of the KIV formed from valine. Thus the rate of oxidation of BCAA can be controlled by factors that influence the rate and direction of BCAA transamination and, thereby, the supply of substrate for BCKD.« less

Rotary drum composting of vegetable waste and tree leaves.

PubMed

Kalamdhad, Ajay S; Singh, Yatish K; Ali, Muntjeer; Khwairakpam, Meena; Kazmi, A A

2009-12-01

High rate composting studies on institutional waste, i.e. vegetable wastes, tree leaves, etc., were conducted on a demonstration-scale (3.5 m(3)) rotary drum composter by evaluating changes in some physico-chemical and biological parameters. During composting, higher temperature (60-70 degrees C) at inlet zone and (50-60 degrees C) at middle zone were achieved which resulted in high degradation in the drum. As a result, all parameters including TOC, C/N ratio, CO(2) evolution and coliforms were decreased significantly within few days of composting. Within a week period, quality compost with total nitrogen (2.6%) and final total phosphorus (6 g/kg) was achieved; but relatively higher final values of fecal coliforms and CO(2) evolution, suggested further maturation. Thus, two conventional composting methods namely windrow (M1) and vermicomposting (M2) tried for maturation of primary stabilized compost. By examining these methods, it was suggested that M2 was found suitable in delivering fine grained, better quality matured compost within 20 days of maturation period.

Inter-annual variability in fossil-fuel CO2 emissions due to temperature anomalies

NASA Astrophysics Data System (ADS)

Bréon, F.-M.; Boucher, O.; Brender, P.

2017-07-01

It is well known that short-term (i.e. interannual) variations in fossil-fuel CO2 emissions are closely related to the evolution of the national economies. Nevertheless, a fraction of the CO2 emissions are linked to domestic and business heating and cooling, which can be expected to be related to the meteorology, independently of the economy. Here, we analyse whether the signature of the inter-annual temperature anomalies is discernible in the time series of CO2 emissions at the country scale. Our analysis shows that, for many countries, there is a clear positive correlation between a heating-degree-person index and the component of the CO2 emissions that is not explained by the economy as quantified by the gross domestic product (GDP). Similarly, several countries show a positive correlation between a cooling-degree-person (CDP) index and CO2 emissions. The slope of the linear relationship for heating is on the order of 0.5-1 kg CO2 (degree-day-person)-1 but with significant country-to-country variations. A similar relationship for cooling shows even greater diversity. We further show that the inter-annual climate anomalies have a small but significant impact on the annual growth rate of CO2 emissions, both at the national and global scale. Such a meteorological effect was a significant contribution to the rather small and unexpected global emission growth rate in 2014 while its contribution to the near zero emission growth in 2015 was insignificant.

Climatic response of annual tree-rings

NASA Astrophysics Data System (ADS)

Ageev, Boris G.; Gruzdev, Aleksandr N.; Ponomarev, Yurii N.; Sapozhnikova, Valeria A.

2014-11-01

Extensive literature devoted to investigations into the influence of environmental conditions on the plant respiration and respiration rate. It is generally accepted that the respired CO2 generated in a stem completely diffuses into the atmosphere. Results obtained from explorations into the CO2 content in disc tree rings by the method proposed in this work shows that a major part of CO2 remains in tree stems and exhibits inter-annual variability. Different methods are used to describe of CO2 and H2O distributions in disc tree rings. The relation of CO2 and H2O variations in a Siberian stone pine disc to meteorological parameters are analyzed with use of wavelet, spectral and cross-spectral techniques. According to a multiple linear regression model, the time evolution of the width of Siberian stone pine rings can be partly explained by a combined influence of air temperature, precipitation, cloudiness and solar activity. Conclusions are made regarding the response of the CO2 and H2O content in coniferous tree disc rings to various climatic factors. Suggested method of CO2, (CO2+H2O) detection can be used for studying of a stem respiration in ecological risk areas.

Reactive transport of CO2-rich fluids in simulated wellbore interfaces: Experiments and models exploring behaviour on length scales of 1 to 6 m

NASA Astrophysics Data System (ADS)

Wolterbeek, T. K. T.; Raoof, A.; Peach, C. J.; Spiers, C. J.

2016-12-01

Defects present at casing-cement interfaces in wellbores constitute potential pathways for CO2 to migrate from geological storage systems. It is essential to understand how the transport properties of such pathways evolve when penetrated by CO2-rich fluids. While numerous studies have explored this problem at the decimetre length-scale, the 1-10-100 m scales relevant for real wellbores have received little attention. The present work addresses the effects of long-range reactive transport on a length scale of 1-6 m. This is done by means of a combined experimental and modelling study. The experimental work consisted of flow-through tests, performed on cement-filled steel tubes, 1-6 m in length, containing artificially debonded cement-interfaces. Four tests were performed, at 60-80 °C, imposing flow-through of CO2-rich fluid at mean pressures of 10-15 MPa, controlling the pressure difference at 0.12-4.8 MPa, while measuring flow-rate. In the modelling work, we developed a numerical model to explore reactive transport in CO2-exposed defects on a similar length scale. The formulation adopted incorporates fluid flow, advective and diffusive solute transport, and CO2-cement chemical reactions. Our results show that long-range reactive transport strongly affects the permeability evolution of CO2-exposed defects. In the experiments, sample permeability decreased by 2-4 orders, which microstructural observations revealed was associated with downstream precipitation of carbonates, possibly aided by migration of fines. The model simulations show precipitation in initially open defects produces a sharp decrease in flow rate, causing a transition from advection to diffusion-dominated reactive transport. While the modelling results broadly reproduce the experimental observations, it is further demonstrated that non-uniformity in initial defect aperture has a profound impact on self-sealing behaviour and system permeability evolution on the metre scale. The implication is that future reactive transport models and wellbore scale analyses must include defects with variable aperture in order to obtain reliable upscaling relations.

Responses of photosynthetic O2 evolution to PPFD in the CAM epiphyte Tillandsia usneoides L. (Bromeliaceae).

PubMed

Martin, C E; McKee, J M; Schmitt, A K

1989-09-01

Past studies of the effects of varying levels of photosynthetic photon flux density (PPFD) on the morphology and physiology of the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides L. (Bromeliaceae) have resulted in two important findings: (1) CAM, measured as integrated nocturnal CO2 uptake or as nocturnal increases in tissue acidity, saturates at relatively low PPFD, and (2) this plant does not acclimate to different PPFD levels, these findings require substantiation using photosynthetic responses immediately attributable to different PPFD levels, e.g., O2 evolution, as opposed to the delayed, nocturnal responses (CO2 uptake and acid accumulation). In the present study, instantaneous responses of O2 evolution to PPFD level were measured using plants grown eight weeks at three PPFD (20-45, 200-350, and 750-800 μmol m(-2)s(-1)) in a growth chamber, and using shoots taken from the exposed upper portions (maximum PPFD of 800 μmol m(-2)s(-1)) and shaded lower portions (maximum PPFD of 140 μmol m(-2)s(-1)) of plants grown ten years in a greenhouse. In addition, nocturnal increases in acidity were measured in the growth chamber plants. Regardless of the PPFD levels during growth, O2 evolution rates saturated around 500 μmol m(-2)s(-1). Furthermore, nocturnal increases in tissue acidity saturated at much lower PPFD. Thus, previous results were confirmed: photosynthesis saturated at low PPFD, and this epiphyte does not acclimate to different levels of PPFD.

In situ photodeposition of cobalt on CdS nanorod for promoting photocatalytic hydrogen production under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Yanhong; Liu, Mei; Gao, Li; Mao, Liqun; Fan, Zeyun; Shangguan, Wenfeng

2018-06-01

Non-noble metal Co were loaded on CdS for enhancing photocatalytic activity of water splitting by a simple and efficient in situ photodeposition method. The Co particles with diameter ca. 5 nm were photoreduced and then loaded on the surface of CdS. The loading of Co can not only effectively promote the separation of electrons and holes photoexcited by CdS, but reduce the overpotential of hydrogen evolution as well, thus enhancing photocatalytic activity of water splitting. The highest photocatalytic H2 evolution rate of Co/CdS reaches up to 1299 μmol h-1 under visible light irradiation(λ > 420 nm) when the amount of loading is 1.0 wt%, which is 17 times of that of pure CdS and achieves 80% of that of 0.5 wt%Pt/CdS. This work not only exhibits a pathway to obtain photocatalysts with high photocatalytic activity for hydrogen production, but provides a possibility for the utilization of low cost Co as a substitute for noble metals in photocatalytic hydrogen production.

Constraining Path-Dependent Processes During Basalt-CO2 Interactions with Observations From Flow-Through and Batch Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Garing, C.; Zahasky, C.; Harrison, A. L.; Bird, D. K.; Benson, S. M.; Oelkers, E. H.; Maher, K.

2017-12-01

Predicting the timing and magnitude of CO2 storage in basaltic rocks relies partly on quantifying the dependence of reactivity on flow path and mineral distribution. Flow-through experiments that use intact cores are advantageous because the spatial heterogeneity of pore space and reactive phases is preserved. Combining aqueous geochemical analyses and petrologic characterization with non-destructive imaging techniques (e.g. micro-computed tomography) constrains the relationship between irreversible reactions, pore connectivity and accessible surface area. Our work enhances these capabilities by dynamically imaging flow through vesicular basalts with Positron Emission Tomography (PET) scanning. PET highlights the path a fluid takes by detecting photons produced during radioactive decay of an injected radiotracer (FDG). We have performed single-phase, CO2-saturated flow-through experiments with basaltic core from Iceland at CO2 sequestration conditions (50 °C; 76-90 bar Ptot). Constant flow rate and continuous pressure measurements at the inlet and outlet of the core constrain permeability. We monitor geochemical evolution through cation and anion analysis of outlet fluid sampled periodically. Before and after reaction, we perform PET scans and characterize the core using micro-CT. The PET scans indicate a discrete, localized flow path that appears to be a micro-crack connecting vesicles, suggesting that vesicle-lining minerals are immediately accessible and important reactants. Rapid increases in aqueous cation concentration, pH and HCO3- indicate that the rock reacts nearly immediately after CO2 injection. After 24 hours the solute release decreases, which may reflect a transition to reaction with phases with slower kinetic dissolution rates (e.g. zeolites and glasses to feldspar), a decrease in available reactive surface area or precipitation. We have performed batch experiments using crushed material of the same rock to elucidate the effect of flow path geometry and mineral accessibility on geochemical evolution. Interestingly, surface area-normalized dissolution rates as evinced by SiO2 release in all experiments approach similar values ( 10-15 mol/cm2/s). Our experiments show how imaging techniques are helpful in interpreting path-dependent processes in open systems.

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

PubMed

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

The effects of a deleterious mutation load on patterns of influenza A/H3N2's antigenic evolution in humans

PubMed Central

Koelle, Katia; Rasmussen, David A

2015-01-01

Recent phylogenetic analyses indicate that RNA virus populations carry a significant deleterious mutation load. This mutation load has the potential to shape patterns of adaptive evolution via genetic linkage to beneficial mutations. Here, we examine the effect of deleterious mutations on patterns of influenza A subtype H3N2's antigenic evolution in humans. By first analyzing simple models of influenza that incorporate a mutation load, we show that deleterious mutations, as expected, act to slow the virus's rate of antigenic evolution, while making it more punctuated in nature. These models further predict three distinct molecular pathways by which antigenic cluster transitions occur, and we find phylogenetic patterns consistent with each of these pathways in influenza virus sequences. Simulations of a more complex phylodynamic model further indicate that antigenic mutations act in concert with deleterious mutations to reproduce influenza's spindly hemagglutinin phylogeny, co-circulation of antigenic variants, and high annual attack rates. DOI: http://dx.doi.org/10.7554/eLife.07361.001 PMID:26371556

The Heavy Links between Geological Events and Vascular Plants Evolution: A Brief Outline

PubMed Central

Piombino, Aldo

2016-01-01

Since the rise of photosynthesis, life has influenced terrestrial atmosphere, particularly the O2 and the CO2 content (the latter being originally more than 95%), changing the chemistry of waters, atmosphere, and soils. Billions of years after, a far offspring of these first unicellular forms conquered emerging lands, not only completely changing landscape, but also modifying geological cycles of deposition and erosion, many chemical and physical characteristics of soils and fresh waters, and, more, the cycle of various elements. So, there are no doubts that vascular plants modified geology; but it is true that also geology has affected (and, more, has driven) plant evolution. New software, PyRate, has determined vascular plant origin and diversification through a Bayesian analysis of fossil record from Silurian to today, particularly observing their origination and extinction rate. A comparison between PyRate data and geological history suggests that geological events massively influenced plant evolution and that also the rise of nonflowering seed plants and the fast diffusion of flowering plants can be explained, almost partly, with the environmental condition changes induced by geological phenomena. PMID:26966609

The Heavy Links between Geological Events and Vascular Plants Evolution: A Brief Outline.

PubMed

Piombino, Aldo

2016-01-01

Since the rise of photosynthesis, life has influenced terrestrial atmosphere, particularly the O2 and the CO2 content (the latter being originally more than 95%), changing the chemistry of waters, atmosphere, and soils. Billions of years after, a far offspring of these first unicellular forms conquered emerging lands, not only completely changing landscape, but also modifying geological cycles of deposition and erosion, many chemical and physical characteristics of soils and fresh waters, and, more, the cycle of various elements. So, there are no doubts that vascular plants modified geology; but it is true that also geology has affected (and, more, has driven) plant evolution. New software, PyRate, has determined vascular plant origin and diversification through a Bayesian analysis of fossil record from Silurian to today, particularly observing their origination and extinction rate. A comparison between PyRate data and geological history suggests that geological events massively influenced plant evolution and that also the rise of nonflowering seed plants and the fast diffusion of flowering plants can be explained, almost partly, with the environmental condition changes induced by geological phenomena.

Efficient reduction of CO2 to CO with high current density using in situ or ex situ prepared Bi-based materials.

PubMed

Medina-Ramos, Jonnathan; DiMeglio, John L; Rosenthal, Joel

2014-06-11

The development of inexpensive electrocatalysts that can promote the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is an important step on the path to renewable production of liquid carbon-based fuels. While precious metals such as gold and silver have historically been the most active cathode materials for CO2 reduction, the price of these materials precludes their use on the scale required for fuel production. Bismuth, by comparison, is an affordable and environmentally benign metal that shows promise for CO2 conversion applications. In this work, we show that a bismuth-carbon monoxide evolving catalyst (Bi-CMEC) can be formed under either aqueous or nonaqueous conditions using versatile electrodeposition methods. In situ formation of this thin-film catalyst on an inexpensive carbon electrode using an organic soluble Bi(3+) precursor streamlines preparation of this material and generates a robust catalyst for CO2 reduction. In the presence of appropriate imidazolium based ionic liquid promoters, the Bi-CMEC platform can selectively catalyze conversion of CO2 to CO without the need for a costly supporting electrolyte. This inexpensive system can catalyze evolution of CO with current densities as high as jCO = 25-30 mA/cm(2) and attendant energy efficiencies of ΦCO ≈ 80% for the cathodic half reaction. These metrics highlight the efficiency of Bi-CMEC, since only noble metals have been previously shown to promote this fuel forming half reaction with such high energy efficiency. Moreover, the rate of CO production by Bi-CMEC ranges from approximately 0.1-0.5 mmol·cm(-2)·h(-1) at an applied overpotential of η ≈ 250 mV for a cathode with surface area equal to 1.0 cm(2). This CO evolution activity is much higher than that afforded by other non-noble metal cathode materials and distinguishes Bi-CMEC as a superior and inexpensive platform for electrochemical conversion of CO2 to fuel.

Biodegradation of 1,2,3- and 1,2,4-Trichlorobenzene in Soil and in Liquid Enrichment Culture †

PubMed Central

Marinucci, A. C.; Bartha, R.

1979-01-01

The biodegradation of radiochemically pure (99%) 1,2,3- and 1,2,4-trichlorobenzene (TCB) in soil was investigated. Experimental difficulties posed by the high volatility and slow biodegradation rate of the TCBs were partially overcome by using a specially designed incubation and trapping apparatus. Evolution of 14CO2 from active versus poisoned soil dosed with 50 μg of the individual TCBs per g gave conclusive proof that both isomers are biodegradable. At 20°C, 1,2,4-TCB was mineralized at an approximate rate of 1 nmol/day per 20 g of soil sample, and 1,2,3-TCB was mineralized at one-half to one-third that rate. Mineral fertilizers or cosubstrates failed to increase TCB mineralization rates in soil. Anaerobic conditions had a negative effect on mineralization, and increased temperatures had a positive effect. With increasing 1,2,4-TCB concentrations, 14CO2 evolution exhibited saturation kinetics with an apparent Km of 55.5 nmol per g of soil. Recovery of total radioactivity was good from soil containing high organic matter concentrations. From low-organic-matter soil, some of the radioactivity was recovered only on combustion, and overall recovery was lower. In soil-inoculated liquid culture, the cosubstrates glucose and benzene caused a slight stimulation of 1,2,4-TCB mineralization. Cochromatography of known standards with the extracts of soil pretreated with [14C]TCBs indicated that 3,4,5-trichlorophenol, 2,6-dichlorophenol and, to a lesser degree, 2,3-dichlorophenol were present in soils incubated with 1,2,3-TCB. 2,4-, 2,5-, and 3,4-dichlorophenol were present in soils incubated with 1,2,4-TCB. PMID:120698

Micro-CT in situ study of carbonate rock microstructural evolution for geologic CO2 storage

NASA Astrophysics Data System (ADS)

Zheng, Y.; Yang, Y.; Rogowska, M.; Gundlach, C.

2017-09-01

To achieve the 2°C target made in the 2016 Paris Agreement, it is essential to reduce the emission of CO2 into the atmosphere. Carbon Capture and Storage (CCS) has been given increasing importance over the last decade. One of the suggested methods for CCS is to inject CO2 into geologic settings such as the carbonate reservoirs in the North Sea. The final aim of our project is to find out how to control the evolution of petrophysical parameters during CO2 injection using an optimal combination of flow rate, injection pressure and chemical composition of the influent. The first step to achieve this is to find a suitable condition to create a stable 3D space in carbonate rock by injecting liquid to prepare space for the later CO2 injection. Micro-CT imaging is a non-destructive 3D method that can be used to study the property changes of carbonate rocks during and after CO2 injection. The advance in lab source based micro-CT has made it capable of in situ experiments. We used a commercial bench top micro-CT (Zeiss Versa XRM410) to study the microstructure changes of chalk during liquid injection. Flexible temporal CT resolution is essential in this study because that the time scales of coupled physical and chemical processes can be very different. The results validated the feasibility of using a bench top CT system with a pressure cell to monitor the mesoscale multiphase interactions in chalk.

Non-Boussinesq Dissolution-Driven Convection in Porous Media

NASA Astrophysics Data System (ADS)

Amooie, M. A.; Soltanian, M. R.; Moortgat, J.

2017-12-01

Geological carbon dioxide (CO2) sequestration in deep saline aquifers has been increasingly recognized as a feasible technology to stabilize the atmospheric carbon concentrations and subsequently mitigate the global warming. Solubility trapping is one of the most effective storage mechanisms, which is associated initially with diffusion-driven slow dissolution of gaseous CO2 into the aqueous phase, followed by density-driven convective mixing of CO2 throughout the aquifer. The convection includes both diffusion and fast advective transport of the dissolved CO2. We study the fluid dynamics of CO2 convection in the underlying single aqueous-phase region. Two modeling approaches are employed to define the system: (i) a constant-concentration condition for CO2 in aqueous phase at the top boundary, and (ii) a sufficiently low, constant injection-rate for CO2 from top boundary. The latter allows for thermodynamically consistent evolution of the CO2 composition and the aqueous phase density against the rate at which the dissolved CO2 convects. Here we accurately model the full nonlinear phase behavior of brine-CO2 mixture in a confined domain altered by dissolution and compressibility, while relaxing the common Boussinesq approximation. We discover new flow regimes and present quantitative scaling relations for global characters of spreading, mixing, and dissolution flux in two- and three-dimensional media for the both model types. We then revisit the universal Sherwood-Rayleigh scaling that is under debate for porous media convective flows. Our findings confirm the sublinear scaling for the constant-concentration case, while reconciling the classical linear scaling for the constant-injection model problem. The results provide a detailed perspective into how the available modeling strategies affect the prediction ability for the total amount of CO2 dissolved in the long term within saline aquifers of different permeabilities.

One-carbon substrate-based biohydrogen production: microbes, mechanism, and productivity.

PubMed

Rittmann, Simon K-M R; Lee, Hyun Sook; Lim, Jae Kyu; Kim, Tae Wan; Lee, Jung-Hyun; Kang, Sung Gyun

2015-01-01

Among four basic mechanisms for biological hydrogen (H2) production, dark fermentation has been considered to show the highest hydrogen evolution rate (HER). H2 production from one-carbon (C1) compounds such as formate and carbon monoxide (CO) is promising because formate is an efficient H2 carrier, and the utilization of CO-containing syngas or industrial waste gas may render the industrial biohydrogen production process cost-effective. A variety of microbes with the formate hydrogen lyase (FHL) system have been identified from phylogenetically diverse groups of archaea and bacteria, and numerous efforts have been undertaken to improve the HER for formate through strain optimization and bioprocess development. CO-dependent H2 production has been investigated to enhance the H2 productivity of various carboxydotrophs via an increase in CO gas-liquid mass transfer rates and the construction of genetically modified strains. Hydrogenogenic CO-conversion has been applied to syngas and by-product gas of the steel-mill process, and this low-cost feedstock has shown to be promising in the production of biomass and H2. Here, we focus on recent advances in the isolation of novel phylogenetic groups utilizing formate or CO, the remarkable genetic engineering that enhances H2 productivity, and the practical implementation of H2 production from C1 substrates. Copyright © 2014 Elsevier Inc. All rights reserved.

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

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

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Wrinkle-free atomically thin CdS nanosheets for photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Pan, Ziwei; Li, Junnan; Zhou, Kebin

2018-05-01

Two-dimensional (2D) nanosheets of atomic thickness have attracted extensive research interest recently. In this work, atomically thin (0.7 nm) flat CdS (F-CdS) nanosheets of several tens of micrometers in lateral size were synthesized by a solvent-thermal method. The as-synthesized F-CdS could maintain flat morphology well in solution, while irreversible wrinkles could be generated after drying, forming wrinkled CdS (W-CdS) samples. It was revealed that the formation of wrinkles could reduce light absorbance, narrow the band gap, move down the conduction band position and accelerate electron–hole recombination. As photocatalysts, the F-CdS achieved a photocatalytic H2 evolution rate of 138.7 mmol g‑1 h‑1 without any co-catalyst under visible light, which was much higher than that of the W-CdS sample (with an H2 evolution rate of only 52.8 mmol g‑1 h‑1). This work demonstrates that great attention should be paid to the wrinkles in 2D materials as photocatalysts.

Ternary Pt/SnO(x)/TiO2 photocatalysts for hydrogen production: consequence of Pt sites for synergy of dual co-catalysts.

PubMed

Gu, Quan; Long, Jinlin; Zhuang, Huaqiang; Zhang, Chaoqiang; Zhou, Yangen; Wang, Xuxu

2014-06-28

A variety of ternary nanoheterostructures composed of Pt nanoparticles (NPs), SnOx species, and anatase TiO2 are designed elaborately to explore the effect of interfacial electron transfer on photocatalytic H2 evolution from a biofuel-water solution. Among numerous factors controlling the H2 evolution, the significance of Pt sites for the H2 evolution is highlighted by tuning the loading procedure of Pt NPs and SnOx species over TiO2. A synergistic enhancement of H2 evolution can be achieved over the Pt/SnOx/TiO2 heterostructures formed by anchoring Pt NPs at atomically-isolated Sn-oxo sites, whereas the Pt/TiO2/SnOx counterparts prepared by grafting single-site Sn-oxo species on Pt/TiO2 show a marked decrease in the rate of H2 evolution. The characterization results clearly reveal that the synergy of Pt NPs and SnOx species originates from the vectorial electron transfer of TiO2 → SnOx → Pt occurring on the former, while the latter results from the competitive electron transfer from TiO2 to SnOx and to Pt NPs.

Synergistically enhanced photocatalytic hydrogen evolution performance of ZnCdS by co-loading graphene quantum dots and PdS dual cocatalysts under visible light

NASA Astrophysics Data System (ADS)

Wang, Fang; Su, Yanhong; Min, Shixiong; Li, Yanan; Lei, Yonggang; Hou, Jianhua

2018-04-01

Here, we report that the co-loading of graphene quantum dots (GQDs) and PdS dual cocatalysts on ZnCdS surface achieves a high efficiency photocatalytic H2 evolution under visible light (≥420 nm). The GQDs/ZnCdS/PdS photocatalyst was prepared by a facile two steps: hydrothermal coupling of GQDs on ZnCdS surface followed by an in-situ chemical deposition of PdS. The resulted GQDs/ZnCdS/PdS exhibits a H2 evolution rate of 517 μmol h-1, which is 15, 7, and 1.7 times higher than that of pure ZnCdS, GQDs/ZnCdS, and ZnCdS/PdS, respectively, demonstrating the synergistic effects of GQDs and PdS dual cocatalysts. A high apparent quantum efficiency (AQE) up to 22.4% can be achieved over GQDs/ZnCdS/PdS at 420 nm. GQDs/ZnCdS/PdS also has a relatively good stability. Such a considerable enhancement of photocatalytic activity was attributable to the co-loading of the GQDs and PdS as respective reduction and oxidation cocatalysts, leading to an efficient charge separation and surface reactions.

Co-composting of vegetable wastes and carton: Effect of carton composition and parameter variations.

PubMed

Rawoteea, Soonita Anjeena; Mudhoo, Ackmez; Kumar, Sunil

2017-03-01

The aim of the study was to investigate the effects of carton in the composting process of mixed vegetable wastes using an experimental composter of capacity 80L. Three different mixes were set-up (Mixes 1, 2 and 3) which consisted of vegetable wastes, 2.0kg paper and bulking agents, vegetable wastes, 1.5kg carton and bulking agents, vegetable wastes, 4.5kg carton and bulking agents, respectively. Temperature evolution, pH trends, moisture levels, respiration rates, percentage volatile solids and electrical conductivity were monitored for a period of 50days. The system remained under thermophilic conditions for a very short period due to the small size of the reactor. The three mixes did not exceed a temperature of 55°C, where sanitization takes place by the destruction of pathogens. The highest peak of CO 2 evolution was observed in Mix 2 indicating that maximum microbial degradation took place in that mix. Copyright © 2016. Published by Elsevier Ltd.

Effects of ploidy level and haplotype on variation of photosynthetic traits: Novel evidence from two Fragaria species

PubMed Central

Gao, Song; Yan, Qiaodi; Chen, Luxi; Song, Yaobin; Fu, Chengxin; Dong, Ming

2017-01-01

To reveal the effects of ploidy level and haplotype on photosynthetic traits, we chose 175 genotypes of wild strawberries belonging to two haplotypes at two types of ploidy levels (diploidy and tetraploidy) and measured photosynthetic traits. Our results revealed that ploidy significantly affected the characteristics of light-response curves, CO2-response curves, and leaf gas exchange parameters, except intercellular CO2 concentration (Ci). Tetraploid species had a lower light saturation point (LSP) and CO2 saturation point (CSP), higher light compensation point (LCP), dark respiration (Rd), and CO2 compensation point (CCP) than diploid species. Furthermore, tetraploid species have lower photosynthetic capacity than diploid species, including net photosynthetic rate (Pn), stomatal conductivity (Gs), and transpiration rate (Tr). In addition, haplotype had a significant effect on LSP, CSP, Tr, and Ci as well as a significant interactive effect between ploidy and haplotype on the maximal photosynethic rate of the light-response curve and Rd. Most of the variance existed within haplotypes among individuals. These results suggest that polyploidization was the main driver for the evolution of photosynthesis with increasing ploidy level (i.e. from diploidy to tetraploidy in Fragaria species), while the origin of a chromosome could also affect the photosynthetic traits and the polyploidization effect on photosynthetic traits. PMID:28644876

Effects of ploidy level and haplotype on variation of photosynthetic traits: Novel evidence from two Fragaria species.

PubMed

Gao, Song; Yan, Qiaodi; Chen, Luxi; Song, Yaobin; Li, Junmin; Fu, Chengxin; Dong, Ming

2017-01-01

To reveal the effects of ploidy level and haplotype on photosynthetic traits, we chose 175 genotypes of wild strawberries belonging to two haplotypes at two types of ploidy levels (diploidy and tetraploidy) and measured photosynthetic traits. Our results revealed that ploidy significantly affected the characteristics of light-response curves, CO2-response curves, and leaf gas exchange parameters, except intercellular CO2 concentration (Ci). Tetraploid species had a lower light saturation point (LSP) and CO2 saturation point (CSP), higher light compensation point (LCP), dark respiration (Rd), and CO2 compensation point (CCP) than diploid species. Furthermore, tetraploid species have lower photosynthetic capacity than diploid species, including net photosynthetic rate (Pn), stomatal conductivity (Gs), and transpiration rate (Tr). In addition, haplotype had a significant effect on LSP, CSP, Tr, and Ci as well as a significant interactive effect between ploidy and haplotype on the maximal photosynethic rate of the light-response curve and Rd. Most of the variance existed within haplotypes among individuals. These results suggest that polyploidization was the main driver for the evolution of photosynthesis with increasing ploidy level (i.e. from diploidy to tetraploidy in Fragaria species), while the origin of a chromosome could also affect the photosynthetic traits and the polyploidization effect on photosynthetic traits.

Assessment of CO2 Mineralization and Dynamic Rock Properties at the Kemper Pilot CO2 Injection Site

NASA Astrophysics Data System (ADS)

Qin, F.; Kirkland, B. L.; Beckingham, L. E.

2017-12-01

CO2-brine-mineral reactions following CO2 injection may impact rock properties including porosity, permeability, and pore connectivity. The rate and extent of alteration largely depends on the nature and evolution of reactive mineral interfaces. In this work, the potential for geochemical reactions and the nature of the reactive mineral interface and corresponding hydrologic properties are evaluated for samples from the Lower Tuscaloosa, Washita-Fredericksburg, and Paluxy formations. These formations have been identified as future regionally extensive and attractive CO2 storage reservoirs at the CO2 Storage Complex in Kemper County, Mississippi, USA (Project ECO2S). Samples from these formations were obtained from the Geological Survey of Alabama and evaluated using a suite of complementary analyses. The mineral composition of these samples will be determined using petrography and powder X-ray Diffraction (XRD). Using these compositions, continuum-scale reactive transport simulations will be developed and the potential CO2-brine-mineral interactions will be examined. Simulations will focus on identifying potential reactive minerals as well as the corresponding rate and extent of reactions. The spatial distribution and accessibility of minerals to reactive fluids is critical to understanding mineral reaction rates and corresponding changes in the pore structure, including pore connectivity, porosity and permeability. The nature of the pore-mineral interface, and distribution of reactive minerals, will be determined through imaging analysis. Multiple 2D scanning electron microscopy (SEM) backscattered electron (BSE) images and energy dispersive x-ray spectroscopy (EDS) images will be used to create spatial maps of mineral distributions. These maps will be processed to evaluate the accessibility of reactive minerals and the potential for flow-path modifications following CO2 injection. The "Establishing an Early CO2 Storage Complex in Kemper, MS" project is funded by the U.S. Department of Energy's National Energy Technology Laboratory and cost-sharing partners.

Early stages in the evolution of the atmosphere and climate on the Earth-group planets

NASA Technical Reports Server (NTRS)

Moroz, V. I.; Mukhin, L. M.

1977-01-01

The early evolution of the atmospheres and climate of the Earth, Mars and Venus is discussed, based on a concept of common initial conditions and main processes (besides known differences in chemical composition and outgassing rate). It is concluded that: (1) liquid water appeared on the surface of the earth in the first few hundred million years; the average surface temperature was near the melting point for about the first two eons; CO2 was the main component of the atmosphere in the first 100-500 million years; (2) much more temperate outgassing and low solar heating led to the much later appearance of liquid water on the Martian surface, only one to two billion years ago; the Martian era of rivers, relatively dense atmosphere and warm climate ended as a result of irreversible chemical bonding of CO2 by Urey equilibrium processes; (3) a great lack of water in the primordial material of Venus is proposed; liquid water never was present on the surface of the planet, and there was practically no chemical bonding of CO2; the surface temperature was over 600 K four billion years ago.

Dione and Rhea seasonal exospheres revealed by Cassini CAPS and INMS

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Waite, J. H.

2016-07-01

A Dione O2 and CO2 exosphere of similar composition and density to Rhea's is confirmed by Cassini spacecraft Ion Neutral Mass Spectrometer (INMS) flyby data. INMS results from three Dione and two Rhea flybys show exospheric spatial and temporal variability indicative of seasonal exospheres, modulated by winter polar gas adsorption and desorption at the equinoxes. Cassini Plasma Spectrometer (CAPS) pickup ion fluxes also show exospheric structure and evolution at Rhea consistent with INMS, after taking into consideration the anticipated charge exchange, electron impact, and photo-ionization rates. Data-model comparisons show the exospheric evolution to be consistent with polar frost diffusion into the surface regolith, which limits surface exposure and loss of the winter frost cap by sputtering. Implied O2 source rates of ∼45(7) × 1021 s-1 at Dione(Rhea) are ∼50(300) times less than expected from known O2 radiolysis yields from ion-irradiated pure water ice measured in the laboratory, ruling out secondary sputtering as a major exospheric contributor, and implying a nanometer scale surface refractory lag layer consisting of concentrated carbonaceous impurities. We estimate ∼30:1(2:1) relative O2:CO2 source rates at Dione(Rhea), consistent with a stoichiometric bulk composition below the lag layer of 0.01(0.13) C atoms per H2O molecule, deriving from endogenic constituents, implanted micrometeoritic organics, and (in particular at Dione) exogenous H2O delivery by E-ring grains. Impact deposition, gardening and vaporization may thereby control the global O2 source rates by fresh H2O ice exposure to surface radiolysis and trapped oxidant ejection.

Magnetic resonance imaging study on near miscible supercritical CO2 flooding in porous media

NASA Astrophysics Data System (ADS)

Song, Yongchen; Zhu, Ningjun; Zhao, Yuechao; Liu, Yu; Jiang, Lanlan; Wang, Tonglei

2013-05-01

CO2 flooding is one of the most popular secondary or tertiary recoveries for oil production. It is also significant for studying the mechanisms of the two-phase and multiphase flow in porous media. In this study, an experimental study was carried out by using magnetic resonance imaging technique to examine the detailed effects of pressure and rates on CO2/decane flow in a bead-pack porous media. The displacing processes were conducted under various pressures in a region near the minimum miscibility pressure (the system tuned from immiscible to miscible as pressure is increasing in this region) and the temperature of 37.8 °C at several CO2 injection volumetric rates of 0.05, 0.10, and 0.15 ml/min (or linear rates of 3.77, 7.54, and 11.3 ft/day). The evolution of the distribution of decane and the characteristics of the two phase flow were investigated and analyzed by considering the pressure and rate. The area and velocity of the transition zone between the two phases were calculated and analyzed to quantify mixing. The area of transition zone decreased with pressure at near miscible region and a certain injection rate and the velocity of the transition zone was always less than the "volumetric velocity" due to mutual solution and diffusion of the two phases. Therefore, these experimental results give the fundamental understanding of tertiary recovery processes at near miscible condition.

Bundle Sheath Diffusive Resistance to CO2 and Effectiveness of C4 Photosynthesis and Refixation of Photorespired CO2 in a C4 Cycle Mutant and Wild-Type Amaranthus edulis1

PubMed Central

Kiirats, Olavi; Lea, Peter J.; Franceschi, Vincent R.; Edwards, Gerald E.

2002-01-01

A mutant of the NAD-malic enzyme-type C4 plant, Amaranthus edulis, which lacks phosphoenolpyruvate carboxylase (PEPC) in the mesophyll cells was studied. Analysis of CO2 response curves of photosynthesis of the mutant, which has normal Kranz anatomy but lacks a functional C4 cycle, provided a direct means of determining the liquid phase-diffusive resistance of atmospheric CO2 to sites of ribulose 1,5-bisphosphate carboxylation inside bundle sheath (BS) chloroplasts (rbs) within intact plants. Comparisons were made with excised shoots of wild-type plants fed 3,3-dichloro-2-(dihydroxyphosphinoyl-methyl)-propenoate, an inhibitor of PEPC. Values of rbs in A. edulis were 70 to 180 m2 s−1 mol−1, increasing as the leaf matured. This is about 70-fold higher than the liquid phase resistance for diffusion of CO2 to Rubisco in mesophyll cells of C3 plants. The values of rbs in A. edulis are sufficient for C4 photosynthesis to elevate CO2 in BS cells and to minimize photorespiration. The calculated CO2 concentration in BS cells, which is dependent on input of rbs, was about 2,000 μbar under maximum rates of CO2 fixation, which is about six times the ambient level of CO2. High re-assimilation of photorespired CO2 was demonstrated in both mutant and wild-type plants at limiting CO2 concentrations, which can be explained by high rbs. Increasing O2 from near zero up to ambient levels under low CO2, resulted in an increase in the gross rate of O2 evolution measured by chlorophyll fluorescence analysis in the PEPC mutant; this increase was simulated from a Rubisco kinetic model, which indicates effective refixation of photorespired CO2 in BS cells. PMID:12376660

Meteoric Metal Chemistry in the Martian Atmosphere

PubMed Central

Carrillo‐Sanchez, J. D.; Mangan, T. P.; Crismani, M. M. J.; Schneider, N. M.; Määttänen, A.

2018-01-01

Abstract Recent measurements by the Imaging Ultraviolet Spectrograph (IUVS) instrument on NASA's Mars Atmosphere and Volatile EvolutioN mission show that a persistent layer of Mg+ ions occurs around 90 km in the Martian atmosphere but that neutral Mg atoms are not detectable. These observations can be satisfactorily modeled with a global meteoric ablation rate of 0.06 t sol−1, out of a cosmic dust input of 2.7 ± 1.6 t sol−1. The absence of detectable Mg at 90 km requires that at least 50% of the ablating Mg atoms ionize through hyperthermal collisions with CO2 molecules. Dissociative recombination of MgO+.(CO2)n cluster ions with electrons to produce MgCO3 directly, rather than MgO, also avoids a buildup of Mg to detectable levels. The meteoric injection rate of Mg, Fe, and other metals—constrained by the IUVS measurements—enables the production rate of metal carbonate molecules (principally MgCO3 and FeCO3) to be determined. These molecules have very large electric dipole moments (11.6 and 9.2 Debye, respectively) and thus form clusters with up to six H2O molecules at temperatures below 150 K. These clusters should then coagulate efficiently, building up metal carbonate‐rich ice particles which can act as nucleating particles for the formation of CO2‐ice clouds. Observable mesospheric clouds are predicted to occur between 65 and 80 km at temperatures below 95 K and above 85 km at temperatures about 5 K colder. PMID:29780678

Modelling (18)O2 and (16)O2 unidirectional fluxes in plants. IV: role of conductance and laws of its regulation in C3 plants.

PubMed

André, Marcel J

2013-08-01

Numerous studies focus on the measurement of conductances for CO2 transfer in plants and especially on their regulatory effects on photosynthesis. Measurement accuracy is strongly dependent on the model used and on the knowledge of the flow of photochemical energy generated by light in chloroplasts. The only accurate and precise method to quantify the linear electron flux (responsible for the production of reductive energy) is the direct measurement of O2 evolution, by (18)O2 labelling and mass spectrometry. The sharing of this energy between the carboxylation (P) and the oxygenation of photorespiration (PR) depends on the plant specificity factor (Sp) and on the corresponding atmospheric concentrations of CO2 and O2 (André, 2013). The concept of plant specificity factor simplifies the equations of the model. It gives a new expression of the effect of the conductance (g) between atmosphere and chloroplasts. Its quantitative effect on photosynthesis is easy to understand because it intervenes in the ratio of the plant specificity factor (Sp) to the specificity of Rubisco (Sr). Using this 'simple' model with the data of (18)O2 experiments, the calculation of conductance variations in response to CO2 and light was carried out. The good fitting of experimental data of O2 and CO2 exchanges confirms the validity of the simple model. The calculation of conductance variation during the increase of external CO2 concentration reveals a linear law of regulation between external and internal CO2 concentrations. During CO2 variations, the effects of g regulation tend to maintain a higher level of oxygenation (PR) in expense of a better carboxylation (P). Contrary to CO2, the variation of O2 creates a negative feedback effect compatible with a stabilization of atmospheric O2. The regulation of g amplifies this result. The effect of light in combination with CO2 is more complex. Below 800μmolquantam(-2)s(-1) the ratio PR/P is maintained unchangeable in expense of carboxylation efficiency. Above that irradiance value, PR/P increases dramatically. It appears that the saturation curves of photosynthesis under high light could be simply due to the regulation by the conductance g and not by any biochemical or biophysical limitation. In conclusion, the regulatory effect of conductance operates in a way that it preserves the rate of photorespiration. This confirms a positive and protective role of photorespiration at the biochemical, whole plant and atmosphere levels. Since the effects of photorespiration are linked to the properties of Rubisco, they add new arguments for a co-evolution of plant and atmosphere, including the evolution of CO2 conductance. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Heterostructured WS2 -MoS2 Ultrathin Nanosheets Integrated on CdS Nanorods to Promote Charge Separation and Migration and Improve Solar-Driven Photocatalytic Hydrogen Evolution.

PubMed

Reddy, D Amaranatha; Park, Hanbit; Ma, Rory; Kumar, D Praveen; Lim, Manho; Kim, Tae Kyu

2017-04-10

Solar-driven photocatalytic hydrogen evolution is important to bring solar-energy-to-fuel energy-conversion processes to reality. However, there is a lack of highly efficient, stable, and non-precious photocatalysts, and catalysts not designed completely with expensive noble metals have remained elusive, which hampers their large-scale industrial application. Herein, for the first time, a highly efficient and stable noble-metal-free CdS/WS 2 -MoS 2 nanocomposite was designed through a facile hydrothermal approach. When assessed as a photocatalyst for water splitting, the CdS/WS 2 -MoS 2 nanostructures exhibited remarkable photocatalytic hydrogen-evolution performance and impressive durability. An excellent hydrogen evolution rate of 209.79 mmol g -1  h -1 was achieved under simulated sunlight irradiation, which is higher than the values for CdS/MoS 2 (123.31 mmol g -1  h -1 ) and CdS/WS 2 nanostructures (169.82 mmol g -1  h -1 ) and the expensive CdS/Pt benchmark catalyst (34.98 mmol g -1  h -1 ). The apparent quantum yield reached 51.4 % at λ=425 nm in 5 h. Furthermore, the obtained hydrogen evolution rate was better than those of several noble-metal-free catalysts reported previously. The observed high rate of hydrogen evolution and remarkable stability may be a result of the ultrafast separation of photogenerated charge carriers and transport between the CdS nanorods and the WS 2 -MoS 2 nanosheets, which thus increases the number of electrons involved in hydrogen production. The proposed designed strategy is believed to potentially open a door to the design of advanced noble-metal-free photocatalytic materials for efficient solar-driven hydrogen production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic study of low-temperature CO2 plasmas under non-equilibrium conditions. I. Relaxation of vibrational energy

NASA Astrophysics Data System (ADS)

Silva, T.; Grofulović, M.; Klarenaar, B. L. M.; Morillo-Candas, A. S.; Guaitella, O.; Engeln, R.; Pintassilgo, C. D.; Guerra, V.

2018-01-01

A kinetic model describing the time evolution of ˜70 individual CO2(X1Σ+) vibrational levels during the afterglow of a pulsed DC glow discharge is developed in order to contribute to the understanding of vibrational energy transfer in CO2 plasmas. The results of the simulations are compared against in situ Fourier transform infrared spectroscopy data obtained in a pulsed DC glow discharge and its afterglow at pressures of a few Torr and discharge currents of around 50 mA. The very good agreement between the model predictions and the experimental results validates the kinetic scheme considered here and the corresponding vibration-vibration and vibration-translation rate coefficients. In this sense, it establishes a reaction mechanism for the vibrational kinetics of these CO2 energy levels and offers a firm basis to understand the vibrational relaxation in CO2 plasmas. It is shown that first-order perturbation theories, namely, the Schwartz-Slawsky-Herzfeld and Sharma-Brau methods, provide a good description of CO2 vibrations under low excitation regimes.

Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

NASA Technical Reports Server (NTRS)

Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

1996-01-01

Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

REDUCING UNCERTAINTIES IN MODEL PREDICTIONS VIA HISTORY MATCHING OF CO2 MIGRATION AND REACTIVE TRANSPORT MODELING OF CO2 FATE AT THE SLEIPNER PROJECT

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

Zhu, Chen

2015-03-31

An important question for the Carbon Capture, Storage, and Utility program is “can we adequately predict the CO2 plume migration?” For tracking CO2 plume development, the Sleipner project in the Norwegian North Sea provides more time-lapse seismic monitoring data than any other sites, but significant uncertainties still exist for some of the reservoir parameters. In Part I, we assessed model uncertainties by applying two multi-phase compositional simulators to the Sleipner Benchmark model for the uppermost layer (Layer 9) of the Utsira Sand and calibrated our model against the time-lapsed seismic monitoring data for the site from 1999 to 2010. Approximatemore » match with the observed plume was achieved by introducing lateral permeability anisotropy, adding CH4 into the CO2 stream, and adjusting the reservoir temperatures. Model-predicted gas saturation, CO2 accumulation thickness, and CO2 solubility in brine—none were used as calibration metrics—were all comparable with the interpretations of the seismic data in the literature. In Part II & III, we evaluated the uncertainties of predicted long-term CO2 fate up to 10,000 years, due to uncertain reaction kinetics. Under four scenarios of the kinetic rate laws, the temporal and spatial evolution of CO2 partitioning into the four trapping mechanisms (hydrodynamic/structural, solubility, residual/capillary, and mineral) was simulated with ToughReact, taking into account the CO2-brine-rock reactions and the multi-phase reactive flow and mass transport. Modeling results show that different rate laws for mineral dissolution and precipitation reactions resulted in different predicted amounts of trapped CO2 by carbonate minerals, with scenarios of the conventional linear rate law for feldspar dissolution having twice as much mineral trapping (21% of the injected CO2) as scenarios with a Burch-type or Alekseyev et al.–type rate law for feldspar dissolution (11%). So far, most reactive transport modeling (RTM) studies for CCUS have used the conventional rate law and therefore simulated the upper bound of mineral trapping. However, neglecting the regional flow after injection, as most previous RTM studies have done, artificially limits the extent of geochemical reactions as if it were in a batch system. By replenishing undersaturated groundwater from upstream, the Utsira Sand is reactive over a time scale of 10,000 years. The results from this project have been communicated via five peer-reviewed journal articles, four conference proceeding papers, and 19 invited and contributed presentations at conferences and seminars.« less

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

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

2017-02-06

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

Enhanced hydrogen release by catalyzed hydrolysis of sodium borohydride-ammonia borane mixtures: a solution-state 11B NMR study.

PubMed

Hannauer, J; Demirci, U B; Geantet, C; Herrmann, J M; Miele, P

2011-03-07

Hydrolysis of mixtures consisting of sodium borohydride NaBH(4) (SB) and ammonia borane NH(3)BH(3) (AB) was studied in the absence/presence of a Co catalyst. The kinetics of the H(2) evolutions was measured. The reactions were followed in situ by solution-state (11)B NMR and the hydrolysis by-products characterized by NMR, XRD and IR. It is demonstrated that the combination of the two compounds gives a synergetic effect. SB rapidly reduces the Co catalyst precursor and the NH(4)(+) ions from AB contribute in the dispersion of the in situ formed Co nanoparticles. As a result, the kinetics of H(2) evolution is greatly improved. For instance, a hydrogen generation rate of 29.6 L min(-1) g(-1)(Co) was found for a mixture consisting of 81 wt% NH(3)BH(3), 9 wt% NaBH(4) and 10 wt% CoCl(2). By (11)B NMR, it was showed that the reaction mechanisms are quite trivial. As soon as the Co catalyst forms in situ, SB, rather than AB, hydrolyzes until it is totally converted. Then, the overall hydrolysis continues with that of AB. Both reactions follow a bimolecular Langmuir-Hinshelwood mechanism; no reaction intermediates were observed during the process. In fact, SB and AB convert directly into B(OH)(4)(-), which comes in equilibrium with a polyborate compound identified as B(3)O(3)(OH)(4)(-). All of these results are discussed herein.

The co-evolution of microstructure features in self-ion irradiated HT9 at very high damage levels

NASA Astrophysics Data System (ADS)

Getto, E.; Vancoevering, G.; Was, G. S.

2017-02-01

Understanding the void swelling and phase evolution of reactor structural materials at very high damage levels is essential to maintaining safety and longevity of components in Gen IV fast reactors. A combination of ion irradiation and modeling was utilized to understand the microstructure evolution of ferritic-martensitic alloy HT9 at high dpa. Self-ion irradiation experiments were performed on alloy HT9 to determine the co-evolution of voids, dislocations and precipitates up to 650 dpa at 460 °C. Modeling of microstructure evolution was conducted using the modified Radiation Induced Microstructure Evolution (RIME) model, which utilizes a mean field rate theory approach with grouped cluster dynamics. Irradiations were performed with 5 MeV raster-scanned Fe2+ ions on samples pre-implanted with 10 atom parts per million He. The swelling, dislocation and precipitate evolution at very high dpa was determined using Analytical Electron Microscopy in Scanning Transmission Electron Microscopy (STEM) mode. Experimental results were then interpreted using the RIME model. A microstructure consisting only of dislocations and voids is insufficient to account for the swelling evolution observed experimentally at high damage levels in a complicated microstructure such as irradiated alloy HT9. G phase was found to have a minimal effect on either void or dislocation evolution. M2X played two roles; a variable biased sink for defects, and as a vehicle for removal of carbon from solution, thus promoting void growth. When accounting for all microstructure interactions, swelling at high damage levels is a dynamic process that continues to respond to other changes in the microstructure as long as they occur.

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

DOE PAGES

Winnick, Matthew J.; Maher, Kate

2018-01-27

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

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

Winnick, Matthew J.; Maher, Kate

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

NASA Astrophysics Data System (ADS)

Winnick, Matthew J.; Maher, Kate

2018-03-01

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. We test this theoretical scaling relationship against reactive transport simulations of chemical weathering profiles under open- and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO2 (y = kxn) where n is dependent on reaction stoichiometry and k is dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO2 at low values and approach open-system scaling at high pCO2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE PAGES

Alfonso, Dominic R.; Kauffman, Douglas R.

2017-08-14

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

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

Alfonso, Dominic R.; Kauffman, Douglas R.

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

In-Vessel Co-Composting of Food Waste Employing Enriched Bacterial Consortium

PubMed Central

2018-01-01

Summary The aim of the present study is to develop a good initial composting mix using a bacterial consortium and 2% lime for effective co-composting of food waste in a 60-litre in-vessel composter. In the experiment that lasted for 42 days, the food waste was first mixed with sawdust and 2% lime (by dry mass), then one of the reactors was inoculated with an enriched bacterial consortium, while the other served as control. The results show that inoculation of the enriched natural bacterial consortium effectively overcame the oil-laden co-composting mass in the composter and increased the rate of mineralization. In addition, CO2 evolution rate of (0.81±0.2) g/(kg·day), seed germination index of (105±3) %, extractable ammonium mass fraction of 305.78 mg/kg, C/N ratio of 16.18, pH=7.6 and electrical conductivity of 3.12 mS/cm clearly indicate that the compost was well matured and met the composting standard requirements. In contrast, control treatment exhibited a delayed thermophilic phase and did not mature after 42 days, as evidenced by the maturity parameters. Therefore, a good composting mix and potential bacterial inoculum to degrade the oil are essential for food waste co-composting systems. PMID:29796000

In-Vessel Co-Composting of Food Waste Employing Enriched Bacterial Consortium.

PubMed

Awasthi, Mukesh Kumar; Wang, Quan; Wang, Meijing; Chen, Hongyu; Ren, Xiuna; Zhao, Junchao; Zhang, Zengqiang

2018-03-01

The aim of the present study is to develop a good initial composting mix using a bacterial consortium and 2% lime for effective co-composting of food waste in a 60-litre in-vessel composter. In the experiment that lasted for 42 days, the food waste was first mixed with sawdust and 2% lime (by dry mass), then one of the reactors was inoculated with an enriched bacterial consortium, while the other served as control. The results show that inoculation of the enriched natural bacterial consortium effectively overcame the oil-laden co-composting mass in the composter and increased the rate of mineralization. In addition, CO 2 evolution rate of (0.81±0.2) g/(kg·day), seed germination index of (105±3) %, extractable ammonium mass fraction of 305.78 mg/kg, C/N ratio of 16.18, pH=7.6 and electrical conductivity of 3.12 mS/cm clearly indicate that the compost was well matured and met the composting standard requirements. In contrast, control treatment exhibited a delayed thermophilic phase and did not mature after 42 days, as evidenced by the maturity parameters. Therefore, a good composting mix and potential bacterial inoculum to degrade the oil are essential for food waste co-composting systems.

Modulation of magmatic processes by CO2 flushing

NASA Astrophysics Data System (ADS)

Caricchi, Luca; Sheldrake, Tom E.; Blundy, Jon

2018-06-01

Magmatic systems are the engines driving volcanic eruptions and the source of fluids responsible for the formation of porphyry-type ore deposits. Sudden variations of pressure, temperature and volume in magmatic systems can produce unrest, which may culminate in a volcanic eruption and/or the abrupt release of ore-forming fluids. Such variations of the conditions within magmatic systems are commonly ascribed to the injection of new magma from depth. However, as magmas fractionating at depth or rising to the upper crust release CO2-rich fluids, the interaction between carbonic fluids and H2O-rich magmas stored in the upper crust (CO2 flushing), must also be a common process affecting the evolution of subvolcanic magma reservoirs. Here, we investigate the effect of gas injection on the stability and chemical evolution of magmatic systems. We calculate the chemical and physical evolution of magmas subjected to CO2-flushing using rhyolite-MELTS. We compare the calculations with a set of melt inclusion data for Mt. St. Helens, Merapi, Etna, and Stromboli volcanoes. We provide an approach that can be used to distinguish between melt inclusions trapped during CO2 flushing, magma ascent and decompression, or those affected by post-entrapment H2O-loss. Our results show that CO2 flushing is a widespread process in both felsic and mafic magmatic systems. Depending upon initial magma crystallinity and duration of CO2 input, flushing can either lead to volcanic eruption or fluid release. We suggest that CO2 flushing is a fundamental process modulating the behaviour and chemical evolution of crustal magmatic systems.

Structural Evolution of Li xNi yMn zCo 1-y-zO 2 Cathode Materials during High-Rate Charge and Discharge

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

Hwang, Sooyeon; Jo, Eunmi; Chung, Kyung Yoon

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport andmore » reduces their capacities. Furthermore, this study establishes a correlation between the high-rate electrochemical performance of the Ni-based materials and their structural evolution, which can provide profound insights for designing novel cathode materials having both high energy and power densities.« less

Structural Evolution of Li xNi yMn zCo 1-y-zO 2 Cathode Materials during High-Rate Charge and Discharge

DOE PAGES

Hwang, Sooyeon; Jo, Eunmi; Chung, Kyung Yoon; ...

2017-11-08

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport andmore » reduces their capacities. Furthermore, this study establishes a correlation between the high-rate electrochemical performance of the Ni-based materials and their structural evolution, which can provide profound insights for designing novel cathode materials having both high energy and power densities.« less

Efficient Electron Transfer across a ZnO-MoS2 -Reduced Graphene Oxide Heterojunction for Enhanced Sunlight-Driven Photocatalytic Hydrogen Evolution.

PubMed

Kumar, Suneel; Reddy, Nagappagari Lakshmana; Kushwaha, Himmat Singh; Kumar, Ashish; Shankar, Muthukonda Venkatakrishnan; Bhattacharyya, Kaustava; Halder, Aditi; Krishnan, Venkata

2017-09-22

The development of noble metal-free catalysts for hydrogen evolution is required for energy applications. In this regard, ternary heterojunction nanocomposites consisting of ZnO nanoparticles anchored on MoS 2 -RGO (RGO=reduced graphene oxide) nanosheets as heterogeneous catalysts show highly efficient photocatalytic H 2 evolution. In the photocatalytic process, the catalyst dispersed in an electrolytic solution (S 2- and SO 3 2- ions) exhibits an enhanced rate of H 2 evolution, and optimization experiments reveal that ZnO with 4.0 wt % of MoS 2 -RGO nanosheets gives the highest photocatalytic H 2 production of 28.616 mmol h -1  g cat -1 under sunlight irradiation; approximately 56 times higher than that on bare ZnO and several times higher than those of other ternary photocatalysts. The superior catalytic activity can be attributed to the in situ generation of ZnS, which leads to improved interfacial charge transfer to the MoS 2 cocatalyst and RGO, which has plenty of active sites available for photocatalytic reactions. Recycling experiments also proved the stability of the optimized photocatalyst. In addition, the ternary nanocomposite displayed multifunctional properties for hydrogen evolution activity under electrocatalytic and photoelectrocatalytic conditions owing to the high electrode-electrolyte contact area. Thus, the present work provides very useful insights for the development of inexpensive, multifunctional catalysts without noble metal loading to achieve a high rate of H 2 generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A unique mode of tissue oxygenation and the adaptive radiation of teleost fishes.

PubMed

Randall, D J; Rummer, J L; Wilson, J M; Wang, S; Brauner, C J

2014-04-15

Teleost fishes constitute 95% of extant aquatic vertebrates, and we suggest that this is related in part to their unique mode of tissue oxygenation. We propose the following sequence of events in the evolution of their oxygen delivery system. First, loss of plasma-accessible carbonic anhydrase (CA) in the gill and venous circulations slowed the Jacobs-Stewart cycle and the transfer of acid between the plasma and the red blood cells (RBCs). This ameliorated the effects of a generalised acidosis (associated with an increased capacity for burst swimming) on haemoglobin (Hb)-O2 binding. Because RBC pH was uncoupled from plasma pH, the importance of Hb as a buffer was reduced. The decrease in buffering was mediated by a reduction in the number of histidine residues on the Hb molecule and resulted in enhanced coupling of O2 and CO2 transfer through the RBCs. In the absence of plasma CA, nearly all plasma bicarbonate ultimately dehydrated to CO2 occurred via the RBCs, and chloride/bicarbonate exchange was the rate-limiting step in CO2 excretion. This pattern of CO2 excretion across the gills resulted in disequilibrium states for CO2 hydration/dehydration reactions and thus elevated arterial and venous plasma bicarbonate levels. Plasma-accessible CA embedded in arterial endothelia was retained, which eliminated the localized bicarbonate disequilibrium forming CO2 that then moved into the RBCs. Consequently, RBC pH decreased which, in conjunction with pH-sensitive Bohr/Root Hbs, elevated arterial oxygen tensions and thus enhanced tissue oxygenation. Counter-current arrangement of capillaries (retia) at the eye and later the swim bladder evolved along with the gas gland at the swim bladder. Both arrangements enhanced and magnified CO2 and acid production and, therefore, oxygen secretion to those specialised tissues. The evolution of β-adrenergically stimulated RBC Na(+)/H(+) exchange protected gill O2 uptake during stress and further augmented plasma disequilibrium states for CO2 hydration/dehydration. Finally, RBC organophosphates (e.g. NTP) could be reduced during hypoxia to further increase Hb-O2 affinity without compromising tissue O2 delivery because high-affinity Hbs could still adequately deliver O2 to the tissues via Bohr/Root shifts. We suggest that the evolution of this unique mode of tissue O2 transfer evolved in the Triassic/Jurassic Period, when O2 levels were low, ultimately giving rise to the most extensive adaptive radiation of extant vertebrates, the teleost fishes.

Galaxy Zoo: evidence for rapid, recent quenching within a population of AGN host galaxies

NASA Astrophysics Data System (ADS)

Smethurst, R. J.; Lintott, C. J.; Simmons, B. D.; Schawinski, K.; Bamford, S. P.; Cardamone, C. N.; Kruk, S. J.; Masters, K. L.; Urry, C. M.; Willett, K. W.; Wong, O. I.

2016-12-01

We present a population study of the star formation history of 1244 Type 2 active galactic nuclei (AGN) host galaxies, compared to 6107 inactive galaxies. A Bayesian method is used to determine individual galaxy star formation histories, which are then collated to visualize the distribution for quenching and quenched galaxies within each population. We find evidence for some of the Type 2 AGN host galaxies having undergone a rapid drop in their star formation rate within the last 2 Gyr. AGN feedback is therefore important at least for this population of galaxies. This result is not seen for the quenching and quenched inactive galaxies whose star formation histories are dominated by the effects of downsizing at earlier epochs, a secondary effect for the AGN host galaxies. We show that histories of rapid quenching cannot account fully for the quenching of all the star formation in a galaxy's lifetime across the population of quenched AGN host galaxies, and that histories of slower quenching, attributed to secular (non-violent) evolution, are also key in their evolution. This is in agreement with recent results showing that both merger-driven and non-merger processes are contributing to the co-evolution of galaxies and supermassive black holes. The availability of gas in the reservoirs of a galaxy, and its ability to be replenished, appear to be the key drivers behind this co-evolution.

Computer modeling of pulsed CO2 lasers for lidar applications

NASA Technical Reports Server (NTRS)

Spiers, Gary D.

1993-01-01

The object of this effort is to develop code to enable the accurate prediction of the performance of pulsed transversely excited (TE) CO2 lasers prior to their construction. This is of particular benefit to the NASA Laser Atmospheric Wind Sounder (LAWS) project. A benefit of the completed code is that although developed specifically for the pulsed CO2 laser much of the code can be modified to model other laser systems of interest to the lidar community. A Boltzmann equation solver has been developed which enables the electron excitation rates for the vibrational levels of CO2 and N2, together with the electron ionization and attachment coefficients to be determined for any CO2 laser gas mixture consisting of a combination of CO2, N2, CO, He and CO. The validity of the model has been verified by comparison with published material. The results from the Boltzmann equation solver have been used as input to the laser kinetics code which is currently under development. A numerical code to model the laser induced medium perturbation (LIMP) arising from the relaxation of the lower laser level has been developed and used to determine the effect of LIMP on the frequency spectrum of the LAWS laser output pulse. The enclosed figures show representative results for a laser operating at 0.5 atm. with a discharge cross-section of 4.5 cm to produce a 20 J pulse with aFWHM of 3.1 microns. The first four plots show the temporal evolution of the laser pulse power, energy evolution, LIMP frequency chirp and electric field magnitude. The electric field magnitude is taken by beating the calculated complex electric field and beating it with a local oscillator signal. The remaining two figures show the power spectrum and energy distribution in the pulse as a function of the varying pulse frequency. The LIMP theory has been compared with experimental data from the NOAA Windvan Lidar and has been found to be in good agreement.

Novel catalysts and photoelectrochemical system for solar fuel production

NASA Astrophysics Data System (ADS)

Zhang, Yan

Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption spectroscopy (XAS). The photocatalytic activities of as-made nanoparticles were investigated using a well-studied visible light driven [Ru(bpy)3]2+-persulfate system. In both Clark electrode and reactor/gas chromatography (GC) systems, Mn-substituted Co3O 4 nanoparticles exhibited the highest turnover frequency (TOF) among all the three kinds of catalysts. The data presented in this paper suggest that the photocatalytic oxygen evolution activity of Co3O 4 spinel catalyst can be further enhanced by Mn3+ substitution at the octahedral sites. The second part of this piece of work was carried out to further investigate cobalt oxide based photocatalytic oxygen evolution catalyst. A new strategy was developed to synthesize nonsupported cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO 3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.0023 per second per cobalt in photocatalytic oxygen evolution reaction. X-ray absorption results suggested that a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen atoms and hydroxide groups in an octahedral arrangement to form 8 Co4O4 cubanes, may be responsible for the exceptionally high oxygen evolution catalysis activity. This thesis work is completed with the development of a photoanode-driven photoelectrochemical cell for CO2 reduction. A NiOx decorated Si photoanode and nanoporous Ag cathode were employed. With an external bias of 2.0 V, a current density at cathode of 10 mA/cm2 and Faradaic efficiency of 70% for CO2 to CO was achieved. Compared to a normal electrochemical cell, the photoelectrochemical cell saves 0.4 V electrical energy by absorbing photo-energy. In addition, post-test photoanodes were carefully characterized by SEM, XAS, and XPS analysis.

Holocene moisture and East Asian summer monsoon evolution in the northeastern Tibetan Plateau recorded by Lake Qinghai and its environs: A review of conflicting proxies

NASA Astrophysics Data System (ADS)

Chatterjee, A.; Schimel, D.; Stephens, B. B.; Crisp, D.; Eldering, A.; Gunson, M. R.; Feely, R. A.; Gierach, M. M.; Keeling, R. F.; Sutton, A. J.; Weir, B.

2016-12-01

The El Nino Southern Oscillation (ENSO) is the most important mode of tropical climate variability on interannual to decadal time scales. Correlations between atmospheric CO2 growth rate and ENSO activity are relatively well known but the magnitude of this correlation, the contribution from tropical marine vs. terrestrial flux components, and the causal mechanisms, are poorly constrained in space and time. The launch of NASA's Orbiting Carbon Observatory-2 (OCO-2) mission in July 2014 was rather timely given the development of strong ENSO conditions over the tropical Pacific Ocean in 2015-2016. In this presentation, we will discuss how the high-density observations from OCO-2 provided us with a novel dataset to resolve the linkages between El Niño and atmospheric CO2. Along with information from in situ observations of ΔpCO2 from NOAA's Tropical Atmosphere Ocean (TAO) project and atmospheric CO2 from the Scripps CO2 Program, and other remote-sensing missions, we are able to piece together the time dependent response of atmospheric CO2 concentrations over the Tropics. Our findings confirm the hypothesis from studies following the 1997-1998 El Niño event that an early reduction in CO2 outgassing from the tropical Pacific Ocean is later reversed by enhanced net CO2 emissions from the terrestrial biosphere. This implies that a component of the interannual variability (IAV) in the growth rate of atmospheric CO2, which has typically been used to constrain the climate sensitivity of tropical land carbon fluxes, is strongly influenced and modified by ocean fluxes during the early phase of the ENSO event. Our analyses shed further light on the understanding of the marine vs. terrestrial partitioning of tropical carbon fluxes during El Niño events, their relative contributions to the global atmospheric CO2 growth rate, and provide clues about the sensitivity of the carbon cycle to climate forcing on interannual time scales.

Investigation into the disparate origin of CO 2 and H 2O outgassing for comet 67P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; VIRTIS Team

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma.We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ~5.0% and ~2.5% for Feb. 28 and April 27 respectively. Because of the highly variable nature of the CO2 evolution we do not believe that these numbers are diagnostic of the comets bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's geometric shape, illumination and past orbital history.Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the sun is 2.5x1026 molecules/s while for April 27 at 1.76 AU it is 4.65x1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the night side. A rough estimate of the water surface evaporation rate of the illuminated nucleus for April 27 yields about 5x1019 molecules/s m2.

Engineering stategies and implications of using higher plants for throttling gas and water exchange in a controlled ecological life support system

NASA Technical Reports Server (NTRS)

Chamberland, Dennis; Wheeler, Raymond M.; Corey, Kenneth A.

1993-01-01

Engineering stategies for advanced life support systems to be used on Lunar and Mars bases involve a wide spectrum of approaches. These range from purely physical-chemical life support strategies to purely biological approaches. Within the context of biological based systems, a bioengineered system can be devised that would utilize the metabolic mechanisms of plants to control the rates of CO2 uptake and O2 evolution (photosynthesis) and water production (transpiration). Such a mechanism of external engineering control has become known as throttling. Research conducted at the John F. Kennedy Space Center's Controlled Ecological Life Support System Breadboard Project has demonstrated the potential of throttling these fluxes by changing environmental parameters affecting the plant processes. Among the more effective environmental throttles are: light and CO2 concentration for controllingthe rate of photsynthesis and humidity and CO2 concentration for controlling transpiration. Such a bioengineered strategy implies control mechanisms that in the past have not been widely attributed to life support systems involving biological components and suggests a broad range of applications in advanced life support system design.

New Methods for Tracking Galaxy and Black Hole Evolution Using Post-Starburst Galaxies

NASA Astrophysics Data System (ADS)

French, Katheryn Decker

2017-08-01

Galaxies in transition from star-forming to quiescence are a natural laboratory for exploring the processes responsible for this evolution. Using a sample of post-starburst galaxies identified to have recently experienced a recent burst of star formation that has now ended, I explore both the fate of the molecular gas that drives star formation and the increased rate of stars disrupted by the central supermassive black hole. Chapter 1 provides an introduction to galaxy evolution through the post-starburst phase and to tidal disruption events, which surprisingly favor post-starburst galaxy hosts. In Chapter 2, I present a survey of the molecular gas properties of 32 post-starburst galaxies traced by CO (1-0) and CO (2-1). In order to accurately put galaxies on an evolutionary sequence, we must select likely progenitors and descendants. We do this by identifying galaxies with similar starburst properties, such as the amount of mass produced in the burst and the burst duration. In Chapter 3, I describe a method to determine the starburst properties and the time elapsed since the starburst ended, and discuss trends in the molecular gas properties of these galaxies with time. In Chapter 4, I present the results of followup observations with ALMA of HCN (1-0) and HCO+ (1-0) in two post-starburst galaxies. CO (1-0) is detected in over half (17/32) the post-starburst sample and the molecular gas mass traced by CO declines on ˜100 Myr timescales after the starburst has ended. HCN (1-0) is not detected in either galaxy targeted, indicating the post-starbursts are now quiescent because of a lack of the denser molecular gas traced by HCN. In Chapter 5 I quantify the increase in TDE rate in quiescent galaxies with strong Balmer absorption to be 30 - 200x higher than in normal galaxies. Using the stellar population fitting method from Chapter 3, I examine possible reasons for the increased TDE rate in post-starburst galaxies in Chapter 6. The TDE rate could be boosted due to a binary supermassive black hole coalescing after a major merger or an increased density of stars or gas remaining near the nucleus after the starburst has ended. In Chapter 7, I present a summary of the findings of this dissertation and an outlook for future work.

Quantification of a maximum injection volume of CO2 to avert geomechanical perturbations using a compositional fluid flow reservoir simulator

NASA Astrophysics Data System (ADS)

Jung, Hojung; Singh, Gurpreet; Espinoza, D. Nicolas; Wheeler, Mary F.

2018-02-01

Subsurface CO2 injection and storage alters formation pressure. Changes of pore pressure may result in fault reactivation and hydraulic fracturing if the pressure exceeds the corresponding thresholds. Most simulation models predict such thresholds utilizing relatively homogeneous reservoir rock models and do not account for CO2 dissolution in the brine phase to calculate pore pressure evolution. This study presents an estimation of reservoir capacity in terms of allowable injection volume and rate utilizing the Frio CO2 injection site in the coast of the Gulf of Mexico as a case study. The work includes laboratory core testing, well-logging data analyses, and reservoir numerical simulation. We built a fine-scale reservoir model of the Frio pilot test in our in-house reservoir simulator IPARS (Integrated Parallel Accurate Reservoir Simulator). We first performed history matching of the pressure transient data of the Frio pilot test, and then used this history-matched reservoir model to investigate the effect of the CO2 dissolution into brine and predict the implications of larger CO2 injection volumes. Our simulation results -including CO2 dissolution- exhibited 33% lower pressure build-up relative to the simulation excluding dissolution. Capillary heterogeneity helps spread the CO2 plume and facilitate early breakthrough. Formation expansivity helps alleviate pore pressure build-up. Simulation results suggest that the injection schedule adopted during the actual pilot test very likely did not affect the mechanical integrity of the storage complex. Fault reactivation requires injection volumes of at least about sixty times larger than the actual injected volume at the same injection rate. Hydraulic fracturing necessitates much larger injection rates than the ones used in the Frio pilot test. Tested rock samples exhibit ductile deformation at in-situ effective stresses. Hence, we do not expect an increase of fault permeability in the Frio sand even in the presence of fault reactivation.

Spatially-controlled NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-01

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

PubMed

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-13

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo 2 O 4 @MnO 2 core-shell nanoarray with hollow NiCo 2 O 4 Cores and MnO 2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo 2 O 4 and MnO 2 compositions.

Hollow Fluffy Co3O4 Cages as Efficient Electroactive Materials for Supercapacitors and Oxygen Evolution Reaction.

PubMed

Zhou, Xuemei; Shen, Xuetao; Xia, Zhaoming; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

2015-09-16

Nano-/micrometer multiscale hierarchical structures not only provide large surface areas for surface redox reactions but also ensure efficient charge conductivity, which is of benefit for utilization in areas of electrochemical energy conversion and storage. Herein, hollow fluffy cages (HFC) of Co3O4, constructed of ultrathin nanosheets, were synthesized by the formation of Co(OH)2 hollow cages and subsequent calcination at 250 °C. The large surface area (245.5 m2 g(-1)) of HFC Co3O4 annealed at 250 °C ensures the efficient interaction between electrolytes and electroactive components and provides more active sites for the surface redox reactions. The hierarchical structures minimize amount of the grain boundaries and facilitate the charge transfer process. Thin thickness of nanosheets (2-3 nm) ensures the highly active sites for the surface redox reactions. As a consequence, HFC Co3O4 as the supercapacitor electrode exhibits a superior rate capability, shows an excellent cycliability of 10,000 cycles at 10 A g(-1), and delivers large specific capacitances of 948.9 and 536.8 F g(-1) at 1 and 40 A g(-1), respectively. Catalytic studies of HFC Co3O4 for oxygen evolution reaction display a much higher turnover frequency of 1.67×10(-2) s(-1) in pH 14.0 KOH electrolyte at 400 mV overpotential and a lower Tafel slope of 70 mV dec(-1). HFC Co3O4 with the efficient electrochemical activity and good stability can remain a promising candidate for the electrochemical energy conversion and storage.

When to care for, abandon, or eat your offspring: the evolution of parental care and filial cannibalism.

PubMed

Klug, Hope; Bonsall, Michael B

2007-12-01

Parental care and filial cannibalism (the consumption of one's own offspring) co-occur in many animals. While parental care typically increases offspring survival, filial cannibalism involves the killing of one's young. Using an evolutionary ecology approach, we evaluate the importance of a range of factors on the evolution of parental care and filial cannibalism. Parental care, no care/total abandonment, and filial cannibalism evolved and often coexisted over a range of parameter space. While no single benefit was essential for the evolution of filial cannibalism, benefits associated with adult or offspring survival and/or reproduction facilitated the evolution of cannibalism. Our model highlights the plausibility of a range of alternative hypotheses. Specifically, the evolution of filial cannibalism was enhanced if (1) parents could selectively cannibalize lower-quality offspring, (2) filial cannibalism increased egg maturation rate, (3) energetic benefits of eggs existed, or (4) cannibalism increased a parent's reproductive rate (e.g., through mate attractiveness). Density-dependent egg survivorship alone did not favor the evolution of cannibalism. However, when egg survival was density dependent, filial cannibalism invaded more often when the density dependence was relatively more intense. Our results suggest that population-level resource competition potentially plays an important role in the evolution of both parental care and filial cannibalism.

CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity

NASA Astrophysics Data System (ADS)

Chen, Yajie; Kang, Chuanhong; Wang, Ruihong; Ren, Zhiyu; Fu, Huiying; Xiao, Yuting; Tian, Guohui

2018-06-01

The CoP/WS2 nanoflake composites were synthesized via the sulfuration and subsequent phosphidation using the pre-prepared WO2.72 nanowires as precursors. Originally, WO2.72 nanowires were prepared and followed by sulfuration to obtain WS2 nanoflakes. The as-prepared WS2 nanoflakes were used as substrates, on which the Co3O4 nanoparticles were uniformly anchored to construct the Co3O4/WS2 nanoflakes. Finally, the Co3O4/WS2 composites were subjected to phosphidation and in-situ converted into CoP/WS2 nanoflakes. Because of the dual functionalities of both CoP and WS2, the abundant interfaces as well as their synergy, the CoP/WS2 nanoflakes exhibited much higher electrocatalytic activity, smaller overpotential (-81 mV), lower Tafel slope (62 mV decade-1), and higher stability toward hydrogen-evolution reaction than those for the single CoP and WS2.

A Carbon Dioxide Limitation-Inducible Protein, ColA, Supports the Growth of Synechococcus sp. PCC 7002

PubMed Central

Shimakawa, Ginga; Watanabe, Satoru; Miyake, Chikahiro

2017-01-01

A limitation in carbon dioxide (CO2), which occurs as a result of natural environmental variation, suppresses photosynthesis and has the potential to cause photo-oxidative damage to photosynthetic cells. Oxygenic phototrophs have strategies to alleviate photo-oxidative damage to allow life in present atmospheric CO2 conditions. However, the mechanisms for CO2 limitation acclimation are diverse among the various oxygenic phototrophs, and many mechanisms remain to be discovered. In this study, we found that the gene encoding a CO2 limitation-inducible protein, ColA, is required for the cyanobacterium Synechococcus sp. PCC 7002 (S. 7002) to acclimate to limited CO2 conditions. An S. 7002 mutant deficient in ColA (ΔcolA) showed lower chlorophyll content, based on the amount of nitrogen, than that in S. 7002 wild-type (WT) under ambient air but not high CO2 conditions. Both thermoluminescence and protein carbonylation detected in the ambient air grown cells indicated that the lack of ColA promotes oxidative stress in S. 7002. Alterations in the photosynthetic O2 evolution rate and relative electron transport rate in the short-term response, within an hour, to CO2 limitation were the same between the WT and ΔcolA. Conversely, these photosynthetic parameters were mostly lower in the long-term response of a few days in ΔcolA than in the WT. These data suggest that ColA is required to sustain photosynthetic activity for living under ambient air in S. 7002. The unique phylogeny of ColA revealed diverse strategies to acclimate to CO2 limitation among cyanobacteria. PMID:29244744

Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4.

PubMed

Long, Ran; Li, Yu; Liu, Yan; Chen, Shuangming; Zheng, Xusheng; Gao, Chao; He, Chaohua; Chen, Nanshan; Qi, Zeming; Song, Li; Jiang, Jun; Zhu, Junfa; Xiong, Yujie

2017-03-29

Photocatalytic conversion of CO 2 to CH 4 , a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H 2 by side reactions. The design of catalytic sites for CO 2 adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO 2 to CH 4 by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO 2 -to-CH 4 conversion: (1) providing the paired Cu-Pd sites for the enhanced CO 2 adsorption and the suppressed H 2 evolution; and (2) elevating the d-band center of Cu sites for the improved CO 2 activation. As a result, the Pd 7 Cu 1 -TiO 2 photocatalyst achieves the high selectivity of 96% for CH 4 production with a rate of 19.6 μmol g cat -1 h -1 . This work provides fresh insights into the catalytic site design for selective photocatalytic CO 2 conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.

Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

NASA Astrophysics Data System (ADS)

Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

2014-12-01

A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

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

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

DOE PAGES

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.; ...

2017-01-06

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations.

PubMed

Zhang, Ning; Chen, Chen; Mei, Zongwei; Liu, Xiaohe; Qu, Xiaolei; Li, Yunxiang; Li, Siqi; Qi, Weihong; Zhang, Yuanjian; Ye, Jinhua; Roy, Vellaisamy A L; Ma, Renzhi

2016-04-27

Exploring surface-exposed highly active crystal facets for photocatalytic oxidations is promising in utilizing monoclinic WO3 semiconductor. However, the previously reported highly active facets for monoclinic WO3 were mainly toward enhancing photocatalytic reductions. Here we report that the WO3 with {100} facet orientation and tuned surface electronic band structure can effectively enhance photocatalytic oxidation properties. The {100} faceted WO3 single crystals are synthesized via a facile hydrothermal method. The UV-visible diffuse reflectance, X-ray photoelectron spectroscopy valence band spectra, and photoelectrochemical measurements suggest that the {100} faceted WO3 has a much higher energy level of valence band maximum compared with the normal WO3 crystals without preferred orientation of the crystal face. The density functional theory calculations reveal that the shift of O 2p and W 5d states in {100} face induce a unique band structure. In comparison with the normal WO3, the {100} faceted WO3 exhibits an O2 evolution rate about 5.1 times in water splitting, and also shows an acetone evolution rate of 4.2 times as well as CO2 evolution rate of 3.8 times in gaseous degradation of 2-propanol. This study demonstrates an efficient crystal face engineering route to tune the surface electronic band structure for enhanced photocatalytic oxidations.

Functional genetic divergence in high CO2 adapted Emiliania huxleyi populations.

PubMed

Lohbeck, Kai T; Riebesell, Ulf; Collins, Sinéad; Reusch, Thorsten B H

2013-07-01

Predicting the impacts of environmental change on marine organisms, food webs, and biogeochemical cycles presently relies almost exclusively on short-term physiological studies, while the possibility of adaptive evolution is often ignored. Here, we assess adaptive evolution in the coccolithophore Emiliania huxleyi, a well-established model species in biological oceanography, in response to ocean acidification. We previously demonstrated that this globally important marine phytoplankton species adapts within 500 generations to elevated CO2 . After 750 and 1000 generations, no further fitness increase occurred, and we observed phenotypic convergence between replicate populations. We then exposed adapted populations to two novel environments to investigate whether or not the underlying basis for high CO2 -adaptation involves functional genetic divergence, assuming that different novel mutations become apparent via divergent pleiotropic effects. The novel environment "high light" did not reveal such genetic divergence whereas growth in a low-salinity environment revealed strong pleiotropic effects in high CO2 adapted populations, indicating divergent genetic bases for adaptation to high CO2 . This suggests that pleiotropy plays an important role in adaptation of natural E. huxleyi populations to ocean acidification. Our study highlights the potential mutual benefits for oceanography and evolutionary biology of using ecologically important marine phytoplankton for microbial evolution experiments. © 2012 The Author(s). Evolution © 2012 The Society for the Study of Evolution.

SILCC-Zoom: the dynamic and chemical evolution of molecular clouds

NASA Astrophysics Data System (ADS)

Seifried, D.; Walch, S.; Girichidis, P.; Naab, T.; Wünsch, R.; Klessen, R. S.; Glover, S. C. O.; Peters, T.; Clark, P.

2017-12-01

We present 3D 'zoom-in' simulations of the formation of two molecular clouds out of the galactic interstellar medium. We model the clouds - identified from the SILCC simulations - with a resolution of up to 0.06 pc using adaptive mesh refinement in combination with a chemical network to follow heating, cooling and the formation of H2 and CO including (self-) shielding. The two clouds are assembled within a few million years with mass growth rates of up to ∼10-2 M⊙ yr-1 and final masses of ∼50 000 M⊙. A spatial resolution of ≲0.1 pc is required for convergence with respect to the mass, velocity dispersion and chemical abundances of the clouds, although these properties also depend on the cloud definition such as based on density thresholds, H2 or CO mass fraction. To avoid grid artefacts, the progressive increase of resolution has to occur within the free-fall time of the densest structures (1-1.5 Myr) and ≳200 time-steps should be spent on each refinement level before the resolution is progressively increased further. This avoids the formation of spurious, large-scale, rotating clumps from unresolved turbulent flows. While CO is a good tracer for the evolution of dense gas with number densities n ≥ 300 cm-3, H2 is also found for n ≲ 30 cm-3 due to turbulent mixing and becomes dominant at column densities around 30-50 M⊙ pc-2. The CO-to-H2 ratio steadily increases within the first 2 Myr, whereas XCO ≃ 1-4 × 1020 cm-2 (K km s-1)-1 is approximately constant since the CO(1-0) line quickly becomes optically thick.

The influence of sperm concentration, length of the gamete co-culture and the evolution of different sperm parameters on the in vitro fertilization of prepubertal goat oocytes.

PubMed

Palomo, M J; Mogas, T; Izquierdo, D; Paramio, M T

2010-11-01

The aims of the present study were: (1) to evaluate the influence of sperm concentration (ranging from 0.5 × 10(6) to 4 × 10(6) spermatozoa/ml) and length of the gamete co-incubation time (2, 4, 6, 8, 10, 12, 16, 20, 24 or 28 h) on in vitro fertilization (IVF), assessing the sperm penetration rate; (2) to investigate the kinetics of different semen parameters as motility, viability and acrosome status during the co-culture period; and (3) to analyse the effect of the presence of cumulus-oocytes complexes (COCs) on these parameters. To achieve these objectives, several experiments were carried out using in vitro matured oocytes from prepubertal goats. The main findings of this work are that: (1) in our conditions, the optimum sperm concentration is 4 × 10(6) sperm/ml, as this sperm:oocyte ratio (approximately 28,000) allowed us to obtain the highest penetration rate, without increasing polyspermy incidence; (2) the highest percentage of viable acrosome-reacted spermatozoa is observed between 8-12 h of gamete co-culture, while the penetration rate is maximum at 12 h of co-incubation; and (3) the presence of COCs seems to favour the acrosome reaction of free spermatozoa on IVF medium, but not significantly. In conclusion, we suggest that a gamete co-incubation for 12-14 h, with a concentration of 4 × 10(6) sperm/ml, would be sufficient to obtain the highest rate of penetration, reducing the exposure of oocytes to high levels of reactive oxygen species produced by spermatozoa, especially when a high sperm concentration is used to increase the caprine IVF outcome.

Maturation and Diversity of the VRC01-Antibody Lineage over 15 Years of Chronic HIV-1 Infection

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

Wu, Xueling; Zhang, Zhenhai; Schramm, Chaim A.

HIV-1-neutralizing antibodies develop in most HIV-1-infected individuals, although highly effective antibodies are generally observed only after years of chronic infection. Here in this paper, we characterize the rate of maturation and extent of diversity for the lineage that produced the broadly neutralizing antibody VRC01 through longitudinal sampling of peripheral B cell transcripts over 15 years and co-crystal structures of lineage members. Next-generation sequencing identified VRC01-lineage transcripts, which encompassed diverse antibodies organized into distinct phylogenetic clades. Prevalent clades maintained characteristic features of antigen recognition, though each evolved binding loops and disulfides that formed distinct recognition surfaces. Over the course of themore » study period, VRC01-lineage clades showed continuous evolution, with rates of ~2 substitutions per 100 nucleotides per year, comparable to that of HIV-1 evolution. This high rate of antibody evolution provides a mechanism by which antibody lineages can achieve extraordinary diversity and, over years of chronic infection, develop effective HIV-1 neutralization.« less

Maturation and Diversity of the VRC01-Antibody Lineage over 15 Years of Chronic HIV-1 Infection.

PubMed

Wu, Xueling; Zhang, Zhenhai; Schramm, Chaim A; Joyce, M Gordon; Kwon, Young Do; Zhou, Tongqing; Sheng, Zizhang; Zhang, Baoshan; O'Dell, Sijy; McKee, Krisha; Georgiev, Ivelin S; Chuang, Gwo-Yu; Longo, Nancy S; Lynch, Rebecca M; Saunders, Kevin O; Soto, Cinque; Srivatsan, Sanjay; Yang, Yongping; Bailer, Robert T; Louder, Mark K; Mullikin, James C; Connors, Mark; Kwong, Peter D; Mascola, John R; Shapiro, Lawrence

2015-04-23

HIV-1-neutralizing antibodies develop in most HIV-1-infected individuals, although highly effective antibodies are generally observed only after years of chronic infection. Here, we characterize the rate of maturation and extent of diversity for the lineage that produced the broadly neutralizing antibody VRC01 through longitudinal sampling of peripheral B cell transcripts over 15 years and co-crystal structures of lineage members. Next-generation sequencing identified VRC01-lineage transcripts, which encompassed diverse antibodies organized into distinct phylogenetic clades. Prevalent clades maintained characteristic features of antigen recognition, though each evolved binding loops and disulfides that formed distinct recognition surfaces. Over the course of the study period, VRC01-lineage clades showed continuous evolution, with rates of ∼2 substitutions per 100 nucleotides per year, comparable to that of HIV-1 evolution. This high rate of antibody evolution provides a mechanism by which antibody lineages can achieve extraordinary diversity and, over years of chronic infection, develop effective HIV-1 neutralization. Copyright © 2015 Elsevier Inc. All rights reserved.

Maturation and Diversity of the VRC01-Antibody Lineage over 15 Years of Chronic HIV-1 Infection

DOE PAGES

Wu, Xueling; Zhang, Zhenhai; Schramm, Chaim A.; ...

2015-04-09

HIV-1-neutralizing antibodies develop in most HIV-1-infected individuals, although highly effective antibodies are generally observed only after years of chronic infection. Here in this paper, we characterize the rate of maturation and extent of diversity for the lineage that produced the broadly neutralizing antibody VRC01 through longitudinal sampling of peripheral B cell transcripts over 15 years and co-crystal structures of lineage members. Next-generation sequencing identified VRC01-lineage transcripts, which encompassed diverse antibodies organized into distinct phylogenetic clades. Prevalent clades maintained characteristic features of antigen recognition, though each evolved binding loops and disulfides that formed distinct recognition surfaces. Over the course of themore » study period, VRC01-lineage clades showed continuous evolution, with rates of ~2 substitutions per 100 nucleotides per year, comparable to that of HIV-1 evolution. This high rate of antibody evolution provides a mechanism by which antibody lineages can achieve extraordinary diversity and, over years of chronic infection, develop effective HIV-1 neutralization.« less

Technologies for ECLSS Evolution

NASA Technical Reports Server (NTRS)

Diamant, Bryce L.

1990-01-01

Viewgraphs and discussion on technologies for Environmental Control and Life Support System (ECLSS) evolution are presented. Topics covered include: atmosphere revitalization including CO2 removal, CO2 reduction, O2 generation, and trace contaminant control; water recovery and management including urine processing, hygiene water processing, and potable water processing; and waste management. ECLSS technology schematics, process diagrams, and fluid interfaces are included.

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

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@eps.s.u-tokyo.ac.jp

The climatic evolution of the Earth depends strongly on the evolution of the insolation from the Sun and the amount of the greenhouse gasses, especially CO{sub 2} in the atmosphere. Here, we investigate the evolution of the climate of hypothetical Earths around stars whose masses are different from the solar mass with a luminosity evolution model of the stars, a mantle degassing model coupled with a parameterized convection model of the planetary interiors, and an energy balance climate model of the planetary surface. In the habitable zone (HZ), the climate of the planets is initially warm or hot, depending onmore » the orbital semimajor axes. We found that, in the inner HZ, the climate of the planets becomes hotter with time owing to the increase in the luminosity of the central stars, while, in the outer HZ, it becomes colder and eventually globally ice-covered owing to the decrease in the CO{sub 2} degassing rate of the planets. The orbital condition for maintaining the warm climate similar to the present Earth becomes very limited, and more interestingly, the planet orbiting in the outer HZ becomes globally ice-covered after a certain critical age (∼3 Gyr for the hypothetical Earth with standard parameters), irrespective of the mass of the central star. This is because the critical age depends on the evolution of the planets and planetary factors, rather than on the stellar mass. The habitability of the Earth-like planet is shown to be limited with age even though it is orbiting within the HZ.« less

The evolution of bacterial cell size: the internal diffusion-constraint hypothesis.

PubMed

Gallet, Romain; Violle, Cyrille; Fromin, Nathalie; Jabbour-Zahab, Roula; Enquist, Brian J; Lenormand, Thomas

2017-07-01

Size is one of the most important biological traits influencing organismal ecology and evolution. However, we know little about the drivers of body size evolution in unicellulars. A long-term evolution experiment (Lenski's LTEE) in which Escherichia coli adapts to a simple glucose medium has shown that not only the growth rate and the fitness of the bacterium increase over time but also its cell size. This increase in size contradicts prominent 'external diffusion' theory (EDC) predicting that cell size should have evolved toward smaller cells. Among several scenarios, we propose and test an alternative 'internal diffusion-constraint' (IDC) hypothesis for cell size evolution. A change in cell volume affects metabolite concentrations in the cytoplasm. The IDC states that a higher metabolism can be achieved by a reduction in the molecular traffic time inside of the cell, by increasing its volume. To test this hypothesis, we studied a population from the LTEE. We show that bigger cells with greater growth and CO 2 production rates and lower mass-to-volume ratio were selected over time in the LTEE. These results are consistent with the IDC hypothesis. This novel hypothesis offers a promising approach for understanding the evolutionary constraints on cell size.

Adaptive Evolution of Synthetic Cooperating Communities Improves Growth Performance

PubMed Central

Zhang, Xiaolin; Reed, Jennifer L.

2014-01-01

Symbiotic interactions between organisms are important for human health and biotechnological applications. Microbial mutualism is a widespread phenomenon and is important in maintaining natural microbial communities. Although cooperative interactions are prevalent in nature, little is known about the processes that allow their initial establishment, govern population dynamics and affect evolutionary processes. To investigate cooperative interactions between bacteria, we constructed, characterized, and adaptively evolved a synthetic community comprised of leucine and lysine Escherichia coli auxotrophs. The co-culture can grow in glucose minimal medium only if the two auxotrophs exchange essential metabolites — lysine and leucine (or its precursors). Our experiments showed that a viable co-culture using these two auxotrophs could be established and adaptively evolved to increase growth rates (by ∼3 fold) and optical densities. While independently evolved co-cultures achieved similar improvements in growth, they took different evolutionary trajectories leading to different community compositions. Experiments with individual isolates from these evolved co-cultures showed that changes in both the leucine and lysine auxotrophs improved growth of the co-culture. Interestingly, while evolved isolates increased growth of co-cultures, they exhibited decreased growth in mono-culture (in the presence of leucine or lysine). A genome-scale metabolic model of the co-culture was also constructed and used to investigate the effects of amino acid (leucine or lysine) release and uptake rates on growth and composition of the co-culture. When the metabolic model was constrained by the estimated leucine and lysine release rates, the model predictions agreed well with experimental growth rates and composition measurements. While this study and others have focused on cooperative interactions amongst community members, the adaptive evolution of communities with other types of interactions (e.g., commensalism, ammensalism or parasitism) would also be of interest. PMID:25299364

MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts

PubMed Central

Li, Hong; Ke, Fei; Zhu, Junfa

2018-01-01

The development of a highly efficient and stable bifunctional electrocatalyst for water splitting is still a challenging issue in obtaining clean and sustainable chemical fuels. Herein, a novel bifunctional catalyst consisting of 2D transition-metal phosphide nanosheets with abundant reactive sites templated by Co-centered metal−organic framework nanosheets, denoted as CoP-NS/C, has been developed through a facile one-step low-temperature phosphidation process. The as-prepared CoP-NS/C has large specific surface area and ultrathin nanosheets morphology providing rich catalytic active sites. It shows excellent electrocatalytic performances for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic and alkaline media, with the Tafel slopes of 59 and 64 mV/dec and a current density of 10 mA/cm2 at the overpotentials of 140 and 292 mV, respectively, which are remarkably superior to those of CoP/C, CoP particles, and comparable to those of commercial noble-metal catalysts. In addition, the CoP-NS/C also shows good durability after a long-term test. PMID:29414838

Clarifying the Controversial Catalytic Performance of Co(OH)2 and Co3O4 for Oxygen Reduction/Evolution Reactions toward Efficient Zn-Air Batteries.

PubMed

Song, Zhishuang; Han, Xiaopeng; Deng, Yida; Zhao, Naiqin; Hu, Wenbin; Zhong, Cheng

2017-07-12

Cobalt-based nanomaterials have been widely studied as catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) due to their remarkable bifunctional catalytic activity, low cost, and easy availability. However, controversial results concerning OER/ORR performance exist between different types of cobalt-based catalysts, especially for Co(OH) 2 and Co 3 O 4 . To address this issue, we develop a facile electrochemical deposition method to grow Co(OH) 2 directly on the skeleton of carbon cloth, and further Co 3 O 4 was obtained by post thermal treatment. The entire synthesis strategy removes the use of any binders and also avoids the additional preparation process (e.g., transfer and slurry coating) of final electrodes. This leads to a true comparison of the ORR/OER catalytic performance between Co(OH) 2 and Co 3 O 4 , eliminating uncertainties arising from the electrode preparation procedures. The surface morphologies, microstructures, and electrochemical behaviors of prepared Co(OH) 2 and Co 3 O 4 catalysts were systemically investigated by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and electrochemical characterization methods. The results revealed that the electrochemically deposited Co(OH) 2 was in the form of vertically aligned nanosheets with average thickness of about 4.5 nm. After the thermal treatment in an air atmosphere, Co(OH) 2 nanosheets were converted into mesoporous Co 3 O 4 nanosheets with remarkably increased electrochemical active surface area (ECSA). Although the ORR/OER activity normalized by the geometric surface area of mesoporous Co 3 O 4 nanosheets is higher than that of Co(OH) 2 nanosheets, the performance normalized by the ECSA of the former is lower than that of the latter. Considering the superior apparent overall activity and durability, the Co 3 O 4 catalyst has been further evaluated by integrating it into a Zn-air battery prototype. The Co 3 O 4 nanosheets in situ supported on carbon cloth cathode enable the assembled Zn-air cells with large peak power density of 106.6 mW cm -2 , low charge and discharge overpotentials (0.67 V), high discharge rate capability (1.18 V at 20 mA cm -2 ), and long cycling stability (400 cycles), which are comparable or even superior to the mixture of state-of-the-art Pt/C and RuO 2 cathode.

Trends in activity for the oxygen evolution reaction on transition metal (M = Fe, Co, Ni) phosphide pre-catalysts† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc05033j

PubMed Central

Xu, Junyuan; Li, Junjie; Xiong, Dehua; Zhang, Bingsen; Liu, Yuefeng; Wu, Kuang-Hsu; Amorim, Isilda; Li, Wei

2018-01-01

Transition metal phosphides (TMPs) have recently emerged as a new class of pre-catalysts that can efficiently catalyze the oxygen evolution reaction (OER). However, how the OER activity of TMPs varies with the catalyst composition has not been systematically explored. Here, we report the alkaline OER electrolysis of a series of nanoparticulate phosphides containing different equimolar metal (M = Fe, Co, Ni) components. Notable trends in OER activity are observed, following the order of FeP < NiP < CoP < FeNiP < FeCoP < CoNiP < FeCoNiP, which indicate that the introduction of a secondary metal(s) to a mono-metallic TMP substantially boosts the OER performance. We ascribe the promotional effect to the enhanced oxidizing power of bi- and tri-metallic TMPs that can facilitate the formation of MOH and chemical adsorption of OH– groups, which are the rate-limiting steps for these catalysts according to our Tafel analysis. Remarkably, the tri-metallic FeCoNiP pre-catalyst exhibits exceptionally high apparent and intrinsic OER activities, requiring only 200 mV to deliver 10 mA cm–2 and showing a high turnover frequency (TOF) of ≥0.94 s–1 at the overpotential of 350 mV. PMID:29780476

Geochemical and Geomechanical Effects on Wellbore Cement Fractures

DOE PAGES

Um, Wooyong; Jung, Hun Bok; Kabilan, Senthil; ...

2014-12-31

Experimental studies were conducted using batch reactors, X-ray microtomograpy (XMT), and computational fluid dynamics (CFD) simulation to determine changes in cement fracture surfaces, fluid flow pathways, and permeability with geochemical and geomechanical processes. Composite Portland cement-basalt caprock core with artificial fractures was prepared and reacted with CO2-saturated groundwater at 50°C and 10 MPa for 3 to 3.5 months under static conditions to understand the geochemical and geomechanical effects on the integrity of wellbores containing defects. Cement-basalt interface samples were subjected to mechanical stress at 2.7 MPa before the CO2 reaction. XMT provided three-dimensional (3-D) visualization of the opening and interconnectionmore » of cement fractures due to mechanical stress. After the CO2 reaction, XMT images revealed that calcium carbonate precipitation occurred extensively within the fractures in the cement matrix, but only partially along fractures located at the cement-basalt interface. The permeability calculated based on CFD simulation was in agreement with the experimentally measured permeability. The experimental results imply that the wellbore cement with fractures is likely to be healed during exposure to CO2-saturated groundwater under static conditions, whereas fractures along the cement-caprock interface are still likely to remain vulnerable to the leakage of CO2. CFD simulation for the flow of different fluids (CO2-saturated brine and supercritical CO2) using a pressure difference of 20 kPa and 200 kPa along ~2 cm-long cement fractures showed that a pressure gradient increase resulted in an increase of CO2 fluids flux by a factor of only ~3-9 because the friction of CO2 fluids on cement fracture surfaces increased with higher flow rate as well. At the same pressure gradient, the simulated flow rate was higher for supercritical CO2 than CO2-saturated brine by a factor of only ~2-3, because the viscosity of supercritical CO2 is much lower than that of CO2-saturated brine. The study suggests that in deep geological reservoirs the geochemical and geomechanical processes have coupled effects on the wellbore cement fracture evolution and fluid flow along the fracture surfaces.« less

Rules of co-occurring mutations characterize the antigenic evolution of human influenza A/H3N2, A/H1N1 and B viruses.

PubMed

Chen, Haifen; Zhou, Xinrui; Zheng, Jie; Kwoh, Chee-Keong

2016-12-05

The human influenza viruses undergo rapid evolution (especially in hemagglutinin (HA), a glycoprotein on the surface of the virus), which enables the virus population to constantly evade the human immune system. Therefore, the vaccine has to be updated every year to stay effective. There is a need to characterize the evolution of influenza viruses for better selection of vaccine candidates and the prediction of pandemic strains. Studies have shown that the influenza hemagglutinin evolution is driven by the simultaneous mutations at antigenic sites. Here, we analyze simultaneous or co-occurring mutations in the HA protein of human influenza A/H3N2, A/H1N1 and B viruses to predict potential mutations, characterizing the antigenic evolution. We obtain the rules of mutation co-occurrence using association rule mining after extracting HA1 sequences and detect co-mutation sites under strong selective pressure. Then we predict the potential drifts with specific mutations of the viruses based on the rules and compare the results with the "observed" mutations in different years. The sites under frequent mutations are in antigenic regions (epitopes) or receptor binding sites. Our study demonstrates the co-occurring site mutations obtained by rule mining can capture the evolution of influenza viruses, and confirms that cooperative interactions among sites of HA1 protein drive the influenza antigenic evolution.

Importance of Electrode Material in the Electrochemical Treatment of Wastewater Containing Organic Pollutants

NASA Astrophysics Data System (ADS)

Panizza, Marco

Electrochemical oxidation is a promising method for the treatment of wastewaters containing organic compounds. As a general rule, the electrochemical incineration of organics at a given electrode can take place at satisfactory rates and without electrode deactivation only at high anodic potentials in the region of the water discharge due to the participation of the intermediates of oxygen evolution. The nature of the electrode material strongly influences both the selectivity and the efficiency of the process. In particular, anodes with low oxygen evolution overpotential (i.e., good catalysts for oxygen evolution reactions), such as graphite, IrO2, RuO2, and Pt only permit the partial oxidation of organics, while anodes with high oxygen evolution overpotential (i.e., anodes that are poor catalysts for oxygen evolution reactions), such as SnO2, PbO2, and boron-doped diamond (BDD) favor the complete oxidation of organics to CO2 and so are ideal electrodes for wastewater treatment.However, the application of SnO2 and PbO2 anodes may be limited by their short service life and the risk of lead contamination, while BDD electrodes exhibit good chemical and electrochemical stability, a long life, and a wide potential window for water discharge, and are thus promising anodes for industrial-scale wastewater treatment.

Lattice Boltzmann simulation of CO2 reactive transport in network fractured media

NASA Astrophysics Data System (ADS)

Tian, Zhiwei; Wang, Junye

2017-08-01

Carbon dioxide (CO2) geological sequestration plays an important role in mitigating CO2 emissions for climate change. Understanding interactions of the injected CO2 with network fractures and hydrocarbons is key for optimizing and controlling CO2 geological sequestration and evaluating its risks to ground water. However, there is a well-known, difficult process in simulating the dynamic interaction of fracture-matrix, such as dynamic change of matrix porosity, unsaturated processes in rock matrix, and effect of rock mineral properties. In this paper, we develop an explicit model of the fracture-matrix interactions using multilayer bounce-back treatment as a first attempt to simulate CO2 reactive transport in network fractured media through coupling the Dardis's LBM porous model for a new interface treatment. Two kinds of typical fracture networks in porous media are simulated: straight cross network fractures and interleaving network fractures. The reaction rate and porosity distribution are illustrated and well-matched patterns are found. The species concentration distribution and evolution with time steps are also analyzed and compared with different transport properties. The results demonstrate the capability of this model to investigate the complex processes of CO2 geological injection and reactive transport in network fractured media, such as dynamic change of matrix porosity.

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

PubMed

Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

2017-08-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assembly constraints drive co-evolution among ribosomal constituents.

PubMed

Mallik, Saurav; Akashi, Hiroshi; Kundu, Sudip

2015-06-23

Ribosome biogenesis, a central and essential cellular process, occurs through sequential association and mutual co-folding of protein-RNA constituents in a well-defined assembly pathway. Here, we construct a network of co-evolving nucleotide/amino acid residues within the ribosome and demonstrate that assembly constraints are strong predictors of co-evolutionary patterns. Predictors of co-evolution include a wide spectrum of structural reconstitution events, such as cooperativity phenomenon, protein-induced rRNA reconstitutions, molecular packing of different rRNA domains, protein-rRNA recognition, etc. A correlation between folding rate of small globular proteins and their topological features is known. We have introduced an analogous topological characteristic for co-evolutionary network of ribosome, which allows us to differentiate between rRNA regions subjected to rapid reconstitutions from those hindered by kinetic traps. Furthermore, co-evolutionary patterns provide a biological basis for deleterious mutation sites and further allow prediction of potential antibiotic targeting sites. Understanding assembly pathways of multicomponent macromolecules remains a key challenge in biophysics. Our study provides a 'proof of concept' that directly relates co-evolution to biophysical interactions during multicomponent assembly and suggests predictive power to identify candidates for critical functional interactions as well as for assembly-blocking antibiotic target sites. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H2 Evolution.

PubMed

Li, Xiaogang; Bi, Wentuan; Zhang, Lei; Tao, Shi; Chu, Wangsheng; Zhang, Qun; Luo, Yi; Wu, Changzheng; Xie, Yi

2016-03-23

Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolutionary bursts in Euphorbia (Euphorbiaceae) are linked with photosynthetic pathway.

PubMed

Horn, James W; Xi, Zhenxiang; Riina, Ricarda; Peirson, Jess A; Yang, Ya; Dorsey, Brian L; Berry, Paul E; Davis, Charles C; Wurdack, Kenneth J

2014-12-01

The mid-Cenozoic decline of atmospheric CO2 levels that promoted global climate change was critical to shaping contemporary arid ecosystems. Within angiosperms, two CO2 -concentrating mechanisms (CCMs)-crassulacean acid metabolism (CAM) and C4 -evolved from the C3 photosynthetic pathway, enabling more efficient whole-plant function in such environments. Many angiosperm clades with CCMs are thought to have diversified rapidly due to Miocene aridification, but links between this climate change, CCM evolution, and increased net diversification rates (r) remain to be further understood. Euphorbia (∼2000 species) includes a diversity of CAM-using stem succulents, plus a single species-rich C4 subclade. We used ancestral state reconstructions with a dated molecular phylogeny to reveal that CCMs independently evolved 17-22 times in Euphorbia, principally from the Miocene onwards. Analyses assessing among-lineage variation in r identified eight Euphorbia subclades with significantly increased r, six of which have a close temporal relationship with a lineage-corresponding CCM origin. Our trait-dependent diversification analysis indicated that r of Euphorbia CCM lineages is approximately threefold greater than C3 lineages. Overall, these results suggest that CCM evolution in Euphorbia was likely an adaptive strategy that enabled the occupation of increased arid niche space accompanying Miocene expansion of arid ecosystems. These opportunities evidently facilitated recent, replicated bursts of diversification in Euphorbia. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Plant water use efficiency over geological time--evolution of leaf stomata configurations affecting plant gas exchange.

PubMed

Assouline, Shmuel; Or, Dani

2013-01-01

Plant gas exchange is a key process shaping global hydrological and carbon cycles and is often characterized by plant water use efficiency (WUE - the ratio of CO2 gain to water vapor loss). Plant fossil record suggests that plant adaptation to changing atmospheric CO2 involved correlated evolution of stomata density (d) and size (s), and related maximal aperture, amax . We interpreted the fossil record of s and d correlated evolution during the Phanerozoic to quantify impacts on gas conductance affecting plant transpiration, E, and CO2 uptake, A, independently, and consequently, on plant WUE. A shift in stomata configuration from large s-low d to small s-high d in response to decreasing atmospheric CO2 resulted in large changes in plant gas exchange characteristics. The relationships between gas conductance, gws , A and E and maximal relative transpiring leaf area, (amax ⋅d), exhibited hysteretic-like behavior. The new WUE trend derived from independent estimates of A and E differs from established WUE-CO2 trends for atmospheric CO2 concentrations exceeding 1,200 ppm. In contrast with a nearly-linear decrease in WUE with decreasing CO2 obtained by standard methods, the newly estimated WUE trend exhibits remarkably stable values for an extended geologic period during which atmospheric CO2 dropped from 3,500 to 1,200 ppm. Pending additional tests, the findings may affect projected impacts of increased atmospheric CO2 on components of the global hydrological cycle.

Revealing the relationship between the photocatalytic property and structure characteristic of reduced TiO2 by hydrogen and carbon monoxide treatment.

PubMed

Liu, Yunpeng; Li, Yuhang; Yang, Siyuan; Lin, Yuan; Zuo, Jianliang; Liang, Hong; Peng, Feng

2018-06-04

The hydrogenation (reduction) has been considered as an effective method to improve the photocatalytic activity of TiO2, however, the underlying relationship between structure and photocatalytic performance has still not been adequately unveiled so far. Herein, to obtain insight into the effect of structure on photocatalytic activity, two types of reduced TiO2 were prepared by CO (CO-TiO2) and H2 (H-TiO2), respectively. For H-TiO2, Ti-H bonds and oxygen vacancies are formed on the surface of H-TiO2, resulting in a more disorder surface lattice. However, for CO-TiO2, the more Ti-OH bonds are formed on the surface and the more bulk oxygen vacancies are introduced, the disorder layer of CO-TiO2 is relatively thin owing to the most of surface vacancies repaired by Ti-OH bonds. Under the simulated solar irradiation, the photocatalytic H2 evolution rate of CO-TiO2 reaches 7.17 mmol g-1 h-1, which is 4.14 and 1.50 times those of TiO2 and H-TiO2, respectively. The photocatalytic degradation rate constant of methyl orange on CO-TiO2 is 2.45 and 6.39 times those on H-TiO2 and TiO2. The superior photocatalytic activity of CO-TiO2 is attributed to the effective separation and transfer of the photo-generated electron-hole pairs, due to the synergistic effects of oxygen vacancies and surface Ti-OH bonds. This study reveals the relation between the photocatalytic property and structure, and provides a new method to prepare highly active TiO2 for H2 production and environmental treatment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution.

PubMed

Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco

2016-12-12

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H 2 per hour at 50 mV overpotential). The Tafel slope of ∼130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J.; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco

2016-12-01

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ~130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

PubMed Central

Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J.; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco

2016-01-01

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ∼130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure. PMID:27941752

Mechanisms of carbon dioxide acquisition and CO2 sensing in marine diatoms: a gateway to carbon metabolism.

PubMed

Matsuda, Yusuke; Hopkinson, Brian M; Nakajima, Kensuke; Dupont, Christopher L; Tsuji, Yoshinori

2017-09-05

Diatoms are one of the most successful marine eukaryotic algal groups, responsible for up to 20% of the annual global CO 2 fixation. The evolution of a CO 2 -concentrating mechanism (CCM) allowed diatoms to overcome a number of serious constraints on photosynthesis in the marine environment, particularly low [CO 2 ] aq in seawater relative to concentrations required by the CO 2 fixing enzyme, ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO), which is partly due to the slow diffusion rate of CO 2 in water and a limited CO 2 formation rate from [Formula: see text] in seawater. Diatoms use two alternative strategies to take up dissolved inorganic carbon (DIC) from the environment: one primarily relies on the direct uptake of [Formula: see text] through plasma-membrane type solute carrier (SLC) 4 family [Formula: see text] transporters and the other is more reliant on passive diffusion of CO 2 formed by an external carbonic anhydrase (CA). Bicarbonate taken up into the cytoplasm is most likely then actively transported into the chloroplast stroma by SLC4-type transporters on the chloroplast membrane system. Bicarbonate in the stroma is converted into CO 2 only in close proximity to RubisCO preventing unnecessary CO 2 leakage. CAs play significant roles in mobilizing DIC as it is progressively moved towards the site of fixation. However, the evolutionary types and subcellular locations of CAs are not conserved between different diatoms, strongly suggesting that this DIC mobilization strategy likely evolved multiple times with different origins. By contrast, the recent discovery of the thylakoid luminal θ-CA indicates that the strategy to supply CO 2 to RubisCO in the pyrenoid may be very similar to that of green algae, and strongly suggests convergent coevolution in CCM function of the thylakoid lumen not only among diatoms but among eukaryotic algae in general. In this review, both experimental and corresponding theoretical models of the diatom CCMs are discussed.This article is part of the themed issue 'The peculiar carbon metabolism in diatoms'. © 2017 The Author(s).

Gas, dust, stars, star formation, and their evolution in M 33 at giant molecular cloud scales

NASA Astrophysics Data System (ADS)

Komugi, Shinya; Miura, Rie E.; Kuno, Nario; Tosaki, Tomoka

2018-06-01

We report on a multi-parameter analysis of giant molecular clouds (GMCs) in the nearby spiral galaxy M 33. A catalog of GMCs identifed in 12CO(J = 3-2) was used to compile associated 12CO(J = 1-0), dust, stellar mass, and star formation rate. Each of the 58 GMCs are categorized by their evolutionary stage. Applying the principal component analysis on these parameters, we construct two principal components, PC1 and PC2, which retain 75% of the information from the original data set. PC1 is interpreted as expressing the total interstellar matter content, and PC2 as the total activity of star formation. Young (< 10 Myr) GMCs occupy a distinct region in the PC1-PC2 plane, with lower interstellar medium (ISM) content and star formation activity compared to intermediate-age and older clouds. Comparison of average cloud properties in different evolutionary stages imply that GMCs may be heated or grow denser and more massive via aggregation of diffuse material in their first ˜ 10 Myr. The PCA also objectively identified a set of tight relations between ISM and star formation. The ratio of the two CO lines is nearly constant, but weakly modulated by massive star formation. Dust is more strongly correlated with the star formation rate than the CO lines, supporting recent findings that dust may trace molecular gas better than CO. Stellar mass contributes weakly to the star formation rate, reminiscent of an extended form of the Schmidt-Kennicutt relation with the molecular gas term substituted by dust.

Gas, dust, stars, star formation, and their evolution in M 33 at giant molecular cloud scales

NASA Astrophysics Data System (ADS)

Komugi, Shinya; Miura, Rie E.; Kuno, Nario; Tosaki, Tomoka

2018-04-01

We report on a multi-parameter analysis of giant molecular clouds (GMCs) in the nearby spiral galaxy M 33. A catalog of GMCs identifed in 12CO(J = 3-2) was used to compile associated 12CO(J = 1-0), dust, stellar mass, and star formation rate. Each of the 58 GMCs are categorized by their evolutionary stage. Applying the principal component analysis on these parameters, we construct two principal components, PC1 and PC2, which retain 75% of the information from the original data set. PC1 is interpreted as expressing the total interstellar matter content, and PC2 as the total activity of star formation. Young (< 10 Myr) GMCs occupy a distinct region in the PC1-PC2 plane, with lower interstellar medium (ISM) content and star formation activity compared to intermediate-age and older clouds. Comparison of average cloud properties in different evolutionary stages imply that GMCs may be heated or grow denser and more massive via aggregation of diffuse material in their first ˜ 10 Myr. The PCA also objectively identified a set of tight relations between ISM and star formation. The ratio of the two CO lines is nearly constant, but weakly modulated by massive star formation. Dust is more strongly correlated with the star formation rate than the CO lines, supporting recent findings that dust may trace molecular gas better than CO. Stellar mass contributes weakly to the star formation rate, reminiscent of an extended form of the Schmidt-Kennicutt relation with the molecular gas term substituted by dust.

Molecular Dynamics Studies of Thermal Induced Chemistry in Tatb

NASA Astrophysics Data System (ADS)

Quenneville, J.; Germann, T. C.; Thompson, A. P.; Kober, E. M.

2007-12-01

A reactive force field (ReaxFF) is used with molecular dynamics to probe the chemistry induced by intense heating (`accelerated cook-off') of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Large-system simulations are desired for TATB because of the high degree of carbon clustering expected in this material. Using small, 32-molecule simulations, we calculate the reaction rate as a function of temperature and compare the Arrhenius-predicted activation energy with experiment. Decomposition product evolution (mainly N2, H2O, CO2 and graphitic carbon clusters) is followed using a 576-molecule larger simulation, which also illustrates the effect of system size on both carbon clustering and reaction rate.

An experimental and computational evolution-based method to study a mode of co-evolution of overlapping open reading frames in the AAV2 viral genome.

PubMed

Kawano, Yasuhiro; Neeley, Shane; Adachi, Kei; Nakai, Hiroyuki

2013-01-01

Overlapping open reading frames (ORFs) in viral genomes undergo co-evolution; however, how individual amino acids coded by overlapping ORFs are structurally, functionally, and co-evolutionarily constrained remains difficult to address by conventional homologous sequence alignment approaches. We report here a new experimental and computational evolution-based methodology to address this question and report its preliminary application to elucidating a mode of co-evolution of the frame-shifted overlapping ORFs in the adeno-associated virus (AAV) serotype 2 viral genome. These ORFs encode both capsid VP protein and non-structural assembly-activating protein (AAP). To show proof of principle of the new method, we focused on the evolutionarily conserved QVKEVTQ and KSKRSRR motifs, a pair of overlapping heptapeptides in VP and AAP, respectively. In the new method, we first identified a large number of capsid-forming VP3 mutants and functionally competent AAP mutants of these motifs from mutant libraries by experimental directed evolution under no co-evolutionary constraints. We used Illumina sequencing to obtain a large dataset and then statistically assessed the viability of VP and AAP heptapeptide mutants. The obtained heptapeptide information was then integrated into an evolutionary algorithm, with which VP and AAP were co-evolved from random or native nucleotide sequences in silico. As a result, we demonstrate that these two heptapeptide motifs could exhibit high degeneracy if coded by separate nucleotide sequences, and elucidate how overlap-evoked co-evolutionary constraints play a role in making the VP and AAP heptapeptide sequences into the present shape. Specifically, we demonstrate that two valine (V) residues and β-strand propensity in QVKEVTQ are structurally important, the strongly negative and hydrophilic nature of KSKRSRR is functionally important, and overlap-evoked co-evolution imposes strong constraints on serine (S) residues in KSKRSRR, despite high degeneracy of the motifs in the absence of co-evolutionary constraints.

Characterization of H2 photoproduction by marine green alga Tetraselmis subcordiformis integrated with an alkaline fuel cell.

PubMed

Guo, Zhen; Li, Ying; Guo, Haiyan

2016-03-01

To investigate the feasibility of coupling carbonyl cyanide m-chlorophenylhydrazone-regulated photohydrogen production by Tetraselmis subcordiformis in a photobioreactor to an alkaline fuel cell (AFC). H2 evolution kinetics in the AFC integrated process was characterized. The duration of H2 evolution was prolonged and its yield was improved about 1.5-fold (to 78 ± 5 ml l(-1)) compared with that of the process without AFC. Improved H2 yield was possibly caused by removal of H2 feedback inhibition by H2 consumption in situ. Decreases in the H2 production rate correlated with the gradual deactivation of PSII and hydrogenase activities. The H2 yield was closely associated with catabolism of starch and protein. A marine green algal CO2-supplemented culture integrated with in situ H2-consumption by an AFC system was developed as a viable protocol for the H2 production.

Facile Modification of TiO2 with Nickel Sulfide and Sulfate Species for Photoreformation of Cellulose into H2.

PubMed

Hao, Hongchang; Zhang, Ling; Wang, Wenzhong; Zeng, Shuwen

2018-06-19

Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H2 evolution. However, the direct photoreformation still suffers from challenges such as the limited solubility of cellulose and dependence on catalytic activity of noble-metals. Herein, we reported a novel photoreformation of cellulose into H2 over TiO2 which is synchronously modified with nickel sulfide (NixSy) and chemisorbed sulfate species (SO42-) by a one-pot approach. A significant elevation in photocatalytic hydrogen evolution rate is achieved, with the maximal value of 3.02 mmol/g/h during the first three hours, almost 76-fold higher than that of P25 and comparable to Pt-P25. Aided by systematic investigation, it is proposed that nickel sulfide and sulfate modification synergistically contribute to the remarkably raised efficiency of biomass transformation. Specifically, NixSy serves as co-catalyst for photocatalytic H2 production, while SO42- ions are inferred to promote cellulose hydrolyzation and consequent accessibility of biomass to catalysts. Further, the accumulated formate intermediates are found to have a poison effect on catalysts, desorption of which can be controlled by tuning aqueous alkalinity. Overall, our strategy for modifying TiO2 with SO42- and NixSy provides a novel perspective of concurrently accelerating cellulose hydrolyzation process and supplementing hydrogen evolution sites, for efficient photocatalytic reformation of cellulose into H2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Landscape Evolution and the Reincarnation of the Residual CO2 Ice Cap of Mars

NASA Astrophysics Data System (ADS)

Byrne, S.; Zuber, M.

2006-12-01

Observations of the southern residual CO2 cap of Mars reveal a wide range of landforms including flat-floored quasi-circular pits with steep walls (dubbed Swiss-cheese features). Interannual comparisons show that these depressions are expanding laterally at rates of ~2m/yr to ~4m/yr, prompting suggestions of climate change. The residual CO2 ice cap is up to 10m thick and underlain by an involatile basement, it also contains layers roughly 2m thick representing different accumulation episodes in the recent past. Changes in the appearance of the residual ice between the Mariner 9 and Viking missions indicate that the top-most layer was deposited in that time-frame, soon after the global dust storm of 1971. The spatial density of the Swiss-cheese features, and the rate at which they expand, mean that it is unlikely that any part of the residual ice cap is older than a few centuries. Given this, we may ask: how can there be a residual cap present today for us to observe? To answer this and other questions we have developed a model to examine the evolution of a CO2 ice landscape. This model reproduces the morphologies and expansion rates seen in the actual residual CO2 ice cap. Our model results indicate that the fate of CO2 ice surfaces is controlled by their surface roughness. Surface roughness always increases with time, which results in an unstable situation. When the surface roughness exceeds a critical point small pits can begin to develop. The walls of these pits rapidly steepen and begin retreating which enlarges and deepens the pit. This situation always occurs even if the surface of the CO2 slab has a high enough albedo to have a net mass gain each year. Once these pits begin expanding they quickly erode the entire ice slab. When the underlying non-CO2 material is exposed, it will not frost over again if Mars were to repeat like clockwork every year. We conclude that interannual climatic variability is actually a requirement for the continued existence of a residual CO2 ice cap. We invoke unusual depositional episodes (which have a surface smoothing effect) after which the cap can begin accumulating mass and growing in thickness again. This continues until the surface roughness again exceeds a stable state and the process repeats itself. The thickness of the residual cap therefore oscillates on timescales of centuries. The total cap volume may also be affected by variations in residual cap extent. The cap is not 'stable' in the usual sense of the word, but instead is constantly being destroyed and recreated. Evidence suggests that these rejuvenating depositional events are linked to global dust storms. The 10m thick stratigraphic record thus provides a unique measure of interannual variability of the current climate, the expanding Swiss-cheese features do not indicate secular climate change, but instead are just part of the larger life-cycle of this ice deposit. We will report on this surface modeling which reproduces other morphologies within the residual cap and present a historical model based on combining our modeling with the feature sizes and ablation rates found within the present residual ice cap.

Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

2017-05-01

The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

Postillumination burst of carbon dioxide in crassalacean Acid metabolism plants.

PubMed

Crews, C E; Vines, H M; Black, C C

1975-04-01

Immediately following exposure to light, a postillumination burst of CO(2) has been detected in Crassulacean acid metabolism plants. A detailed study with pineapple (Ananas comosus) leaves indicates that the postillumination burst changes its amplitude and kinetics during the course of a day. In air, the postillumination burst in pineapple leaves generally is exhibited as two peaks. The postillumination burst is sensitive to atmospheric CO(2) and O(2) concentrations as well as to the light intensity under which plants are grown. We propose that the CO(2) released in the first postillumination burst peak is indicative of photorespiration since it is sensitive to either O(2) or CO(2) concentration while the second CO(2) evolution peak is likely due to decarboxylation of organic acids involved in Crassulacean acid metabolism.In marked contrast to other higher plants, the postillumination burst in Crassulacean acid metabolism plants can be equal to or greater than the rate of photosynthesis. Photosynthesis in pineapple leaves also varies throughout a day. Both photosynthesis and the postillumination burst have a daily variation which apparently is a complex function of degree of leaf acidity, growth light intensity, ambient gas phase, and the time a plant has been exposed to a given gas.

Mode-medium instability and its correction with a Gaussian-reflectivity mirror

NASA Technical Reports Server (NTRS)

Webster, K. L.; Sung, C. C.

1992-01-01

A high-power CO2 laser beam is known to deteriorate after a few microseconds due to a mode-medium instability (MMI) which results from an intensity-dependent heating rate related to the vibrational-to-translational decay of the upper and lower CO2 lasing levels. An iterative numerical technique is developed to model the time evolution of the beam as it is affected by the MMI. The technique is used to study the MMI in an unstable CO2 resonator with a hard-edge output mirror for different parameters like the Fresnel number and the gas density. The results show that the mode of the hard edge unstable resonator deteriorates because of the diffraction ripples in the mode. A Gaussian-reflectivity mirror was used to correct the MMI. This mirror produces a smoother intensity profile which significantly reduces the effects of the MMI. Quantitative results on peak density variation and beam quality are presented.

Mode-medium instability and its correction with a Gaussian reflectivity mirror

NASA Technical Reports Server (NTRS)

Webster, K. L.; Sung, C. C.

1990-01-01

A high power CO2 laser beam is known to deteriorate after a few microseconds due to a mode-medium instability (MMI) which results from an intensity dependent heating rate related to the vibrational-to-translational decay of the upper and lower CO2 lasing levels. An iterative numerical technique is developed to model the time evolution of the beam as it is affected by the MMI. The technique is used to study the MMI in an unstable CO2 resonator with a hard-edge output mirror for different parameters like the Fresnel number and the gas density. The results show that the mode of the hard edge unstable resonator deteriorates because of the diffraction ripples in the mode. A Gaussian-reflectivity mirror was used to correct the MMI. This mirror produces a smoother intensity profile which significantly reduces the effects of the MMI. Quantitative results on peak density variation and beam quality are presented.

γ' Precipitation Study of a Co-Ni-Based Alloy

NASA Astrophysics Data System (ADS)

Locq, D.; Martin, M.; Ramusat, C.; Fossard, F.; Perrut, M.

2018-05-01

A Co-Ni-based alloy strengthened by γ'-(L12) precipitates was utilized to investigate the precipitation evolution after various cooling rates and several aging conditions. In this study, the precipitate size and volume fraction have been studied via scanning electron microscopy and transmission electron microscopy. The influence of the precipitation evolution was measured via microhardness tests. The cooling rate study shows a more sluggish γ' precipitation reaction compared to that observed in a Ni-based superalloy. Following a rapid cooling rate, the application of appropriate double aging treatments allows for the increase of the γ' volume fraction as well as the control of the size and distribution of the precipitates. The highest hardness values reach those measured on supersolvus cast and wrought Ni-based superalloys. The observed γ' precipitation behavior should have implications for the production, the heat treatment, the welding, or the additive manufacturing of this new class of high-temperature materials.

Analysis of Regional Effects on Market Segment Production

DTIC Science & Technology

2016-06-01

REGIONAL EFFECTS ON MARKET SEGMENT PRODUCTION by James D. Moffitt June 2016 Thesis Advisor: Lyn R. Whitaker Co-Advisor: Jonathan K. Alt...REPORT TYPE AND DATES COVERED Master’s thesis 4. TITLE AND SUBTITLE ANALYSIS OF REGIONAL EFFECTS ON MARKET SEGMENT PRODUCTION 5. FUNDING NUMBERS 6...accessions in Potential Rating Index Zip Code Market New Evolution (PRIZM NE) market segments. This model will aid USAREC G2 analysts involved in

Enhanced compositing of radiation disinfected sewage sludge

NASA Astrophysics Data System (ADS)

Kawakami, W.; Hashimoto, S.

Studies on isothermal composting of radiation disinfected sewage sludge and liquid chromatography of water extracts of the products were carried out. The optimum temperature and pH were around 50 °C and 7-8, respectively. The repeated use of products as seeds increased the rate of CO 2 evolution. The rate reached a maximum within 10 hours and decreased rapidly, and the CO 2 evolution ceased after about 3 days. The conversion of organic carbon to carbon dioxide attained to about 40% for the repeated use of products as seeds at the optimum conditions. As long as seeds in available were used, no remarkable difference was found in the composting of unirradiated and irradiated sludges. The composting process using radiation, however, can be carried out at the optimum conditions and is expected to shorten the composting period, because it is not necessary to keep fermentation temperature higher to reduce pathogen in sludge. Liquid chromatographic studies of the products showed that low molecular components decreased and higher molecular ones increased with fermentation. An index expressing the degree of reduction of easily decomposable organics was presented. The index also showed that the optimum temperature for fermentation was 50 °C, and that the easily decomposable organics disappeared above 30% of the conversion of organic carbon.

Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

PubMed

Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

2008-01-01

The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

Comprehensive study of the evolution of gas-liquid partitioning of aroma compounds during wine alcoholic fermentation.

PubMed

Morakul, Sumallika; Athes, Violaine; Mouret, Jean-Roch; Sablayrolles, Jean-Marie

2010-09-22

Calculating the gas-liquid partitioning of aromatic molecules during winemaking fermentation is essential to minimize the loss of aroma and to optimize the fermentation conditions. In this study, the effect of the main fermentation parameters on the partition coefficients (ki) of higher alcohols (2-methylpropan-1-ol and 3-methyl butan-1-ol) and esters (ethyl acetate, 3-methyl-1-butyl acetate, and 2-ethyl hexanoate) was assessed. The values of ki were first determined in synthetic media simulating must and wine. They varied considerably with both the hydrophobicity of the compound and the composition of the medium. Then, the effect of temperature on ki was quantified. The absence of any effect of gas composition was also established by replacing air with CO2. Finally, the impact of CO2 stripping was assessed by running specific fermentations in which the rate of CO2 production was kept constant by perfusion with assimilable nitrogen. These fermentations showed that in contrast to temperature and must composition, CO2 stripping did not change the gas-liquid partitioning of higher alcohols and esters.

Plate tectonic controls on atmospheric CO2 levels since the Triassic.

PubMed

Van Der Meer, Douwe G; Zeebe, Richard E; van Hinsbergen, Douwe J J; Sluijs, Appy; Spakman, Wim; Torsvik, Trond H

2014-03-25

Climate trends on timescales of 10s to 100s of millions of years are controlled by changes in solar luminosity, continent distribution, and atmosphere composition. Plate tectonics affect geography, but also atmosphere composition through volcanic degassing of CO2 at subduction zones and midocean ridges. So far, such degassing estimates were based on reconstructions of ocean floor production for the last 150 My and indirectly, through sea level inversion before 150 My. Here we quantitatively estimate CO2 degassing by reconstructing lithosphere subduction evolution, using recent advances in combining global plate reconstructions and present-day structure of the mantle. First, we estimate that since the Triassic (250-200 My) until the present, the total paleosubduction-zone length reached up to ∼200% of the present-day value. Comparing our subduction-zone lengths with previously reconstructed ocean-crust production rates over the past 140 My suggests average global subduction rates have been constant, ∼6 cm/y: Higher ocean-crust production is associated with longer total subduction length. We compute a strontium isotope record based on subduction-zone length, which agrees well with geological records supporting the validity of our approach: The total subduction-zone length is proportional to the summed arc and ridge volcanic CO2 production and thereby to global volcanic degassing at plate boundaries. We therefore use our degassing curve as input for the GEOCARBSULF model to estimate atmospheric CO2 levels since the Triassic. Our calculated CO2 levels for the mid Mesozoic differ from previous modeling results and are more consistent with available proxy data.

Plate tectonic controls on atmospheric CO2 levels since the Triassic

PubMed Central

Van Der Meer, Douwe G.; Zeebe, Richard E.; van Hinsbergen, Douwe J. J.; Sluijs, Appy; Spakman, Wim; Torsvik, Trond H.

2014-01-01

Climate trends on timescales of 10s to 100s of millions of years are controlled by changes in solar luminosity, continent distribution, and atmosphere composition. Plate tectonics affect geography, but also atmosphere composition through volcanic degassing of CO2 at subduction zones and midocean ridges. So far, such degassing estimates were based on reconstructions of ocean floor production for the last 150 My and indirectly, through sea level inversion before 150 My. Here we quantitatively estimate CO2 degassing by reconstructing lithosphere subduction evolution, using recent advances in combining global plate reconstructions and present-day structure of the mantle. First, we estimate that since the Triassic (250–200 My) until the present, the total paleosubduction-zone length reached up to ∼200% of the present-day value. Comparing our subduction-zone lengths with previously reconstructed ocean-crust production rates over the past 140 My suggests average global subduction rates have been constant, ∼6 cm/y: Higher ocean-crust production is associated with longer total subduction length. We compute a strontium isotope record based on subduction-zone length, which agrees well with geological records supporting the validity of our approach: The total subduction-zone length is proportional to the summed arc and ridge volcanic CO2 production and thereby to global volcanic degassing at plate boundaries. We therefore use our degassing curve as input for the GEOCARBSULF model to estimate atmospheric CO2 levels since the Triassic. Our calculated CO2 levels for the mid Mesozoic differ from previous modeling results and are more consistent with available proxy data. PMID:24616495

FLAVODIIRON2 and FLAVODIIRON4 Proteins Mediate an Oxygen-Dependent Alternative Electron Flow in Synechocystis sp. PCC 6803 under CO2-Limited Conditions1[OPEN

PubMed Central

Shimakawa, Ginga; Shaku, Keiichiro; Nishi, Akiko; Hayashi, Ryosuke; Yamamoto, Hiroshi; Sakamoto, Katsuhiko; Makino, Amane; Miyake, Chikahiro

2015-01-01

This study aims to elucidate the molecular mechanism of an alternative electron flow (AEF) functioning under suppressed (CO2-limited) photosynthesis in the cyanobacterium Synechocystis sp. PCC 6803. Photosynthetic linear electron flow, evaluated as the quantum yield of photosystem II [Y(II)], reaches a maximum shortly after the onset of actinic illumination. Thereafter, Y(II) transiently decreases concomitantly with a decrease in the photosynthetic oxygen evolution rate and then recovers to a rate that is close to the initial maximum. These results show that CO2 limitation suppresses photosynthesis and induces AEF. In contrast to the wild type, Synechocystis sp. PCC 6803 mutants deficient in the genes encoding FLAVODIIRON2 (FLV2) and FLV4 proteins show no recovery of Y(II) after prolonged illumination. However, Synechocystis sp. PCC 6803 mutants deficient in genes encoding proteins functioning in photorespiration show AEF activity similar to the wild type. In contrast to Synechocystis sp. PCC 6803, the cyanobacterium Synechococcus elongatus PCC 7942 has no FLV proteins with high homology to FLV2 and FLV4 in Synechocystis sp. PCC 6803. This lack of FLV2/4 may explain why AEF is not induced under CO2-limited photosynthesis in S. elongatus PCC 7942. As the glutathione S-transferase fusion protein overexpressed in Escherichia coli exhibits NADH-dependent oxygen reduction to water, we suggest that FLV2 and FLV4 mediate oxygen-dependent AEF in Synechocystis sp. PCC 6803 when electron acceptors such as CO2 are not available. PMID:25540330

Vectorial electron transfer for improved hydrogen evolution by mercaptopropionic-acid-regulated CdSe quantum-dots-TiO2 -Ni(OH)2 assembly.

PubMed

Yu, Shan; Li, Zhi-Jun; Fan, Xiang-Bing; Li, Jia-Xin; Zhan, Fei; Li, Xu-Bing; Tao, Ye; Tung, Chen-Ho; Wu, Li-Zhu

2015-02-01

A visible-light-induced hydrogen evolution system based on a CdSe quantum dots (QDs)-TiO2 -Ni(OH)2 ternary assembly has been constructed under an ambient environment, and a bifunctional molecular linker, mercaptopropionic acid, is used to facilitate the interaction between CdSe QDs and TiO2 . This hydrogen evolution system works effectively in a basic aqueous solution (pH 11.0) to achieve a hydrogen evolution rate of 10.1 mmol g(-1)  h(-1) for the assembly and a turnover frequency of 5140 h(-1) with respect to CdSe QDs (10 h); the latter is comparable with the highest value reported for QD systems in an acidic environment. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and control experiments demonstrate that Ni(OH)2 is an efficient hydrogen evolution catalyst. In addition, inductively coupled plasma optical emission spectroscopy and the emission decay of the assembly combined with the hydrogen evolution experiments show that TiO2 functions mainly as the electron mediator; the vectorial electron transfer from CdSe QDs to TiO2 and then from TiO2 to Ni(OH)2 enhances the efficiency for hydrogen evolution. The assembly comprises light antenna CdSe QDs, electron mediator TiO2 , and catalytic Ni(OH)2 , which mimics the strategy of photosynthesis exploited in nature and takes us a step further towards artificial photosynthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

NASA Astrophysics Data System (ADS)

Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

2018-06-01

A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

Effect of Mars Atmospheric Loss on Snow Melt Potential in a 3.5 Gyr Mars Climate Evolution Model

NASA Astrophysics Data System (ADS)

Mansfield, Megan; Kite, Edwin S.; Mischna, Michael A.

2018-04-01

Post-Noachian Martian paleochannels indicate the existence of liquid water on the surface of Mars after about 3.5 Gya (Irwin et al., 2015, https://doi.org/10.1016/j.geomorph.2014.10.012; Palucis et al., 2016, https://doi.org/10.1002/2015JE004905). In order to explore the effects of variations in CO2 partial pressure and obliquity on the possibility of surface water, we created a zero-dimensional surface energy balance model. We combine this model with physically consistent orbital histories to track conditions over the last 3.5 Gyr of Martian history. We find that melting is allowed for atmospheric pressures corresponding to exponential loss rates of dP/dt∝t-3.73 or faster, but this rate is within 0.5σ of the rate calculated from initial measurements made by the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission, if we assume all the escaping oxygen measured by MAVEN comes from atmospheric CO2 (Lillis et al., 2017, https://doi.org/10.1002/2016JA023525; Tu et al., 2015, https://doi.org/10.1051/0004-6361/201526146). Melting at this loss rate matches selected key geologic constraints on the formation of Hesperian river networks, assuming optimal melt conditions during the warmest part of each Mars year (Irwin et al., 2015, https://doi.org/10.1016/j.geomorph.2014.10.012; Kite, Gao, et al., 2017, https://doi.org/10.1038/ngeo3033; Kite, Sneed et al., 2017, https://doi.org/10.1002/2017GL072660; Stopar et al., 2006, https://doi.org/10.1016/j.gca.2006.07.039). The atmospheric pressure has a larger effect on the surface energy than changes in Mars's mean obliquity. These results show that initial measurements of atmosphere loss by MAVEN are consistent with atmospheric loss being the dominant process that switched Mars from a melt-permitting to a melt-absent climate (Jakosky et al., 2017, https://doi.org/10.1126/science.aai7721), but non-CO2 warming will be required if <2 Gya paleochannels are confirmed or if most of the escaping oxygen measured by MAVEN comes from H2O.

Effects of Plutonium on Soil Microorganisms

PubMed Central

Wildung, Raymond E.; Garland, Thomas R.

1982-01-01

As a first phase in an investigation of the role of the soil microflora in Pu complex formation and solubilization in soil, the effects of Pu concentration, form, and specific activity on microbial types, colony-forming units, and CO2 evolution rate were determined in soils amended with C and N sources to optimize microbial activity. The effects of Pu differed with organism type and incubation time. After 30 days of incubation, aerobic sporeforming and anaerobic bacteria were significantly affected by soil Pu levels as low as 1 μg/g when Pu was added as the hydrolyzable 239Pu(NO3)4 (solubility, <0.1% in soil). Other classes of organisms, except the fungi, were significantly affected at soil Pu levels of 10 μg/g. Fungi were affected only at soil Pu levels of 180 μg/g. Soil CO2 evolution rate and total accumulated CO2 were affected by Pu only at the 180 μg/g level. Because of the possible role of resistant organisms in complex formation, the mechanisms of effects of Pu on the soil fungi were further evaluated. The effect of Pu on soil fungal colony-forming units was a function of Pu solubility in soil and Pu specific activity. When Pu was added in a soluble, complexed form [238Pu2(diethylenetriaminepentaacetate)3], effects occurred at Pu levels of 1 μg/g and persisted for at least 95 days. Toxicity was due primarily to radiation effects rather than to chemical effects, suggesting that, at least in the case of the fungi, formation of Pu complexes would result primarily from ligands associated with normal (in contrast to chemically-induced) biochemical pathways. PMID:16345947

2-Oxoacid Metabolism in Methanogenic CoM and CoB Biosynthesis

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

Graham, David E

Coenzyme M (CoM) and coenzyme B (CoB) are essential for methane production by the euryarchaea that employ this specialized anaerobic metabolism. Two pathways are known to produce CoM, 2-mercaptoethanesulfonate, and both converge on the 2-oxoacid sulfopyruvate. These cells have recruited the rich biochemistry of amino acid and 2-oxoacid metabolizing enzymes to produce a compound that resembles oxaloacetate, but with a more stable and acidic sulfonate group. 7-Mercaptoheptanoylthreonine phosphate, CoB, likewise owes its carbon backbone to a 2-oxoacid. Three enzymes recruited from leucine biosynthesis have evolved to catalyze the elongation of 2-oxoglutarate to 2-oxosuberate in CoB biosynthesis. This chapter describes themore » enzymology, synthesis and analytical techniques used to study 2-oxoacid metabolism in these pathways. Protein structure and mechanistic information from enzymes provides insight into the evolution of new enzymatic activity, and the evolution of substrate specificity from promiscuous enzyme scaffolds.« less

The Habitability of a Stagnant-Lid Earth

NASA Astrophysics Data System (ADS)

Tosi, N.; Godolt, M.; Stracke, B.; Ruedas, T.; Grenfell, L.; Höning, D.; Nikolaou, A.; Plesa, A. C.; Breuer, D.; Spohn, T.

2017-12-01

Plate tectonics is a fundamental component for the habitability of the Earth. Yet whether it is a recurrent feature of terrestrial bodies orbiting other stars or unique to the Earth is unknown. The stagnant lid may rather be the most common tectonic expression on such bodies. To understand whether a stagnant-lid planet can be habitable, i.e. host liquid water at its surface, we model the thermal evolution of the mantle, volcanic outgassing of H2O and CO2, and resulting climate of an Earth-like planet lacking plate tectonics. We used a 1D model of parameterized convection to simulate the evolution of melt generation and the build-up of an atmosphere of H2O and CO2 over 4.5 Gyr. We then employed a 1D radiative-convective atmosphere model to calculate the global mean atmospheric temperature and the boundaries of the habitable zone (HZ). The evolution of the interior is characterized by the initial production of a large amount of partial melt accompanied by a rapid outgassing of H2O and CO2. At 1 au, the obtained temperatures generally allow for liquid water on the surface nearly over the entire evolution. While the outer edge of the HZ is mostly influenced by the amount of outgassed CO2, the inner edge presents a more complex behaviour that is dependent on the partial pressures of both gases. At 1 au, the stagnant-lid planet considered would be regarded as habitable. The width of the HZ at the end of the evolution, albeit influenced by the amount of outgassed CO2, can vary in a non-monotonic way depending on the extent of the outgassed H2O reservoir. Our results suggest that stagnant-lid planets can be habitable over geological timescales and that joint modelling of interior evolution, volcanic outgassing, and accompanying climate is necessary to robustly characterize planetary habitability.

Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

NASA Astrophysics Data System (ADS)

Merino-Garcia, I.; Albo, J.; Irabien, A.

2018-01-01

Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

Methane Transmission and Oxidation throughout the Soil Column from Three Central Florida Sites

NASA Astrophysics Data System (ADS)

Bond-Lamberty, B. P.; Fansler, S.; Becker, K. E.; Hinkle, C. R.; Bailey, V. L.

2015-12-01

When methane (CH4) is generated in anoxic soil sites, it may be subsequently re-oxidized to carbon dioxide (CO2). Understanding the controls on, and magnitudes of, these processes is necessary to accurately represent greenhouse gas production and emission from soils. We used a laboratory incubation to examine the influence of variable conditions on methane transmission and oxidation, and identify critical reaction zones throughout the soil column. Sandy soils were sampled from three different sites at Disney Wilderness Preserve (DWP), Florida, USA: a depression marsh characterized by significant surface organic matter accumulation, a dry pine flatwood site with water intrusion and organic horizon at depth (200+ cm); and an intermediate-drainage site. Contiguous, 30-cm long cores were sampled from N=4 random boreholes at each site, from the surface to the water table (varying from 90 to 240 cm). In the lab, each core was monitored for 50 hours to quantify baseline (pretreatment) gas fluxes before injection with 6 ml CH4 (an amount commensurate with previous field collar measurements) at the base of each core. We then monitored CH4 and CO2 evolution for 100 hours after injection, calculating per-gas and total C evolution. Methane emissions spiked ~10 hours after injection for all cores, peaking at 0.001 μmol/g soil/hr, ~30x larger than pre-injection flux rates. On a C basis, CO2 emissions were orders of magnitude larger, and rose significantly after injection, with elevated rates generally sustained throughout the incubation. Cores from the depression marsh and shallower depths had significantly higher fluxes of both gases. We estimate that 99.1% of the original CH4 injection was oxidized to CO2. These findings suggest either that the methane measured in the field at DWP originates from within a few centimeters of the surface, or that it is produced in much larger quantities deeper in the profile before most is subsequently oxidized. This highlights the need for better understanding and modeling the multiple processes that result in soil-atmosphere CO2 and CH4 fluxes.

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

NASA Astrophysics Data System (ADS)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

2018-01-01

Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

PubMed

Uddin, M; Coombe, D

2014-03-20

Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to indicate the macroscopic consequences of this analysis.

Dissolution-precipitation reactions and permeability evolution from reactions of CO2-rich aqueous solutions with fractured basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Bae, Y.; Sesti, E.; Skemer, P. A.; Giammar, D.; Conradi, M.; Ellis, B. R.; Hayes, S. E.

2015-12-01

The injection of CO2 into fractured basalts is one of several possible solutions to mitigate global climate change; however, research on carbonation in natural basalts in relation to carbon sequestration is limited, which impedes our understanding of the processes that may influence the viability of this strategy. We are conducting bench-scale experiments to characterize the mineral dissolution and precipitation and the evolution of permeability in synthetic and natural basalts exposed to CO2-rich fluids. Analytical methods include optical and electron microscopy, electron microprobe, Raman spectroscopy, nuclear magnetic resonance (NMR), and micro X-ray computed tomography (μCT) with variable flow rates. Reactive rock and mineral samples consist of 1) packed powders of olivine or natural basalt, and 2) sintered cores of olivine or a synthetic basalt mixture. Each sample was reacted in a batch reactor at 100 °C, and 100 bars CO2. Magnesite is detected within one day in olivine packed beds, and within 15 days in olivine sintered cores. Forsterite and synthetic basalt sinters were also reacted in an NMR apparatus at 102 °C and 65 bars CO2. Carbonate signatures are observed within 72 days of reaction. Longer reaction times are needed for carbonate precipitation in natural basalt samples. Cores from the Columbia River flood basalt flows that contain Mg-rich olivine and a serpentinized basalt from Colorado were cut lengthwise, the interface mechanically roughened or milled, and edges sealed with epoxy to simulate a fractured interface. The cores were reacted in a batch reactor at 50-150 °C and 100 bars CO2. At lower temperatures, calcite precipitation is rare within the fracture after 4 weeks. At higher temperatures, numerous calcite and aragonite crystals are observed within 1 mm of the fracture entrance along the roughened fracture surface. In flow-through experiments, permeability decreased along the fracture paths within a few hours to several days of flow.

The Carbonate-Silicate Cycle on Earth-like Planets Near The End Of Their Habitable Lifetimes

NASA Astrophysics Data System (ADS)

Rushby, A. J.; Mills, B.; Johnson, M.; Claire, M.

2016-12-01

The terrestrial cycle of silicate weathering and metamorphic outgassing buffers atmospheric CO2 and global climate over geological time on Earth. To first order, the operation of this cycle is assumed to occur on Earth-like planets in the orbit of other main-sequence stars in the galaxy that exhibit similar continent/ocean configurations. This has important implications for studies of planetary habitability, atmospheric and climatic evolution, and our understanding of the potential distribution of life in the Universe. We present results from a simple biogeochemical carbon cycle model developed to investigate the operation of the carbonate-silicate cycle under conditions of differing planet mass and position within the radiative habitable zone. An active carbonate-silicate cycle does extend the length of a planet's habitable period through the regulation of the CO2 greenhouse. However, the breakdown of the negative feedback between temperature, pCO2, and weathering rates towards the end of a planet's habitable lifespan results in a transitory regime of `carbon starvation' that would inhibit the ability of oxygenic photoautotrophs to metabolize, and result in the collapse of any putative biosphere supported by these organisms, suggesting an earlier limit for the initiation of inhabitable conditions than when considering temperature alone. This conclusion stresses the importance of considering the full suite of planetary properties when determining potential habitability. A small sample of exoplanets was tested using this model, and the length of their habitable periods were found to be significantly longer than that of the Earth, primarily as a function of the differential rates of stellar evolution expected from their host stars. Furthermore, we carried out statistical analysis of a series of model input parameters, determining that both the mass of the planet and the sensitivity of seafloor weathering processes to dissolved CO2 exhibit significant controls on the length of a planet's habitable period.

Evolution of Spin fluctuations in CaFe2As2 with Co-doping.

NASA Astrophysics Data System (ADS)

Sapkota, A.; Das, P.; Böhmer, A. E.; Abernathy, D. L.; Canfield, P. C.; Kreyssig, A.; McQueeney, R. J.; Goldman, A. I.

Spin fluctuations are an essential ingredient for superconductivity in Fe-based supercondcutors. In Co-doped BaFe2As2, the system goes from the antiferromagnetic (AFM) state to the superconducting (SC) state with Co doping, and the spin fluctuations also evolve from well-defined spin waves with spin gap in the AFM regime to gapless overdamped or diffused fluctuations in the SC regime. CaFe2As2 has a stronger magneto-elastic coupling than BaFe2As2 and no co-existence of SC and AFM region as observed in BaFe2As2 with Co doping. Here, we will discuss the evolution of spin fluctuations in CaFe2As2 with Co doping. Work at the Ames Laboratory was supported by US DOE, Basic Energy Sciences, Division of Material Sciences and Engineering, under contract No. DE-AC02-07CH11358. This research used resources of SNS, a DOE office of science user facility operated by ORNL.

Crystallization behaviour of hydroxide cobalt carbonates by aging: Environmental implications.

NASA Astrophysics Data System (ADS)

González-López, Jorge; Fernández-González, Angeles; Jimenez, Amalia

2014-05-01

Cobalt is a naturally occurring element widely distributed in water, sediments and air that is essential for living species, since it is a component of B12 vitamin and it is also a strategic and critical element used in a number of commercial, industrial and military applications. However, relatively high accumulations of cobalt in environment can be toxic for human and animal health. Cobalt usually occurs as Co2+ and Co3+ in aqueous solutions, where Co2+ is the most soluble and hence its mobility in water is higher. The study of the precipitation of cobalt carbonates is of great interest due to the abundance of carbonate minerals in contact with surface water and groundwater which can be polluted with Co2+. Previous works have demonstrated that the formation of Co-bearing calcium carbonates and Co-rich low crystallinity phases takes place at ambient conditions. With the aim of investigating the crystallization behavior of Co- bearing carbonates at ambient temperature, macroscopic batch-type experiments have been carried out by mixing aqueous solutions of CoCl2 (0.05M) and Na2CO3 (0.05M) during increasing reaction times (5 minutes and 1, 5, 24, 48, 96, 168, 720 and 1440 hours). The main goals of this work were (i) to analyse the physicochemical evolution of the system and (ii) to study the evolution of the crystallinity of the solid phases during aging. After a given reaction period, pH, alkalinity and dissolved Co2+ in the aqueous solutions were analysed. The evolution of the morphology and chemical composition of the solids with aging time was examined by SEM and TEM. The precipitates were also analyzed by X-ray powder diffraction (XRD) and the crystallinity degree was followed by the intensity and the full width at high medium (FWHM) of the main peaks. The results show that a low crystallinity phase was obtained at the very beginning of aging. This phase evolves progressively to form hydroxide carbonate cobalt (Co2CO3(OH)2) which crystallize with the spatial group P21/a (monoclinic system) after about 4 days. At the same time, the most important fall of cobalt content takes place, but pH and alkalinity values do not show significant changes. The evolution of the aqueous solutions is closely related to the increases of crystallinity degree. TEM study confirms the evolution of the shape of crystals, which exhibit platelet morphology at the end of aging time.

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

PubMed

Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

2017-11-28

Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

En Route to Destruction: the Evolution in Composition of Ices in Comet D 2012 S1 (ISON) Between 1.2 and 0.34 Au from the Sun as Revealed at Infrared Wavelengths

NASA Technical Reports Server (NTRS)

Disanti, M. A.; Bonev, B. P.; Gibb, L. E.; Paganini, L.; Villanueva, G.; Mumma, M. J.; Keane, J. V.; Blake, G. A.; Dello Russo, N.; Meech, K. J.;

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO2 in Heterogeneous Shallow Aquifers

NASA Astrophysics Data System (ADS)

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.; Illangasekare, Tissa H.

2017-12-01

To assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO2 migration behavior in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross section of a shallow aquifer with layered geologic heterogeneity. As water with aqueous CO2 was injected into the system to mimic a CO2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO2 evolution processes. Significant CO2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow redissolution of gas phase CO2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO2 migration. This improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO 2 in Heterogeneous Shallow Aquifers

DOE PAGES

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.; ...

2017-11-15

In order to assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO 2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO 2 migration behaviour in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross-section of a shallowmore » aquifer with layered geologic heterogeneity. As water with aqueous CO 2 was injected into the system to mimic a CO 2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO 2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO 2 evolution processes. Significant CO 2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow re-dissolution of gas phase CO 2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO 2 migration. In conclusion, this improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.« less

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO 2 in Heterogeneous Shallow Aquifers

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

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.

In order to assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO 2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO 2 migration behaviour in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross-section of a shallowmore » aquifer with layered geologic heterogeneity. As water with aqueous CO 2 was injected into the system to mimic a CO 2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO 2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO 2 evolution processes. Significant CO 2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow re-dissolution of gas phase CO 2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO 2 migration. In conclusion, this improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.« less

The Kinetics of Oxygen Atom Recombination in the Presence of Carbon Dioxide

NASA Astrophysics Data System (ADS)

Jamieson, C. S.; Garcia, R. M.; Pejakovic, D.; Kalogerakis, K.

2009-12-01

Understanding processes involving atomic oxygen is crucial for the study and modeling of composition, energy transfer, airglow, and transport dynamics in planetary atmospheres. Significant gaps and uncertainties exist in the understanding of these processes and often the relevant input from laboratory measurements is missing or outdated. We are conducting laboratory experiments to measure the rate coefficient for O + O + CO2 recombination and investigating the O2 excited states produced following the recombination. These measurements will provide key input for a quantitative understanding and reliable modeling of the atmospheres of the CO2 planets and their airglow. An excimer laser providing pulsed output at either 193 nm or 248 nm is employed to produce O atoms by dissociating carbon dioxide, nitrous oxide, or ozone. In an ambient-pressure background of CO2, O atoms recombine in a time scale of a few milliseconds. Detection of laser-induced fluorescence at 845 nm following two-photon excitation near 226 nm monitors the decay of the oxygen atom population. From the temporal evolution of the signal the recombination rate coefficient is extracted. Fluorescence spectroscopy is used to detect the products of O-atom recombination and subsequent relaxation in CO2. This work is supported by the US National Science Foundation’s (NSF) Planetary Astronomy Program. Rosanne Garcia’s participation was funded by the NSF Research Experiences for Undergraduates (REU) Program.

Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis.

PubMed

Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang; Cai, Jinyan; Wu, Shaoyang; Kang, Jian; Zhou, Jianbin; Chen, Zhiyan; Zheng, Xusheng; Xiao, Xiangheng; Wang, Gongming

2018-04-12

Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo 2 S 4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm -2 and a Tafel slope of 37 mV dec -1 , which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo 2 S 4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.

A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles.

PubMed

Kim, Hyejung; Kim, Min Gyu; Jeong, Hu Young; Nam, Haisol; Cho, Jaephil

2015-03-11

Structural degradation of Ni-rich cathode materials (LiNi(x)M(1-x)O2; M = Mn, Co, and Al; x > 0.5) during cycling at both high voltage (>4.3 V) and high temperature (>50 °C) led to the continuous generation of microcracks in a secondary particle that consisted of aggregated micrometer-sized primary particles. These microcracks caused deterioration of the electrochemical properties by disconnecting the electrical pathway between the primary particles and creating thermal instability owing to oxygen evolution during phase transformation. Here, we report a new concept to overcome those problems of the Ni-rich cathode material via nanoscale surface treatment of the primary particles. The resultant primary particles' surfaces had a higher cobalt content and a cation-mixing phase (Fm3̅m) with nanoscale thickness in the LiNi0.6Co0.2Mn0.2O2 cathode, leading to mitigation of the microcracks by suppressing the structural change from a layered to rock-salt phase. Furthermore, the higher oxidation state of Mn(4+) at the surface minimized the oxygen evolution at high temperatures. This approach resulted in improved structural and thermal stability in the severe cycling-test environment at 60 °C between 3.0 and 4.45 V and at elevated temperatures, showing a rate capability that was comparable to that of the pristine sample.

The Roles of Tidal Evolution and Evaporative Mass Loss in the Origin of CoRoT-7 b

NASA Technical Reports Server (NTRS)

Jackson, Brian; Miller, Neil; Barnes, Rory; Raymond, Sean N.; Fortney, Jonathan J.; Greenberg, Richard

2010-01-01

CoRoT-7 b is the first confirmed rocky exoplanet, but, with an orbital semimajor axis of 0.0172 au, its origins may be unlike any rocky planet in our Solar System. In this study, we consider the roles of tidal evolution and evaporative mass loss in CoRoT-7 b's history, which together have modified the planet's mass and orbit. If CoRoT-7 b has always been a rocky body, evaporation may have driven off almost half its original mass, but the mass loss may depend sensitively on the extent of tidal decay of its orbit. As tides caused CoRoT-7 b's orbit to decay, they brought the planet closer to its host star, thereby enhancing the mass loss rate. Such a large mass loss also suggests the possibility that CoRoT-7 b began as a gas giant planet and had its original atmosphere completely evaporated. In this case, we find that CoRoT-7 b's original mass probably did not exceed 200 Earth masses (about two-third of a Jupiter mass). Tides raised on the host star by the planet may have significantly reduced the orbital semimajor axis, perhaps causing the planet to migrate through mean-motion resonances with the other planet in the system, CoRoT-7 c. The coupling between tidal evolution and mass loss may be important not only for CoRoT-7 b but also for other close-in exoplanets, and future studies of mass loss and orbital evolution may provide insight into the origin and fate of close-in planets, both rocky and gaseous.

Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand

PubMed Central

2015-01-01

The cobalt complex [CoIIIN4H(Br)2]+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (fCO= 45% ± 6.4) near the CoI/0 redox couple for [CoIIIN4H(Br)2]+ (E1/2 = −1.88 V FeCp2+/0) with simultaneous H2 evolution (fH2= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal CoI/0redox couple, and attempts were made to isolate the triply reduced compound (“[Co0N4H]”). Instead, the doubly reduced (“CoI”) compounds [CoN4] and [CoN4H(MeCN)]+ were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H2 evolution and CO2 reduction electrocatalysis. PMID:24773584

SOIL RESPIRATION RESPONSE TO THREE YEARS OF ELEVATED CO-2 AND N FERTILIZATION IN PONDEROSA PINE (PINUS PONDEROSA DOUG. EX LAWS.)

EPA Science Inventory

We measured growing season soil CO-2 evolution under elevated atmospheric (CO-2) and soil nitrogen (N) additions. Our objectives were to determine treatment effects, quantify seasonal variation, and compare two measurement techniques. Elevated (CO-2) treatments were applied in op...

Ancient papillomavirus-host co-speciation in Felidae

PubMed Central

Rector, Annabel; Lemey, Philippe; Tachezy, Ruth; Mostmans, Sara; Ghim, Shin-Je; Van Doorslaer, Koenraad; Roelke, Melody; Bush, Mitchell; Montali, Richard J; Joslin, Janis; Burk, Robert D; Jenson, Alfred B; Sundberg, John P; Shapiro, Beth; Van Ranst, Marc

2007-01-01

Background Estimating evolutionary rates for slowly evolving viruses such as papillomaviruses (PVs) is not possible using fossil calibrations directly or sequences sampled over a time-scale of decades. An ability to correlate their divergence with a host species, however, can provide a means to estimate evolutionary rates for these viruses accurately. To determine whether such an approach is feasible, we sequenced complete feline PV genomes, previously available only for the domestic cat (Felis domesticus, FdPV1), from four additional, globally distributed feline species: Lynx rufus PV type 1, Puma concolor PV type 1, Panthera leo persica PV type 1, and Uncia uncia PV type 1. Results The feline PVs all belong to the Lambdapapillomavirus genus, and contain an unusual second noncoding region between the early and late protein region, which is only present in members of this genus. Our maximum likelihood and Bayesian phylogenetic analyses demonstrate that the evolutionary relationships between feline PVs perfectly mirror those of their feline hosts, despite a complex and dynamic phylogeographic history. By applying host species divergence times, we provide the first precise estimates for the rate of evolution for each PV gene, with an overall evolutionary rate of 1.95 × 10-8 (95% confidence interval 1.32 × 10-8 to 2.47 × 10-8) nucleotide substitutions per site per year for the viral coding genome. Conclusion Our work provides evidence for long-term virus-host co-speciation of feline PVs, indicating that viral diversity in slowly evolving viruses can be used to investigate host species evolution. These findings, however, should not be extrapolated to other viral lineages without prior confirmation of virus-host co-divergence. PMID:17430578

Evolution of magnetic properties and microstructure of Hf2Co11B alloys

DOE PAGES

McGuire, Michael A.; Rios, Orlando

2015-02-05

Amorphous Hf 2Co 11B alloys produced by melt-spinning have been crystallized by annealing at 500-800 °C, and the products have been investigated using magnetization measurements, x-ray diffraction, and scanning electron microscopy. The results reveal the evolution of the phase fractions, microstructure, and magnetic properties with both annealing temperature and time. Crystallization of the phase denoted HfCo 7, which is associated with the development of coercivity, occurs slowly at 500 °C. Annealing at intermediate temperatures produces mixed phase samples containing some of the HfCo 7 phase with the highest values of remanent magnetization and coercivity. The equilibrium structure at 800 °Cmore » contains HfCo3B 2, Hf 6Co 23 and Co, and displays soft ferromagnetism. Maximum values for the remanent magnetization, intrinsic coercivity, and magnetic energy product among the samples are approximately 5.2 kG, 2.0 kOe, and 3.1 MGOe, respectively, which indicates that the significantly higher values observed in crystalline, melt-spun Hf 2Co 11B ribbons are a consequence of the non-equilibrium solidification during the melt-spinning process. Application of high magnetic fields during annealing is observed to strongly affect the microstructural evolution, which may provide access to higher performance materials in Zr/Hf-Co hard ferromagnets. The crystal structure of HfCo 7 and the related Zr analogues is unknown, and without knowledge of atomic positions powder diffraction cannot distinguish among proposed unit cells and symmetries found in the literature.« less

Variations on seepage water geochemistry induced by natural and anthropogenic microclimatic changes: Implications for the speleothems growth conditions

NASA Astrophysics Data System (ADS)

Fernandez-Cortes, A.; Sanchez-Moral, S.; Canaveras, J. C.; Cuevas, J.; Cuezva, S.; Andreu, J. M.; Abella, R.

2009-04-01

During an annual cycle the effect of microclimatic changes (natural and anthropogenic origin) on the geochemical characteristics of seepage water and mineral precipitation rates was analyzed, for two karstic caves under opposing environmental stability and energy exchange with exterior. On the one hand Castañar cave (Caceres, Spain), an extremely controlled show cave with limited visitation showing a minimum exchange rate of energy with the outer atmosphere and, secondly, Canelobre cave (Alicante, Spain), a widely visited cave where the anthropogenic impact generates both high-speed and high-energy environmental changes. Microclimatic variations play a key role in CO2-dessgasing caused by the imbalance of pCO2 between the karstic water and the cave air, favoring the slow processes of mineral precipitation. Thus, a pCO2-range of seepage water have been detected for each cave (from 10-2.30/-2.35 to 10-2.47/-2.52 bar for Castañar cave, and from 10-2.8/-2.85 to 10-2.95/-3.0 bar for Canelobre cave) where the mineral oversaturation prevails, determining the type and rate of mineral precipitation in each cave. Finally, it analyzes how the changes on the oversaturation/ precipitation states are controlled by microclimatic variations, such as: 1) natural underground air renewal through the porous system of upper soil and the network of host-rock fissures (isolating membranes), or else through the cave entrance, 2) cumulative disruptions in the pCO2 levels of cave air due to the presence of visitors, and 3) forced ventilation of the subterranean atmosphere due to the uncontrolled opening of cave entrances. The obtained results reinforce the significance of the microclimatic fluctuations on short time scales in the dynamic and evolution of the subterranean karst system, in terms of rates of mineral precipitation and growth of speleothems. Likewise the interpretations are useful in order to ensure the constant climate required for the conservation of caves.

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

DOE PAGES

Chen, Dawei; Dong, Chung-Li; Zou, Yuqin; ...

2017-07-24

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

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

Chen, Dawei; Dong, Chung-Li; Zou, Yuqin

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

A Hierarchical Z-Scheme α-Fe2 O3 /g-C3 N4 Hybrid for Enhanced Photocatalytic CO2 Reduction.

PubMed

Jiang, Zhifeng; Wan, Weiming; Li, Huaming; Yuan, Shouqi; Zhao, Huijun; Wong, Po Keung

2018-03-01

The challenge in the artificial photosynthesis of fossil resources from CO 2 by utilizing solar energy is to achieve stable photocatalysts with effective CO 2 adsorption capacity and high charge-separation efficiency. A hierarchical direct Z-scheme system consisting of urchin-like hematite and carbon nitride provides an enhanced photocatalytic activity of reduction of CO 2 to CO, yielding a CO evolution rate of 27.2 µmol g -1 h -1 without cocatalyst and sacrifice reagent, which is >2.2 times higher than that produced by g-C 3 N 4 alone (10.3 µmol g -1 h -1 ). The enhanced photocatalytic activity of the Z-scheme hybrid material can be ascribed to its unique characteristics to accelerate the reduction process, including: (i) 3D hierarchical structure of urchin-like hematite and preferable basic sites which promotes the CO 2 adsorption, and (ii) the unique Z-scheme feature efficiently promotes the separation of the electron-hole pairs and enhances the reducibility of electrons in the conduction band of the g-C 3 N 4 . The origin of such an obvious advantage of the hierarchical Z-scheme is not only explained based on the experimental data but also investigated by modeling CO 2 adsorption and CO adsorption on the three different atomic-scale surfaces via density functional theory calculation. The study creates new opportunities for hierarchical hematite and other metal-oxide-based Z-scheme system for solar fuel generation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of oxygen concentration on the combustion of a fuel/oxidizer mixture

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

Biteau, H.; Institut National de l'Environnement Industriel et des Risques, Parc Technologique Alata, Verneuil en Halatte; Fuentes, A.

2010-04-15

The aim of the present study is to investigate the influence of the O{sub 2} concentration on the combustion behaviour of a fuel/oxidizer mixture. The material tested is a ternary mixture of lactose, starch, and potassium nitrate, which has already been used in an attempt to estimate heat release rate using the FM-Global Fire Propagation Apparatus. It provides a well-controlled combustion chamber to study the evolution of the combustion products when varying the O{sub 2} concentration, between air and low oxidizer conditions. Different chemical behaviours have been exhibited. When the O{sub 2} concentration was reduced beyond 18%, large variations weremore » observed in the CO{sub 2} and CO concentrations. This critical O{sub 2} concentration seems to be the limit before which the material only uses its own oxidizer to react. On the other hand, mass loss did not highlight this change in chemical reactions and remained similar whatever the test conditions. This presumes that the oxidation of CO into CO{sub 2} are due to reactions occurring in the gas phase especially for large O{sub 2} concentrations. This actual behaviour can be verified using a simplified flammability limit model adapted for the current work. Finally, a sensitivity analysis has been carried out to underline the influence of CO concentration in the evaluation of heat release rate using typical calorimetric methods. The results of this study provide a critical basis for the investigation of the combustion of a fuel/oxidizer mixture and for the validation of future numerical models. (author)« less

RubisCO selection using the vigorously aerobic and metabolically versatile bacterium Ralstonia eutropha.

PubMed

Satagopan, Sriram; Tabita, F Robert

2016-08-01

Recapturing atmospheric CO2 is key to reducing global warming and increasing biological carbon availability. Ralstonia eutropha is a biotechnologically useful aerobic bacterium that uses the Calvin-Benson-Bassham (CBB) cycle and the enzyme ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO) for CO2 utilization, suggesting that it may be a useful host to bioselect RubisCO molecules with improved CO2 -capture capabilities. A host strain of R. eutropha was constructed for this purpose after deleting endogenous genes encoding two related RubisCOs. This strain could be complemented for CO2 -dependent growth by introducing native or heterologous RubisCO genes. Mutagenesis and suppressor selection identified amino acid substitutions in a hydrophobic region that specifically influences RubisCO's interaction with its substrates, particularly O2 , which competes with CO2 at the active site. Unlike most RubisCOs, the R. eutropha enzyme has evolved to retain optimal CO2 -fixation rates in a fast-growing host, despite the presence of high levels of competing O2 . Yet its structure-function properties resemble those of several commonly found RubisCOs, including the higher plant enzymes, allowing strategies to engineer analogous enzymes. Because R. eutropha can be cultured rapidly under harsh environmental conditions (e.g., with toxic industrial flue gas), in the presence of near saturation levels of oxygen, artificial selection and directed evolution studies in this organism could potentially impact efforts toward improving RubisCO-dependent biological CO2 utilization in aerobic environments. d-ribulose 1,5-bisphosphate carboxylase/oxygenase, EC 4.1.1.39; phosphoribulokinase, EC 2.7.1.19. © 2016 Federation of European Biochemical Societies.

Movement and persistence of aldicarb in certain soils.

PubMed

Coppedge, J R; Bull, D L; Ridgway, R L

1977-01-01

When the rate of movement and the persistence of aldicarb in 4 types of soils were investigated in laboratory and field studies some leaching was detected in coarse sand; however, leaching was quite limited in clay loam and muck soils. These data indicated that aldicarb degraded quite rapidly in the selected soils and most of the applied radioactivity volatilized from these soil columns as 14CO2. The evolution of 14CO2 from the treated soil suggested severe degradation of the aldicarb molecule and consequently provided indirect evidence against the accumulation of significant quantities of toxic metabolites in the soil types evaluated. Under field conditions this toxicant appeared to have a half-life of about 7 days in loam soil.

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

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

Wang, Xiang; Shi, Hui; Kwak, Ja Hun

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2O 3. The drastically different rate expressions and apparentmore » energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2, H 2 and CO 2+H 2. The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more strongly with CO, which is mainly in multi-bound forms and remains stable in He flow at high temperatures, but is reactive towards adsorbed H atoms on Pd leading eventually to CH 4 formation. 5% Pd/Al 2O 3 contains a larger fraction of terrace sites favorable for forming these more stable CO species than 0.5% Pd/Al 2O 3. Consequently, we propose that the difference in the formation rate and selectivity to CH 4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. JS gratefully acknowledges the financial support of this work by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.« less

The Evolution of Volatile Production in Comet C-2009 P1(Garradd) During its 2011-2012 Apparition

NASA Technical Reports Server (NTRS)

Gicquel, A.; Milam, S. N.; Coulson, I. M.; Villaneuva, G. L.; Cordiner, M. A.; Charnley, S. B.; DiSanti, M. A.; Mumma, M. J.; Szutowicz, S.

2015-01-01

We report observations at millimeter and submillimeter wavelengths of comet C/2009 P1 (Garradd) from 2011 December 28 to 2012 April 24, using the Arizona Radio Observatory submillimeter telescope (SMT) and the James Clerk Maxwell Telescope (JCMT). Garradd is a dynamically young long-period comet from the Oort Cloud, with a periodicity of 127,000 years, that reached perihelion on 2011 December 23 (at Heliocentric distance (Rh) = 1.55 Astronomical Units and delta = 20.1 Astronomical Units ) and made its closest approach to the Earth on 2012 March 05 (at Heliocentric distance (Rh) = 1.84 Astronomical Units and delta = 1.26 Astronomical Units). We obtained gas production rates, and molecular abundances relative to water for HCN, ortho-H2CO, CS, CO and CH3OH. A rotational temperature, T (sub rot) approximately equal to 50 degrees Kelvin, was determined by observing multiple methanol lines with the JCMT. By averaging the abundance ratio relative to water from the SMT and the JCMT we derive: CO: 7.03 plus or minus 1.84 percent, HCN: 0.04 plus or minus 0.01 percent, ortho H2CO: 0.14 plus or minus 0.03 percent as a parent molecule (and 0.28 plus or minus 0.06 percent as an extended source), CS: 0.03 plus or minus 0.01 percent and CH3OH: 3.11 for a range from plus 1:86 to minus 0.51 percent. We concluded that Garradd is normal in CH3OH, depleted in HCN, ortho-H2CO and CS and slightly enriched in CO with respect to typically observed cometary mixing ratios. We also studied the temporal evolution of HCN and CO and find that the production of HCN has a trend similar to water (but with short-term variation), with a decrease after perihelion, while that of CO shows contrary behavior: remaining constant or increasing after perihelion.

Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

PubMed

Pan, Yun-xiang; Zhuang, Huaqiang; Hong, Jindui; Fang, Zheng; Liu, Hai; Liu, Bin; Huang, Yizhong; Xu, Rong

2014-09-01

In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 μmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 μmol h(-1)), Pt/Ga2O3 (0.12 μmol h(-1)), and Pt/In2O3 (0.05 μmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Control of electrochemical properties of nickel-rich layered cathode materials for lithium ion batteries by variation of the manganese to cobalt ratio

NASA Astrophysics Data System (ADS)

Sun, Ho-Hyun; Choi, Wonchang; Lee, Joong Kee; Oh, In-Hwan; Jung, Hun-Gi

2015-02-01

Various Ni-rich layered oxide cathodes (above 0.80 Ni content), such as LiNi1-y-zCoyAlzO2 (NCA), are used in electric vehicles (EVs) due to their high capacity (∼200 mAh g-1 for NCA). However, to improve cycle performance and thermal stability and to ensure longer and safer usage, numerous studies have investigated surface modification, coating, and doping of cathode materials. In this study, we have investigated the characteristics of Li[Ni0.85CoxMn0.15-x]O2 with various Mn to Co ratios (x = 0-0.15) synthesized by a coprecipitation method. The discharge capacities of the Li[Ni0.85CoxMn0.15-x]O2 cathodes are similar at around 206 mAh g-1 at room temperature and 213.8 mAh g-1 at 55 °C between 2.7 and 4.3 V at a 0.2C rate, while the cyclability, thermal stability, and rate capability of all samples differ according to the Mn and Co ratio. The Li[Ni0.85Co0.05Mn0.10]O2 cathode shows the most promising electrochemical properties under different conditions among the various cathodes evaluated; it displays a high rate capacity (approximately 163 mAh g-1 at 5C rate) at 25 °C and good thermal stability (main exothermic temperature of 233.7 °C and relatively low heat evolution of 857.3 J g-1).

Continuous Monitoring of Photolysis Products by Thz Spectroscopy

NASA Astrophysics Data System (ADS)

Omar, Abdelaziz; Cuisset, Arnaud; Mouret, Gaël; Hindle, Francis; Eliet, Sophie; Bocquet, Robin

2015-06-01

We demonstrate the potential of THz spectroscopy to monitor the real time evolution of the gas phase concentration of photolysis products and determine the kinetic reaction rate constant. In the primary work, we have chosen to examine the photolysis of formaldehyde (H_2CO). Exposure of H_2CO to a UVB light (250 to 360 nm) in a single pass of 135 cm length cell leads to decomposition via two mechanisms: the radical channel with production of HCO and the molecular channel with production of CO. A commercial THz source (frequency multiplication chain) operating in the range 600-900 GHz was used to detect and quantify the various chemical species as a function of time. Monitoring the concentrations of CO and H_2CO via rotational transitions, allowed the kinetic rate of H_2CO consummation to be obtained, and an estimation of the rate constants for both the molecular and radical photolysis mechanisms. We have modified our experimental setup to increase the sensitivity of the spectrometer and changed sample preparation protocol specifically to quantify the HCO concentration. Acetaldehyde was used as the precursor for photolysis by UVC resulting in the decompositon mechanism can be described by: CH_3CHO+hν→ CH_3 + HCO → CH_4 + CO Frequency modulation of the source and Zeeman modulation is used to achieve the high sensitivity required. Particular attention has been paid to the mercury photosensitization effect that allowed us to increase the HCO production enabling quantification of the monitored radical. We quantify the HCO radical and start a spectroscopic study of the line positions. H. M. Pickett and T. L. Boyd, Chem. Phys. Lett, Vol 58, 446-449, (1978) S. Eliet, A. Cuisset, M Guinet, F. Hindle, G. Mouret, R. Bocquet, and J. Demaison, Journal of Molecular Spectroscopy, Vol 279, 12-15 (2012). G. Mouret, M. Guinet, A. Cuisset, L. Croizé, S. Eliet, R. Bocquet and F. Hindle, Sensors Journal. IEEE, Vol 13, 133 - 138, (2013)

A Metal-Organic Framework Approach toward Highly Nitrogen-Doped Graphitic Carbon as a Metal-Free Photocatalyst for Hydrogen Evolution.

PubMed

Zhao, Xiuxia; Yang, Hao; Jing, Peng; Shi, Wei; Yang, Guangming; Cheng, Peng

2017-03-01

Zeolitic imidazolate framework-8 (ZIF-8)-derived N-doped graphene analogous polyhedrons (ZNGs) obtained via the direct carbonation of ZIF-8 are applied to photocatalytic hydrogen evolution for the first time. The contents of different types of nitrogen atoms in ZNGs can be fine-tuned via the calcination temperature, which significantly influences the hydrogen evolution rate of the ZNGs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-latitude arc–continent collision as a driver for global cooling

PubMed Central

Jagoutz, Oliver; Macdonald, Francis A.; Royden, Leigh

2016-01-01

New constraints on the tectonic evolution of the Neo-Tethys Ocean indicate that at ∼90–70 Ma and at ∼50–40 Ma, vast quantities of mafic and ultramafic rocks were emplaced at low latitude onto continental crust within the tropical humid belt. These emplacement events correspond temporally with, and are potential agents for, the global climatic cooling events that terminated the Cretaceous Thermal Maximum and the Early Eocene Climatic Optimum. We model the temporal effects of CO2 drawdown from the atmosphere due to chemical weathering of these obducted ophiolites, and of CO2 addition to the atmosphere from arc volcanism in the Neo-Tethys, between 100 and 40 Ma. Modeled variations in net CO2-drawdown rates are in excellent agreement with contemporaneous variation of ocean bottom water temperatures over this time interval, indicating that ophiolite emplacement may have played a major role in changing global climate. We demonstrate that both the lithology of the obducted rocks (mafic/ultramafic) and a tropical humid climate with high precipitation rate are needed to produce significant consumption of CO2. Based on these results, we suggest that the low-latitude closure of ocean basins along east–west trending plate boundaries may also have initiated other long-term global cooling events, such as Middle to Late Ordovician cooling and glaciation associated with the closure of the Iapetus Ocean. PMID:27091966

Low-latitude arc-continent collision as a driver for global cooling.

PubMed

Jagoutz, Oliver; Macdonald, Francis A; Royden, Leigh

2016-05-03

New constraints on the tectonic evolution of the Neo-Tethys Ocean indicate that at ∼90-70 Ma and at ∼50-40 Ma, vast quantities of mafic and ultramafic rocks were emplaced at low latitude onto continental crust within the tropical humid belt. These emplacement events correspond temporally with, and are potential agents for, the global climatic cooling events that terminated the Cretaceous Thermal Maximum and the Early Eocene Climatic Optimum. We model the temporal effects of CO2 drawdown from the atmosphere due to chemical weathering of these obducted ophiolites, and of CO2 addition to the atmosphere from arc volcanism in the Neo-Tethys, between 100 and 40 Ma. Modeled variations in net CO2-drawdown rates are in excellent agreement with contemporaneous variation of ocean bottom water temperatures over this time interval, indicating that ophiolite emplacement may have played a major role in changing global climate. We demonstrate that both the lithology of the obducted rocks (mafic/ultramafic) and a tropical humid climate with high precipitation rate are needed to produce significant consumption of CO2 Based on these results, we suggest that the low-latitude closure of ocean basins along east-west trending plate boundaries may also have initiated other long-term global cooling events, such as Middle to Late Ordovician cooling and glaciation associated with the closure of the Iapetus Ocean.

Effects of oxygen partial pressure on Li-air battery performance

NASA Astrophysics Data System (ADS)

Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

2017-10-01

For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

An evaluation of the effects of exogenous ethephon, an ethylene releasing compound, on photosynthesis of mustard (Brassica juncea) cultivars that differ in photosynthetic capacity

PubMed Central

Khan, NA

2004-01-01

Background The stimulatory effect of CO2 on ethylene evolution in plants is known, but the extent to which ethylene controls photosynthesis is not clear. Studies on the effects of ethylene on CO2 metabolism have shown conflicting results. Increase or inhibition of photosynthesis by ethylene has been reported. To understand the physiological processes responsible for ethylene-mediated changes in photosynthesis, stomatal and mesophyll effects on photosynthesis and ethylene biosynthesis in response to ethephon treatment in mustard (Brassica juncea) cultivars differing in photosynthetic capacity were studied. Results The effects of ethephon on photosynthetic rate (PN), stomatal conductance (gS), carbonic anhydrase (CA) activity, 1-aminocyclopropane carboxylic acid synthase (ACS) activity and ethylene evolution were similar in both the cultivars. Increasing ethephon concentration up to 1.5 mM increased PN, gS and CA maximally, whereas 3.0 mM ethephon proved inhibitory. ACS activity and ethylene evolution increased with increasing concentrations of ethephon. The corresponding changes in gs and CA activity suggest that the changes in photosynthesis in response to ethephon were triggered by altered stomatal and mesophyll processes. Stomatal conductance changed in parallel with changes in mesophyll photosynthetic properties. In both the cultivars ACS activity and ethylene increased up to 3.0 mM ethephon, but 1.5 mM ethephon caused maximum effects on photosynthetic parameters. Conclusion These results suggest that ethephon affects foliar gas exchange responses. The changes in photosynthesis in response to ethephon were due to stomatal and mesophyll effects. The changes in gS were a response maintaining stable intercellular CO2 concentration (Ci) under the given treatment in both the cultivars. Also, the high photosynthetic capacity cultivar, Varuna responded less to ethephon than the low photosynthetic capacity cultivar, RH30. The photosynthetic capacity of RH30 increased with the increase in ethylene evolution due to 1.5 mM ethephon application. PMID:15625009

Misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ for the hydrogen evolution reaction: beyond van der Waals heterostructures.

PubMed

Chua, Chun Kiang; Sofer, Zdeněk; Jankovský, Ondřej; Pumera, Martin

2015-03-16

Recent research on stable 2D nanomaterials has led to the discovery of new materials for energy-conversion and energy-storage applications. A class of layered heterostructures known as misfit-layered chalcogenides consists of well-defined atomic layers and has previously been applied as thermoelectric materials for use as high-temperature thermoelectric batteries. The performance of such misfit-layered chalcogenides in electrochemical applications, specifically the hydrogen evolution reaction, is currently unexplored. Herein, a misfit-layered chalcogenide consisting of CoO2 layers interleaved with an SrO-BiO-BiO-SrO rock-salt block and having the formula Bi1.85 Sr2 Co1.85 O7.7-δ is synthesized and examined for its structural and electrochemical properties. The hydrogen-evolution performance of misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ , which has an overpotential of 589 mV and a Tafel slope of 51 mV per decade, demonstrates the promising potential of misfit-layered chalcogenides as electrocatalysts instead of classical carbon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of elevated CO2 and N fertilization on soil respiration from ponderosa pine (Pine ponderosa) in open-top chambers

Treesearch

James M. Vose; Katherine J. Elliott; Dale W. Johnson; Roger F. Walker; Mark G. Johnson; David T. Tingey

1995-01-01

We measured growing season soil CO2 evolution under elevated atmospheric CO2 and soil nitrogen (N) additions. Our objectives were to determine treatment effects, quantify seasonal variation, and determine regulating mechanisms. Elevated CO2 treatments were applied in open-top chambers containing 3-...

Soil respiration response to three years of elevated CO2 and N fertilization in ponderosa pine (Pinus ponderosa Doug. ex Laws.)

Treesearch

James M. Vose; Katherine J. Elliott; Dale W. Johnson; David T. Tingey; Mark G. Johnson

1997-01-01

We measured growing season soil CO2 evolution under elevated atmospheric [CO2 and soil nitrogen (N) additions. Our objectives were to determine treatment effects, quantify seasonal variation, and compare two measurement techniques. Elevated [CO2] treatments were applied in open-top chambers...

The role of Rubisco kinetics and pyrenoid morphology in shaping the CCM of haptophyte microalgae.

PubMed

Heureux, Ana M C; Young, Jodi N; Whitney, Spencer M; Eason-Hubbard, Maeve R; Lee, Renee B Y; Sharwood, Robert E; Rickaby, Rosalind E M

2017-06-01

The haptophyte algae are a cosmopolitan group of primary producers that contribute significantly to the marine carbon cycle and play a major role in paleo-climate studies. Despite their global importance, little is known about carbon assimilation in haptophytes, in particular the kinetics of their Form 1D CO2-fixing enzyme, Rubisco. Here we examine Rubisco properties of three haptophytes with a range of pyrenoid morphologies (Pleurochrysis carterae, Tisochrysis lutea, and Pavlova lutheri) and the diatom Phaeodactylum tricornutum that exhibit contrasting sensitivities to the trade-offs between substrate affinity (Km) and turnover rate (kcat) for both CO2 and O2. The pyrenoid-containing T. lutea and P. carterae showed lower Rubisco content and carboxylation properties (KC and kCcat) comparable with those of Form 1D-containing non-green algae. In contrast, the pyrenoid-lacking P. lutheri produced Rubisco in 3-fold higher amounts, and displayed a Form 1B Rubisco kCcat-KC relationship and increased CO2/O2 specificity that, when modeled in the context of a C3 leaf, supported equivalent rates of photosynthesis to higher plant Rubisco. Correlation between the differing Rubisco properties and the occurrence and localization of pyrenoids with differing intracellular CO2:O2 microenvironments has probably influenced the divergent evolution of Form 1B and 1D Rubisco kinetics. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Laboratory Investigation of Coal Deformation Behavior and Its Influence on Permeability Evolution During Methane Displacement by CO2

NASA Astrophysics Data System (ADS)

Fan, Jingjing; Feng, Ruimin; Wang, Jin; Wang, Yanbin

2017-07-01

Geological sequestration of CO2 in coal seams is of significant interest to both academia and industry. A thorough laboratory investigation of mechanical and flow behaviors is crucial for understanding the complex response of coalbeds to CO2 injection-enhanced coalbed methane recovery (CO2-ECBM) operation. In this work, systematic experiments were carried out on cylindrical coal core specimens under different uniform confining stresses. The coal deformation caused by variations in effective stress as well as the sorption-induced matrix swelling/shrinkage was monitored. The competitive gas sorption characteristics and permeability evolution during the process of methane displacement by CO2 were also investigated. The measured volumetric strain results indicate that sorption-induced strain is the dominant factor in the coal deformation. The relationship between the volumetric strain and the adsorbed gas volume has been revealed to be a linear function. Experimental results obtained under different stress conditions suggest that higher confining stress suppresses the increase in both volumetric strain and the adsorbed gas volume. Furthermore, both methane displacement and CO2 injection are reduced when applying higher confining stresses. In addition, the permeability enhancement is heavily suppressed at higher confining stress. At a certain confining stress, a characteristic "U-shaped" trend of permeability is presented as a function of decreasing pore pressure. This study contributes to the understanding of coal deformation and its impact on permeability evolution under uniformly stressed condition, which has practical significance for CO2 sequestration and CO2-ECBM operation in the Qinshui basin.

A detailed view of the gas shell around R Sculptoris with ALMA

NASA Astrophysics Data System (ADS)

Maercker, M.; Vlemmings, W. H. T.; Brunner, M.; De Beck, E.; Humphreys, E. M.; Kerschbaum, F.; Lindqvist, M.; Olofsson, H.; Ramstedt, S.

2016-02-01

Context. During the asymptotic giant branch (AGB) phase, stars undergo thermal pulses - short-lived phases of explosive helium burning in a shell around the stellar core. Thermal pulses lead to the formation and mixing-up of new elements to the stellar surface. They are hence fundamental to the chemical evolution of the star and its circumstellar envelope. A further consequence of thermal pulses is the formation of detached shells of gas and dust around the star, several of which have been observed around carbon-rich AGB stars. Aims: We aim to determine the physical properties of the detached gas shell around R Sculptoris, in particular the shell mass and temperature, and to constrain the evolution of the mass-loss rate during and after a thermal pulse. Methods: We analyse 12CO(1-0), 12CO(2-1), and 12CO(3-2) emission, observed with the Atacama Large Millimeter/submillimeter Array (ALMA) during Cycle 0 and complemented by single-dish observations. The spatial resolution of the ALMA data allows us to separate the detached shell emission from the extended emission inside the shell. We perform radiative transfer modelling of both components to determine the shell properties and the post-pulse mass-loss properties. Results: The ALMA data show a gas shell with a radius of 19.̋5 expanding at 14.3 km s-1. The different scales probed by the ALMA Cycle 0 array show that the shell must be entirely filled with gas, contrary to the idea of a detached shell. The comparison to single-dish spectra and radiative transfer modelling confirms this. We derive a shell mass of 4.5 × 10-3 M⊙ with a temperature of 50 K. Typical timescales for thermal pulses imply a pulse mass-loss rate of 2.3 × 10-5 M⊙ yr-1. For the post-pulse mass-loss rate, we find evidence for a gradual decline of the mass-loss rate, with an average value of 1.6 × 10-5 M⊙ yr-1. The total amount of mass lost since the last thermal pulse is 0.03 M⊙, a factor four higher compared to classical models, with a sharp decline in mass-loss rate immediately after the pulse. Conclusions: We find that the mass-loss rate after a thermal pulse has to decline more slowly than generally expected from models of thermal pulses. This may cause the star to lose significantly more mass during a thermal pulse cycle, which affects the lifetime on the AGB and the chemical evolution of the star, its circumstellar envelope, and the interstellar medium.

Evidence of susceptibility to lamivudine-based HAART and genetic stability of hepatitis B virus (HBV) in HIV co-infected patients: A South African longitudinal HBV whole genome study.

PubMed

Amponsah-Dacosta, Edina; Rakgole, J Nare; Gededzha, Maemu P; Lukhwareni, Azwidowi; Blackard, Jason T; Selabe, Selokela G; Mphahlele, M Jeffrey

2016-09-01

Reports on the concomitant impact of HIV co-infection and long term highly active anti-retroviral therapy (HAART) on the genetic stability and molecular evolution of HBV are limited in sub-Saharan Africa. This retrospective study investigated the molecular evolution of chronic HBV in HIV co-infected patients on lamivudine (3TC)-based HAART over a 5year period. Four HIV co-infected patients, consecutively recruited and followed-up, were screened for hepatitis B serological markers, and their viral loads determined. The HBV genome was amplified from longitudinal samples and characterized by Bayesian inference, mutational analysis, and identification of immune selection pressure. All patients exhibited persistent chronic HBV infection at baseline, as well as over the course of follow-up despite exposure to 3TC-based HAART. The polymerase gene in all isolates was relatively variable prior to HAART initiation at baseline and during the course of follow-up, although primary drug resistance mutations were not detected. All but one patient were infected with HBV subgenotype A1. The divergence rates between baseline and the last follow-up sequences ranged from 0 to 2.0×10(-3) substitutions per site per year (s/s/y). Positive selection pressure was evident within the surface and core genes. Despite persistent HBV infection in the HIV co-infected patients exposed to long term 3TC-based HAART, the molecular evolution of HBV over a 5year period was unremarkable. In addition, HBV exhibited minimal genetic variability overtime. Copyright © 2016 Elsevier B.V. All rights reserved.

Targeted Pressure Management During CO 2 Sequestration: Optimization of Well Placement and Brine Extraction

DOE PAGES

Cihan, Abdullah; Birkholzer, Jens; Bianchi, Marco

2014-12-31

Large-scale pressure increases resulting from carbon dioxide (CO 2) injection in the subsurface can potentially impact caprock integrity, induce reactivation of critically stressed faults, and drive CO 2 or brine through conductive features into shallow groundwater. Pressure management involving the extraction of native fluids from storage formations can be used to minimize pressure increases while maximizing CO2 storage. However, brine extraction requires pumping, transportation, possibly treatment, and disposal of substantial volumes of extracted brackish or saline water, all of which can be technically challenging and expensive. This paper describes a constrained differential evolution (CDE) algorithm for optimal well placement andmore » injection/ extraction control with the goal of minimizing brine extraction while achieving predefined pressure contraints. The CDE methodology was tested for a simple optimization problem whose solution can be partially obtained with a gradient-based optimization methodology. The CDE successfully estimated the true global optimum for both extraction well location and extraction rate, needed for the test problem. A more complex example application of the developed strategy was also presented for a hypothetical CO 2 storage scenario in a heterogeneous reservoir consisting of a critically stressed fault nearby an injection zone. Through the CDE optimization algorithm coupled to a numerical vertically-averaged reservoir model, we successfully estimated optimal rates and locations for CO 2 injection and brine extraction wells while simultaneously satisfying multiple pressure buildup constraints to avoid fault activation and caprock fracturing. The study shows that the CDE methodology is a very promising tool to solve also other optimization problems related to GCS, such as reducing ‘Area of Review’, monitoring design, reducing risk of leakage and increasing storage capacity and trapping.« less

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

Rapid molecular evolution of human bocavirus revealed by Bayesian coalescent inference.

PubMed

Zehender, Gianguglielmo; De Maddalena, Chiara; Canuti, Marta; Zappa, Alessandra; Amendola, Antonella; Lai, Alessia; Galli, Massimo; Tanzi, Elisabetta

2010-03-01

Human bocavirus (HBoV) is a linear single-stranded DNA virus belonging to the Parvoviridae family that has recently been isolated from the upper respiratory tract of children with acute respiratory infection. All of the strains observed so far segregate into two genotypes (1 and 2) with a low level of polymorphism. Given the recent description of the infection and the lack of epidemiological and molecular data, we estimated the virus's rates of molecular evolution and population dynamics. A dataset of forty-nine dated VP2 sequences, including also eight new isolates obtained from pharyngeal swabs of Italian patients with acute respiratory tract infections, was submitted to phylogenetic analysis. The model parameters, evolutionary rates and population dynamics were co-estimated using a Bayesian Markov Chain Monte Carlo approach, and site-specific positive and negative selection was also investigated. Recombination was investigated by seven different methods and one suspected recombinant strain was excluded from further analysis. The estimated mean evolutionary rate of HBoV was 8.6x10(-4)subs/site/year, and that of the 1st+2nd codon positions was more than 15 times less than that of the 3rd codon position. Viral population dynamics analysis revealed that the two known genotypes diverged recently (mean tMRCA: 24 years), and that the epidemic due to HBoV genotype 2 grew exponentially at a rate of 1.01year(-1). Selection analysis of the partial VP2 showed that 8.5% of sites were under significant negative pressure and the absence of positive selection. Our results show that, like other parvoviruses, HBoV is characterised by a rapid evolution. The low level of polymorphism is probably due to a relatively recent divergence between the circulating genotypes and strong purifying selection acting on viral antigens.

Combined effects of CO2 and light on the N2-fixing cyanobacterium Trichodesmium IMS101: a mechanistic view.

PubMed

Levitan, Orly; Kranz, Sven A; Spungin, Dina; Prásil, Ondrej; Rost, Björn; Berman-Frank, Ilana

2010-09-01

The marine diazotrophic cyanobacterium Trichodesmium responds to elevated atmospheric CO(2) partial pressure (pCO(2)) with higher N(2) fixation and growth rates. To unveil the underlying mechanisms, we examined the combined influence of pCO(2) (150 and 900 microatm) and light (50 and 200 micromol photons m(-2) s(-1)) on Trichodesmium IMS101. We expand on a complementary study that demonstrated that while elevated pCO(2) enhanced N(2) fixation and growth, oxygen evolution and carbon fixation increased mainly as a response to high light. Here, we investigated changes in the photosynthetic fluorescence parameters of photosystem II, in ratios of the photosynthetic units (photosystem I:photosystem II), and in the pool sizes of key proteins involved in the fixation of carbon and nitrogen as well as their subsequent assimilation. We show that the combined elevation in pCO(2) and light controlled the operation of the CO(2)-concentrating mechanism and enhanced protein activity without increasing their pool size. Moreover, elevated pCO(2) and high light decreased the amounts of several key proteins (NifH, PsbA, and PsaC), while amounts of AtpB and RbcL did not significantly change. Reduced investment in protein biosynthesis, without notably changing photosynthetic fluxes, could free up energy that can be reallocated to increase N(2) fixation and growth at elevated pCO(2) and light. We suggest that changes in the redox state of the photosynthetic electron transport chain and posttranslational regulation of key proteins mediate the high flexibility in resources and energy allocation in Trichodesmium. This strategy should enable Trichodesmium to flourish in future surface oceans characterized by elevated pCO(2), higher temperatures, and high light.

Initial Events during the Evolution of C4 Photosynthesis in C3 Species of Flaveria1[W][OPEN

PubMed Central

Sage, Tammy L.; Busch, Florian A.; Johnson, Daniel C.; Friesen, Patrick C.; Stinson, Corey R.; Stata, Matt; Sultmanis, Stefanie; Rahman, Beshar A.; Rawsthorne, Stephen; Sage, Rowan F.

2013-01-01

The evolution of C4 photosynthesis in many taxa involves the establishment of a two-celled photorespiratory CO2 pump, termed C2 photosynthesis. How C3 species evolved C2 metabolism is critical to understanding the initial phases of C4 plant evolution. To evaluate early events in C4 evolution, we compared leaf anatomy, ultrastructure, and gas-exchange responses of closely related C3 and C2 species of Flaveria, a model genus for C4 evolution. We hypothesized that Flaveria pringlei and Flaveria robusta, two C3 species that are most closely related to the C2 Flaveria species, would show rudimentary characteristics of C2 physiology. Compared with less-related C3 species, bundle sheath (BS) cells of F. pringlei and F. robusta had more mitochondria and chloroplasts, larger mitochondria, and proportionally more of these organelles located along the inner cell periphery. These patterns were similar, although generally less in magnitude, than those observed in the C2 species Flaveria angustifolia and Flaveria sonorensis. In F. pringlei and F. robusta, the CO2 compensation point of photosynthesis was slightly lower than in the less-related C3 species, indicating an increase in photosynthetic efficiency. This could occur because of enhanced refixation of photorespired CO2 by the centripetally positioned organelles in the BS cells. If the phylogenetic positions of F. pringlei and F. robusta reflect ancestral states, these results support a hypothesis that increased numbers of centripetally located organelles initiated a metabolic scavenging of photorespired CO2 within the BS. This could have facilitated the formation of a glycine shuttle between mesophyll and BS cells that characterizes C2 photosynthesis. PMID:24064930

Initial events during the evolution of C4 photosynthesis in C3 species of Flaveria.

PubMed

Sage, Tammy L; Busch, Florian A; Johnson, Daniel C; Friesen, Patrick C; Stinson, Corey R; Stata, Matt; Sultmanis, Stefanie; Rahman, Beshar A; Rawsthorne, Stephen; Sage, Rowan F

2013-11-01

The evolution of C4 photosynthesis in many taxa involves the establishment of a two-celled photorespiratory CO2 pump, termed C2 photosynthesis. How C3 species evolved C2 metabolism is critical to understanding the initial phases of C4 plant evolution. To evaluate early events in C4 evolution, we compared leaf anatomy, ultrastructure, and gas-exchange responses of closely related C3 and C2 species of Flaveria, a model genus for C4 evolution. We hypothesized that Flaveria pringlei and Flaveria robusta, two C3 species that are most closely related to the C2 Flaveria species, would show rudimentary characteristics of C2 physiology. Compared with less-related C3 species, bundle sheath (BS) cells of F. pringlei and F. robusta had more mitochondria and chloroplasts, larger mitochondria, and proportionally more of these organelles located along the inner cell periphery. These patterns were similar, although generally less in magnitude, than those observed in the C2 species Flaveria angustifolia and Flaveria sonorensis. In F. pringlei and F. robusta, the CO2 compensation point of photosynthesis was slightly lower than in the less-related C3 species, indicating an increase in photosynthetic efficiency. This could occur because of enhanced refixation of photorespired CO2 by the centripetally positioned organelles in the BS cells. If the phylogenetic positions of F. pringlei and F. robusta reflect ancestral states, these results support a hypothesis that increased numbers of centripetally located organelles initiated a metabolic scavenging of photorespired CO2 within the BS. This could have facilitated the formation of a glycine shuttle between mesophyll and BS cells that characterizes C2 photosynthesis.

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Radiocarbon constraints on the extent and evolution of the South Pacific glacial carbon pool

PubMed Central

Ronge, T. A.; Tiedemann, R.; Lamy, F.; Köhler, P.; Alloway, B. V.; De Pol-Holz, R.; Pahnke, K.; Southon, J.; Wacker, L.

2016-01-01

During the last deglaciation, the opposing patterns of atmospheric CO2 and radiocarbon activities (Δ14C) suggest the release of 14C-depleted CO2 from old carbon reservoirs. Although evidences point to the deep Pacific as a major reservoir of this 14C-depleted carbon, its extent and evolution still need to be constrained. Here we use sediment cores retrieved along a South Pacific transect to reconstruct the spatio-temporal evolution of Δ14C over the last 30,000 years. In ∼2,500–3,600 m water depth, we find 14C-depleted deep waters with a maximum glacial offset to atmospheric 14C (ΔΔ14C=−1,000‰). Using a box model, we test the hypothesis that these low values might have been caused by an interaction of aging and hydrothermal CO2 influx. We observe a rejuvenation of circumpolar deep waters synchronous and potentially contributing to the initial deglacial rise in atmospheric CO2. These findings constrain parts of the glacial carbon pool to the deep South Pacific. PMID:27157845

Brownmillerite-type Ca2 FeCoO5 as a Practicable Oxygen Evolution Reaction Catalyst.

PubMed

Tsuji, Etsushi; Motohashi, Teruki; Noda, Hiroyuki; Kowalski, Damian; Aoki, Yoshitaka; Tanida, Hajime; Niikura, Junji; Koyama, Yukinori; Mori, Masahiro; Arai, Hajime; Ioroi, Tsutomu; Fujiwara, Naoko; Uchimoto, Yoshiharu; Ogumi, Zempachi; Habazaki, Hiroki

2017-07-21

Here, we report remarkable oxygen evolution reaction (OER) catalytic activity of brownmillerite (BM)-type Ca 2 FeCoO 5 . The OER activity of this oxide is comparable to or beyond those of the state-of-the-art perovskite (PV)-catalyst Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) and a precious-metal catalyst RuO 2 , emphasizing the importance of the characteristic BM structure with multiple coordination environments of transition metal (TM) species. Also, Ca 2 FeCoO 5 is clearly advantageous in terms of expense/laboriousness of the material synthesis. These facts make this oxide a promising OER catalyst used in many energy conversion technologies such as metal-air secondary batteries and hydrogen production from electrochemical/photocatalytic water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser-Induced Graphene Formation on Wood.

PubMed

Ye, Ruquan; Chyan, Yieu; Zhang, Jibo; Li, Yilun; Han, Xiao; Kittrell, Carter; Tour, James M

2017-10-01

Wood as a renewable naturally occurring resource has been the focus of much research and commercial interests in applications ranging from building construction to chemicals production. Here, a facile approach is reported to transform wood into hierarchical porous graphene using CO 2 laser scribing. Studies reveal that the crosslinked lignocellulose structure inherent in wood with higher lignin content is more favorable for the generation of high-quality graphene than wood with lower lignin content. Because of its high electrical conductivity (≈10 Ω per square), graphene patterned on wood surfaces can be readily fabricated into various high-performance devices, such as hydrogen evolution and oxygen evolution electrodes for overall water splitting with high reaction rates at low overpotentials, and supercapacitors for energy storage with high capacitance. The versatility of this technique in formation of multifunctional wood hybrids can inspire both research and industrial interest in the development of wood-derived graphene materials and their nanodevices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hepatitis C virus quasispecies and pseudotype analysis from acute infection to chronicity in HIV-1 co-infected individuals.

PubMed

Ferns, R Bridget; Tarr, Alexander W; Hue, Stephane; Urbanowicz, Richard A; McClure, C Patrick; Gilson, Richard; Ball, Jonathan K; Nastouli, Eleni; Garson, Jeremy A; Pillay, Deenan

2016-05-01

HIV-1 infected patients who acquire HCV infection have higher rates of chronicity and liver disease progression than patients with HCV mono-infection. Understanding early events in this pathogenic process is important. We applied single genome sequencing of the E1 to NS3 regions and viral pseudotype neutralization assays to explore the consequences of viral quasispecies evolution from pre-seroconversion to chronicity in four co-infected individuals (mean follow up 566 days). We observed that one to three founder viruses were transmitted. Relatively low viral sequence diversity, possibly related to an impaired immune response, due to HIV infection was observed in three patients. However, the fourth patient, after an early purifying selection displayed increasing E2 sequence evolution, possibly related to being on suppressive antiretroviral therapy. Viral pseudotypes generated from HCV variants showed relative resistance to neutralization by autologous plasma but not to plasma collected from later time points, confirming ongoing virus escape from antibody neutralization. Copyright © 2016 Elsevier Inc. All rights reserved.

Insights into recent and ancient trends in the co-evolution of Earth and life as revealed by microbial genomics

NASA Astrophysics Data System (ADS)

Anderson, R. E.; Huber, J. A.; Parsons, C.; Stüeken, E.

2017-12-01

Since the origin of life over 4 billion years ago, life has fundamentally altered the habitability of Earth. Similarly, the environment molds the evolutionary trajectory of life itself through natural selection. Microbial genomes retain a "memory" of the co-evolution of life and Earth and can be analyzed to better understand trends and events in both the recent and distant past. To examine evolutionary trends in the more recent past, we have used metagenomics analyses to investigate which environmental factors play the strongest role in driving the evolution of microbes in deep-sea hydrothermal vents, which are thought to have been important habitats in the earliest stages of life's evolution. We have shown that microbial populations in a deep, basalt-hosted system appear to be under stronger purifying selection than populations inhabiting a cooler serpentinizing system less than 20 km away, suggesting that environmental context and geochemistry have an important impact on evolutionary rates and trends. We also found evidence that viruses play an important role in driving evolution in these habitats. Changing environmental conditions may also effect long-term evolutionary trends in Earth's distant past, as revealed by comparative genomics. By reconciling phylogenetic trees for microbial species with trees of metabolic genes, we can determine approximately when crucial metabolic genes began to spread across the tree of life through horizontal gene transfer. Using these methods, we conducted an analysis of the relative timing of the spread of genes related to the nitrogen cycle. Our results indicate that the rate of horizontal gene transfer for important genes related to denitrification increased after the Great Oxidation Event, concurrent with geochemical evidence for increasing availability of nitrate, suggesting that the oxygenation of the atmosphere and surface ocean may have been an important determining factor for the spread of denitrification genes across the tree of life. In contrast, genes related to nitrogen fixation display much more consistent rates of horizontal gene transfer throughout Earth's history. Studies that couple genomics approaches with geochemistry have the potential to reveal insights into the co-evolution of life and Earth both in the recent and distant past.

Toward High-Performance and Low-Cost Hydrogen Evolution Reaction Electrocatalysts: Nanostructuring Cobalt Phosphide (CoP) Particles on Carbon Fiber Paper.

PubMed

Yu, Shu Hearn; Chua, Daniel H C

2018-05-02

In this communication, we facily fabricated nanostructured CoP particles (150 to 200 nm) on carbon fiber paper (CFP) for hydrogen evolution reaction (HER) by a simple two-step process via a green route. In the first step, crystalline Co 3 O 4 nanocubes (150-200 nm) were loaded on CFP through a hydrothermal process at low temperature (120 °C). Interestingly, crystalline Co 3 O 4 nanocubes with a size 150-200 nm exhibited different growth mechanisms in contrast to the crystalline Co 3 O 4 nanocubes with a size <100 nm reported earlier. In the second step, these crystalline Co 3 O 4 nanocubes were converted to catalytically active CoP particles through chemical vapor deposition (CVD) phosphorization (denoted as CoP/CFP-H). Remarkably, CoP/CFP-H exhibited a low Tafel slope of 49.7 mV/dec and only required overpotentials of 128.1, 144.4, and 190.8 mV to drive geometric current densities of -10, -20, and -100 mA cm -2 , respectively. Besides, the CoP/CFP-H also demonstrated an excellent durability in an acidic environment under 2000 sweeps at a high scan rate (100 mV s -1 ) and a 24 h chronopotentiometry testing. For comparison, CoP was also fabricated through the electrodeposition method, followed by CVD phosphorization (denoted as CoP/CFP-E). It was found that the latter had exhibited inferior activity compared to CoP/CFP-H. The good performances of CoP/CFP-H are essentially due to the rational designs of electrode: (i) the applications of highly HER active CoP electrocatalyst, (ii) the intimate contact of nanostructured CoP on carbon fibers, and (iii) the large electrochemical surface area at electrocatalyst/electrolyte interface due to the large retaining of particles features after phosphorization. Notably, the intermediate Co 3 O 4 /CFP can serve as a platform to develop other cobalt-based functional materials.

ALMA reveals sunburn: CO dissociation around AGB stars in the globular cluster 47 Tucanae

NASA Astrophysics Data System (ADS)

McDonald, I.; Zijlstra, A. A.; Lagadec, E.; Sloan, G. C.; Boyer, M. L.; Matsuura, M.; Smith, R. J.; Smith, C. L.; Yates, J. A.; van Loon, J. Th.; Jones, O. C.; Ramstedt, S.; Avison, A.; Justtanont, K.; Olofsson, H.; Blommaert, J. A. D. L.; Goldman, S. R.; Groenewegen, M. A. T.

2015-11-01

Atacama Large Millimetre Array observations show a non-detection of carbon monoxide around the four most luminous asymptotic giant branch (AGB) stars in the globular cluster 47 Tucanae. Stellar evolution models and star counts show that the mass-loss rates from these stars should be ˜1.2-3.5 × 10-7 M⊙ yr-1. We would naïvely expect such stars to be detectable at this distance (4.5 kpc). By modelling the ultraviolet radiation field from post-AGB stars and white dwarfs in 47 Tuc, we conclude that CO should be dissociated abnormally close to the stars. We estimate that the CO envelopes will be truncated at a few hundred stellar radii from their host stars and that the line intensities are about two orders of magnitude below our current detection limits. The truncation of CO envelopes should be important for AGB stars in dense clusters. Observing the CO (3-2) and higher transitions and targeting stars far from the centres of clusters should result in the detections needed to measure the outflow velocities from these stars.

No way out? The double-bind in seeking global prosperity alongside mitigated climate change

NASA Astrophysics Data System (ADS)

Garrett, T. J.

2012-01-01

In a prior study (Garrett, 2011), I introduced a simple economic growth model designed to be consistent with general thermodynamic laws. Unlike traditional economic models, civilization is viewed only as a well-mixed global whole with no distinction made between individual nations, economic sectors, labor, or capital investments. At the model core is a hypothesis that the global economy's current rate of primary energy consumption is tied through a constant to a very general representation of its historically accumulated wealth. Observations support this hypothesis, and indicate that the constant's value is λ = 9.7 ± 0.3 milliwatts per 1990 US dollar. It is this link that allows for treatment of seemingly complex economic systems as simple physical systems. Here, this growth model is coupled to a linear formulation for the evolution of globally well-mixed atmospheric CO2 concentrations. While very simple, the coupled model provides faithful multi-decadal hindcasts of trajectories in gross world product (GWP) and CO2. Extending the model to the future, the model suggests that the well-known IPCC SRES scenarios substantially underestimate how much CO2 levels will rise for a given level of future economic prosperity. For one, global CO2 emission rates cannot be decoupled from wealth through efficiency gains. For another, like a long-term natural disaster, future greenhouse warming can be expected to act as an inflationary drag on the real growth of global wealth. For atmospheric CO2 concentrations to remain below a "dangerous" level of 450 ppmv (Hansen et al., 2007), model forecasts suggest that there will have to be some combination of an unrealistically rapid rate of energy decarbonization and nearly immediate reductions in global civilization wealth. Effectively, it appears that civilization may be in a double-bind. If civilization does not collapse quickly this century, then CO2 levels will likely end up exceeding 1000 ppmv; but, if CO2 levels rise by this much, then the risk is that civilization will gradually tend towards collapse.

Investigation into the disparate origin of CO2 and H2O outgassing for Comet 67/P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Bieler, André; Capaccioni, Fabrizio; Bockelée-Morvan, Dominique; Filacchione, Gianrico; Erard, Stephane; Leyrat, Cedric; Blecka, Maria; Capria, Maria Teresa; Combi, Michael; Crovisier, Jacques; De Sanctis, Maria Cristina; Fougere, Nicolas; Taylor, Fred; Migliorini, Alessandra; Piccioni, Giuseppe

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma. We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ∼5.0% and ∼2.5% for Feb. 28 and April 27, respectively. Because of the highly variable nature of the CO2 evolution from the surface we do not believe that these numbers are diagnostic of the comet's bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's rotational orientation combined with its complex geometric shape which can result in quite variable rates of erosion for different surface areas such as the northern and southern hemisphere. Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the Sun is 2.5 × 1026 molecules/s while for April 27 at 1.76 AU it is 4.65 × 1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the night side. We also make an attempt to obtain the fraction of the H2O production coming from the highly active neck of the comet versus the rest of the illuminated surface from the pole-on view of Feb. 28 and estimate that about 60% of the H2O derives from the neck area. A rough estimate of the water surface evaporation rate of the illuminated nucleus for April 27 yields about 5 × 1019 molecules/s/m2. Spatial radial profiles of H2O on April 27 on the illuminated side of the comet, extending from 1.78 to 6.47 km from the nucleus center, show that water follows model predictions quite well, with the gas accelerating as it expands into the coma. Our dayside radial profile allows us to make an empirical determination of the expansion velocity of water. On the night side the spatial profile of water follows 1/ρ. The CO2 profiles do not exhibit any acceleration into the coma but are closely matched by a 1/ρ profile.

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

He-accreting carbon-oxygen white dwarfs and Type Ia supernovae

NASA Astrophysics Data System (ADS)

Wang, Bo; Podsiadlowski, Philipp; Han, Zhanwen

2017-12-01

He accretion on to carbon-oxygen white dwarfs (CO WDs) plays a fundamental role when studying the formation of Type Ia supernovae (SNe Ia). Employing the MESA stellar evolution code, we calculated the long-term evolution of He-accreting CO WDs. Previous studies usually supposed that a WD can grow in mass to the Chandrasekhar limit in the stable He burning region and finally produce an SN Ia. However, in this study, we find that off-centre carbon ignition occurs in the stable He burning region if the accretion rate is above a critical value (∼2.05 × 10-6 M⊙ yr-1), resulting in accretion-induced collapse rather than an SN Ia. If the accretion rate is below the critical value, explosive carbon ignition will eventually happen in the centre producing an SN Ia. Taking into account the possibility of off-centre carbon ignition, we have re-determined the initial parameter space that produces SNe Ia in the He star donor channel, one of the promising channels to produce SNe Ia in young populations. Since this parameter space is smaller than was found in the previous study of Wang et al. (2009), the SN Ia rates are also correspondingly smaller. We also determined the chemical abundance profile of the He-accreting WDs at the moment of explosive carbon ignition, which can be used as initial input for SN Ia explosion models.

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

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

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less

Metal organic framework-derived CoPS/N-doped carbon for efficient electrocatalytic hydrogen evolution.

PubMed

Li, Yuzhi; Niu, Siqi; Rakov, Dmitrii; Wang, Ying; Cabán-Acevedo, Miguel; Zheng, Shijian; Song, Bo; Xu, Ping

2018-04-19

Electrocatalytic hydrogen evolution has attracted a great deal of attention due to the urgent need for clean energy. Herein, we demonstrate the synthesis of ternary pyrite-type cobalt phosphosulphide (CoPS) nanoparticles supported on a nitrogen-doped carbon matrix, CoPS/N-C, through carbonization and subsequent phosphosulfurization of Co-based zeolitic imidazolate frameworks (ZIF-67), as promising hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline solutions. The polyhedral structure of ZIF-67 can be well maintained in the as-prepared CoPS/N-C nanocomposites. In particular, CoPS/N-C provides a geometric catalytic current density of -10 mA cm-2 at overpotentials of -80 and -148 mV vs. a reversible hydrogen electrode (RHE) and a Tafel slope of 68 and 78 mV dec-1 in 0.5 M H2SO4 and 1 M KOH, respectively, which is superior to most of the transition metal phosphosulfide materials. This MOF-derived synthesis of a transition metal phosphosulfide supported heteroatom-doped carbon matrix provides a promising opportunity for the development of highly efficient electrocatalysts for renewable energy devices.

Heterogeneous Electrocatalyst with Molecular Cobalt Ions Serving as the Center of Active Sites.

PubMed

Wang, Jiong; Ge, Xiaoming; Liu, Zhaolin; Thia, Larissa; Yan, Ya; Xiao, Wei; Wang, Xin

2017-02-08

Molecular Co 2+ ions were grafted onto doped graphene in a coordination environment, resulting in the formation of molecularly well-defined, highly active electrocatalytic sites at a heterogeneous interface for the oxygen evolution reaction (OER). The S dopants of graphene are suggested to be one of the binding sites and to be responsible for improving the intrinsic activity of the Co sites. The turnover frequency of such Co sites is greater than that of many Co-based nanostructures and IrO 2 catalysts. Through a series of carefully designed experiments, the pathway for the evolution of the Co cation-based molecular catalyst for the OER was further demonstrated on such a single Co-ion site for the first time. The Co 2+ ions were successively oxidized to Co 3+ and Co 4+ states prior to the OER. The sequential oxidation was coupled with the transfer of different numbers of protons/hydroxides and generated an active Co 4+ ═O fragment. A side-on hydroperoxo ligand of the Co 4+ site is proposed as a key intermediate for the formation of dioxygen.

The Co-Evolution of Knowledge and Event Memory

ERIC Educational Resources Information Center

Nelson, Angela B.; Shiffrin, Richard M.

2013-01-01

We present a theoretical framework and a simplified simulation model for the co-evolution of knowledge and event memory, both termed SARKAE (Storing and Retrieving Knowledge and Events). Knowledge is formed through the accrual of individual events, a process that operates in tandem with the storage of individual event memories. In 2 studies, new…

Nucleation, growth, and repair of a cobalt-based oxygen evolving catalyst.

PubMed

Surendranath, Yogesh; Lutterman, Daniel A; Liu, Yi; Nocera, Daniel G

2012-04-11

The mechanism of nucleation, steady-state growth, and repair is investigated for an oxygen evolving catalyst prepared by electrodeposition from Co(2+) solutions in weakly basic electrolytes (Co-OEC). Potential step chronoamperometry and atomic force microscopy reveal that nucleation of Co-OEC is progressive and reaches a saturation surface coverage of ca. 70% on highly oriented pyrolytic graphite substrates. Steady-state electrodeposition of Co-OEC exhibits a Tafel slope approximately equal to 2.3 × RT/F. The electrochemical rate law exhibits a first order dependence on Co(2+) and inverse orders on proton (third order) and proton acceptor, methylphosphonate (first order for 1.8 mM ≤ [MeP(i)] ≤ 18 mM and second order dependence for 32 mM ≤ [MeP(i)] ≤ 180 mM). These electrokinetic studies, combined with recent XAS studies of catalyst structure, suggest a mechanism for steady state growth at intermediate MeP(i) concentration (1.8-18 mM) involving a rapid solution equilibrium between aquo Co(II) and Co(III) hydroxo species accompanied with a rapid surface equilibrium involving electrolyte dissociation and deprotonation of surface bound water. These equilibria are followed by a chemical rate-limiting step for incorporation of Co(III) into the growing cobaltate clusters comprising Co-OEC. At higher concentrations of MeP(i) ([MeP(i)] ≥ 32 mM), MePO(3)(2-) equilibrium binding to Co(II) in solution is suggested by the kinetic data. Consistent with the disparate pH profiles for oxygen evolution electrocatalysis and catalyst formation, NMR-based quantification of catalyst dissolution as a function of pH demonstrates functional stability and repair at pH values >6 whereas catalyst corrosion prevails at lower pH values. These kinetic insights provide a basis for developing and operating functional water oxidation (photo)anodes under benign pH conditions. © 2012 American Chemical Society

Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

PubMed Central

T. Weller, Mark

2018-01-01

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

Vibrational and rotational excitation of CO in comets. Part 1: Non-equilibrium calculations. Part 2: Results of the calculation for standard bright comet, comet Iras-Araki-Alcock and comet Halley

NASA Technical Reports Server (NTRS)

Chin, G.; Weaver, H. A.

1984-01-01

The vibrational and rotational excitation of the CO molecule in cometary comae were investigated using a model which includes IR vibrational pumping by the solar flux, vibrational and rotational radiative decay, and collisional coupling among rotational states. Steady state was not assumed in solving the rate equations. The evolution of a shell of CO gas was monitored as it expanded from the nucleus into the outer coma. Collisional effects were treated using a kinetic temperature profile derived from theoretical work on the coma energy balance. The kinetic temperature was assumed to be extremely cold in the inner coma; this has significant consequences for the CO excitation. If optical depth effects are ignored, only low J transitions will be significantly excited in comets observed at high spatial resolution. Ground-based observations of CO co-vibrational and rotational transitions will be extremely difficult due to lack of sensitivity and/or terrestrial absorption. However, CO should be detectable from a large comet with favorable observing geometry if the CO is a parent molecule present at the 10% level (or greater) relative to H2O. Observations using cooled, spaceborne instruments should be capable of detecting CO emission from even moderately bright comets.

Vibrational and rotational excitation of CO in comets. Part 1: Non-equilibrium calculations. Part 2: Results of the calculation for standard bright comet, comet Iras-Araki-Alcock and comet Halley

NASA Astrophysics Data System (ADS)

Chin, G.; Weaver, H. A.

1984-05-01

The vibrational and rotational excitation of the CO molecule in cometary comae were investigated using a model which includes IR vibrational pumping by the solar flux, vibrational and rotational radiative decay, and collisional coupling among rotational states. Steady state was not assumed in solving the rate equations. The evolution of a shell of CO gas was monitored as it expanded from the nucleus into the outer coma. Collisional effects were treated using a kinetic temperature profile derived from theoretical work on the coma energy balance. The kinetic temperature was assumed to be extremely cold in the inner coma; this has significant consequences for the CO excitation. If optical depth effects are ignored, only low J transitions will be significantly excited in comets observed at high spatial resolution. Ground-based observations of CO co-vibrational and rotational transitions will be extremely difficult due to lack of sensitivity and/or terrestrial absorption. However, CO should be detectable from a large comet with favorable observing geometry if the CO is a parent molecule present at the 10% level (or greater) relative to H2O. Observations using cooled, spaceborne instruments should be capable of detecting CO emission from even moderately bright comets.

Separating the influence of temperature, drought, and fire on interannual variability in atmospheric CO2

PubMed Central

Keppel-Aleks, Gretchen; Wolf, Aaron S; Mu, Mingquan; Doney, Scott C; Morton, Douglas C; Kasibhatla, Prasad S; Miller, John B; Dlugokencky, Edward J; Randerson, James T

2014-01-01

The response of the carbon cycle in prognostic Earth system models (ESMs) contributes significant uncertainty to projections of global climate change. Quantifying contributions of known drivers of interannual variability in the growth rate of atmospheric carbon dioxide (CO2) is important for improving the representation of terrestrial ecosystem processes in these ESMs. Several recent studies have identified the temperature dependence of tropical net ecosystem exchange (NEE) as a primary driver of this variability by analyzing a single, globally averaged time series of CO2 anomalies. Here we examined how the temporal evolution of CO2 in different latitude bands may be used to separate contributions from temperature stress, drought stress, and fire emissions to CO2 variability. We developed atmospheric CO2 patterns from each of these mechanisms during 1997–2011 using an atmospheric transport model. NEE responses to temperature, NEE responses to drought, and fire emissions all contributed significantly to CO2 variability in each latitude band, suggesting that no single mechanism was the dominant driver. We found that the sum of drought and fire contributions to CO2 variability exceeded direct NEE responses to temperature in both the Northern and Southern Hemispheres. Additional sensitivity tests revealed that these contributions are masked by temporal and spatial smoothing of CO2 observations. Accounting for fires, the sensitivity of tropical NEE to temperature stress decreased by 25% to 2.9 ± 0.4 Pg C yr−1 K−1. These results underscore the need for accurate attribution of the drivers of CO2 variability prior to using contemporary observations to constrain long-term ESM responses. PMID:26074665

Separating the influence of temperature, drought, and fire on interannual variability in atmospheric CO2.

PubMed

Keppel-Aleks, Gretchen; Wolf, Aaron S; Mu, Mingquan; Doney, Scott C; Morton, Douglas C; Kasibhatla, Prasad S; Miller, John B; Dlugokencky, Edward J; Randerson, James T

2014-11-01

The response of the carbon cycle in prognostic Earth system models (ESMs) contributes significant uncertainty to projections of global climate change. Quantifying contributions of known drivers of interannual variability in the growth rate of atmospheric carbon dioxide (CO 2 ) is important for improving the representation of terrestrial ecosystem processes in these ESMs. Several recent studies have identified the temperature dependence of tropical net ecosystem exchange (NEE) as a primary driver of this variability by analyzing a single, globally averaged time series of CO 2 anomalies. Here we examined how the temporal evolution of CO 2 in different latitude bands may be used to separate contributions from temperature stress, drought stress, and fire emissions to CO 2 variability. We developed atmospheric CO 2 patterns from each of these mechanisms during 1997-2011 using an atmospheric transport model. NEE responses to temperature, NEE responses to drought, and fire emissions all contributed significantly to CO 2 variability in each latitude band, suggesting that no single mechanism was the dominant driver. We found that the sum of drought and fire contributions to CO 2 variability exceeded direct NEE responses to temperature in both the Northern and Southern Hemispheres. Additional sensitivity tests revealed that these contributions are masked by temporal and spatial smoothing of CO 2 observations. Accounting for fires, the sensitivity of tropical NEE to temperature stress decreased by 25% to 2.9 ± 0.4 Pg C yr -1  K -1 . These results underscore the need for accurate attribution of the drivers of CO 2 variability prior to using contemporary observations to constrain long-term ESM responses.

Directions for Optimization of Photosynthetic Carbon Fixation: RuBisCO's Efficiency May Not Be So Constrained After All.

PubMed

Cummins, Peter L; Kannappan, Babu; Gready, Jill E

2018-01-01

The ubiquitous enzyme Ribulose 1,5-bisphosphate carboxylase-oxygenase (RuBisCO) fixes atmospheric carbon dioxide within the Calvin-Benson cycle that is utilized by most photosynthetic organisms. Despite this central role, RuBisCO's efficiency surprisingly struggles, with both a very slow turnover rate to products and also impaired substrate specificity, features that have long been an enigma as it would be assumed that its efficiency was under strong evolutionary pressure. RuBisCO's substrate specificity is compromised as it catalyzes a side-fixation reaction with atmospheric oxygen; empirical kinetic results show a trend to tradeoff between relative specificity and low catalytic turnover rate. Although the dominant hypothesis has been that the active-site chemistry constrains the enzyme's evolution, a more recent study on RuBisCO stability and adaptability has implicated competing selection pressures. Elucidating these constraints is crucial for directing future research on improving photosynthesis, as the current literature casts doubt on the potential effectiveness of site-directed mutagenesis to improve RuBisCO's efficiency. Here we use regression analysis to quantify the relationships between kinetic parameters obtained from empirical data sets spanning a wide evolutionary range of RuBisCOs. Most significantly we found that the rate constant for dissociation of CO 2 from the enzyme complex was much higher than previous estimates and comparable with the corresponding catalytic rate constant. Observed trends between relative specificity and turnover rate can be expressed as the product of negative and positive correlation factors. This provides an explanation in simple kinetic terms of both the natural variation of relative specificity as well as that obtained by reported site-directed mutagenesis results. We demonstrate that the kinetic behaviour shows a lesser rather than more constrained RuBisCO, consistent with growing empirical evidence of higher variability in relative specificity. In summary our analysis supports an explanation for the origin of the tradeoff between specificity and turnover as due to competition between protein stability and activity, rather than constraints between rate constants imposed by the underlying chemistry. Our analysis suggests that simultaneous improvement in both specificity and turnover rate of RuBisCO is possible.

Helium ignition in rotating magnetized CO white dwarfs leading to fast and faint rather than classical Type Ia supernovae

NASA Astrophysics Data System (ADS)

Neunteufel, P.; Yoon, S.-C.; Langer, N.

2017-06-01

Context. Based mostly on stellar models that do not include rotation, CO white dwarfs that accrete helium at rates of about 10-8M⊙/ yr have been put forward as candidate progenitors for a number of transient astrophysical phenomena, including Type Ia supernovae and the peculiar and fainter Type Iax supernovae. Aims: Here we study the impact of accretion-induced spin-up including the subsequent magnetic field generation, angular momentum transport, and viscous heating on the white dwarf evolution up to the point of helium ignition. Methods: We resolve the structure of the helium accreting white dwarf models with a one-dimensional Langrangian hydrodynamic code, modified to include rotational and magnetic effects, in 315 model sequences adopting different mass-transfer rates (10-8-10-7M⊙/ yr), and initial white dwarf masses (0.54-1.10 M⊙) and luminosities (0.01-1 L⊙). Results: We find magnetic angular momentum transport, which leads to quasi-solid-body rotation, profoundly impacts the evolution of the white dwarf models, and the helium ignition conditions. Our rotating lower mass (0.54 and 0.82 M⊙) models accrete up to 50% more mass up to ignition than the non-rotating case, while it is the opposite for our more massive models. Furthermore, we find that rotation leads to helium ignition densities that are up to ten times smaller, except for the lowest adopted initial white dwarf mass. Ignition densities on the order of 106 g/cm3 are only found for the lowest accretion rates and for large amounts of accreted helium (≳0.4M⊙). However, correspondingly massive donor stars would transfer mass at much higher rates. We therefore expect explosive He-shell burning to mostly occur as deflagrations and at Ṁ > 2 × 10-8M⊙/ yr, regardless of white dwarf mass. Conclusions: Our results imply that helium accretion onto CO white dwarfs at the considered rates is unlikely to lead to the explosion of the CO core or to classical Type Ia supernovae, but may instead produce events that belong to the recently identified classes of faint and fast hydrogen-free supernovae.

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

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

Favaro, Marco; Yang, Jinhui; Nappini, Silvia

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Favaro, Marco; Yang, Jinhui; Nappini, Silvia; ...

2017-06-09

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Induction of Reduced Photorespiratory Activity in Submersed and Amphibious Aquatic Macrophytes 1

PubMed Central

Salvucci, Michael E.; Bowes, George

1981-01-01

Incubation under water in a 30 C/14-hour or 12 C/10-hour photoperiod caused the CO2 compensation points of 10 aquatic macrophytes to decrease below 25 or increase above 50 microliters CO2 per liter, respectively. Submerged and aerial leaves of two amphibious angiosperms (Myriophyllum brasiliense and Proserpinaca palustris) maintained high compensation points when incubated in air but, when the submerged or aerial leaves of Proserpinaca were incubated under water, the compensation points dropped as low as 10. This suggests that, in addition to temperature and photoperiod, some factor associated with submergence regulates the compensation point of aquatic plants. In the high-compensation point plants, photorespiration, as a percentage of net photosynthesis, was equivalent to that in terrestrial C3 plants. For Hydrilla verticillata, the decreasing CO2 compensation points (110, 40, and 10) were associated with reduced photorespiration, as indicated by decreased O2 inhibition, decreased rates of CO2 evolution into CO2-free air, and increased net photosynthetic rates. The decrease in the CO2 compensation points of Hydrilla, Egeria densa, and Cabomba caroliniana was accompanied by an increase in the activity of phosphoenolpyruvate, but not of ribulose bisphosphate, carboxylase. In Hydrilla, several C4 enzymes also increased in activity to the following levels (micromoles per gram fresh weight per hour): pyruvate Pi dikinase (35), pyrophosphatase (716), adenylate kinase (525), NAD and NADP malate dehydrogenase (6565 and 30), NAD and NADP malic enzymes (239 and 44), and aspartate and alanine aminotransferases (357 and 85), whereas glycolate oxidase (6) and phosphoglycolate and phosphoglycerate phosphatases (76 and 32) showed no change. Glycolate dehydrogenase and phosphoenolpyruvate carboxykinase were undetectable. The reduced photorespiration in these plants may be due to increased CO2 fixation via a C4 acid pathway. However, for three Myriophyllum species, some other mechanism appears operative, as phosphoenolpyruvate carboxylase was not increased in the low compensation point state, and ribulose bisphosphate carboxylase remained the predominant carboxylation enzyme. PMID:16661670

The persistence of natural CO2 accumulations over millennial timescales: Integrating noble gas and reservoir data at Bravo Dome, NM

NASA Astrophysics Data System (ADS)

Akhbari, D.

2017-12-01

Bravo Dome, the largest CO2 reservoir in the US, is a hydrogeologically closed system that has stored a very large amount of CO2 on millennial time scales. The pre-production gas pressures in Bravo Dome indicate that the reservoir is highly under-pressured and is divided into separate pressure compartments that do not communicate hydrologically. Previous studies used the noble gas composition at Bravo Dome to constrain the amount of dissolved CO2 into the brine. This CO2 dissolution into brine plays an important role in the observed under-pressure at the reservoir. However, the dissolution rates and transport mechanisms remain unknown. In this study, we are looking into reservoir pressures and noble gas composition in the northeastern section of the reservoir to constrain timescales of CO2 dissolution. We are interested in northeastern part of the reservoir because the largest amount of CO2 was dissolved into brine in this section. Also, we specifically look into the evolution of the CO2/3He and 20Ne concentration during convective CO2 dissolution at Bravo Dome. 20Ne has atmospheric origin and is initially in the brine, while 3He and CO2 have magmatic sources and were introduced with the gas. CO2/3He decreases as more CO2 dissolves into brine, due to the higher solubility of CO2 compare to that of 3He. However, 20Ne concentration in the gas increases due to exsolution of 20Ne from brine into the gas phase. We present 2D numerical simulation that demonstrate the persistence of CO2 over 1Ma and reproduce the observed reservoir pressures and noble gas compositions. Our results indicate that convection is required to produce observed changes in gas composition. But diffusion makes a significant contribution to mass transport.

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Rational Construction of Hollow Core-Branch CoSe2 Nanoarrays for High-Performance Asymmetric Supercapacitor and Efficient Oxygen Evolution.

PubMed

Chen, Tian; Li, Songzhan; Wen, Jian; Gui, Pengbin; Guo, Yaxiong; Guan, Cao; Liu, Jinping; Fang, Guojia

2018-02-01

Metal selenides have great potential for electrochemical energy storage, but are relatively scarce investigated. Herein, a novel hollow core-branch CoSe 2 nanoarray on carbon cloth is designed by a facile selenization reaction of predesigned CoO nanocones. And the electrochemical reaction mechanism of CoSe 2 in supercapacitor is studied in detail for the first time. Compared with CoO, the hollow core-branch CoSe 2 has both larger specific surface area and higher electrical conductivity. When tested as a supercapacitor positive electrode, the CoSe 2 delivers a high specific capacitance of 759.5 F g -1 at 1 mA cm -2 , which is much larger than that of CoO nanocones (319.5 F g -1 ). In addition, the CoSe 2 electrode exhibits excellent cycling stability in that a capacitance retention of 94.5% can be maintained after 5000 charge-discharge cycles at 5 mA cm -2 . An asymmetric supercapacitor using the CoSe 2 as cathode and an N-doped carbon nanowall as anode is further assembled, which show a high energy density of 32.2 Wh kg -1 at a power density of 1914.7 W kg -1 , and maintains 24.9 Wh kg -1 when power density increased to 7354.8 W kg -1 . Moreover, the CoSe 2 electrode also exhibits better oxygen evolution reaction activity than that of CoO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Urchin-Like Ni1/3Co2/3(CO3)1/2(OH)·0.11H2O for Ultrahigh-Rate Electrochemical Supercapacitors: Structural Evolution from Solid to Hollow.

PubMed

Wei, Wutao; Cui, Shizhong; Ding, Luoyi; Mi, Liwei; Chen, Weihua; Hu, Xianluo

2017-11-22

Portable electronics and electric or hybrid electric vehicles are developing in the trend of fast charge and long electric mileage, which ask us to design a novel electrode with sufficient electronic and ionic transport channels at the same time. Herein, we fabricate a uniform hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material through an easy self-generated and resacrificial template method. The one-dimensional chain-like crystal structure unit containing the metallic bonding and the intercalated OH - and H 2 O endow this electrode material with abundant electronic and ionic transport channels. The hollow-urchin-like structure built by nanorods contributes to the large electrode-electrolyte contact area ensuring the supply of ions at high current. CNTs are employed to transport electrons between electrode material and current collector. The as-assembled NC-CNT-2//AC supercapacitor device exhibits a high specific capacitance of 108.3 F g -1 at 20 A g -1 , a capacitance retention ratio of 96.2% from 0.2 to 20 A g -1 , and long cycle life. Comprehensive investigations unambiguously highlight that the unique hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material would be the right candidate for advanced next-generation supercapacitors.

Effects of low atmospheric CO2 and elevated temperature during growth on the gas exchange responses of C3, C3-C4 intermediate, and C4 species from three evolutionary lineages of C4 photosynthesis.

PubMed

Vogan, Patrick J; Sage, Rowan F

2012-06-01

This study evaluates acclimation of photosynthesis and stomatal conductance in three evolutionary lineages of C(3), C(3)-C(4) intermediate, and C(4) species grown in the low CO(2) and hot conditions proposed to favo r the evolution of C(4) photosynthesis. Closely related C(3), C(3)-C(4), and C(4) species in the genera Flaveria, Heliotropium, and Alternanthera were grown near 380 and 180 μmol CO(2) mol(-1) air and day/night temperatures of 37/29°C. Growth CO(2) had no effect on photosynthetic capacity or nitrogen allocation to Rubisco and electron transport in any of the species. There was also no effect of growth CO(2) on photosynthetic and stomatal responses to intercellular CO(2) concentration. These results demonstrate little ability to acclimate to low CO(2) growth conditions in closely related C(3) and C(3)-C(4) species, indicating that, during past episodes of low CO(2), individual C(3) plants had little ability to adjust their photosynthetic physiology to compensate for carbon starvation. This deficiency could have favored selection for more efficient modes of carbon assimilation, such as C(3)-C(4) intermediacy. The C(3)-C(4) species had approximately 50% greater rates of net CO(2) assimilation than the C(3) species when measured at the growth conditions of 180 μmol mol(-1) and 37°C, demonstrating the superiority of the C(3)-C(4) pathway in low atmospheric CO(2) and hot climates of recent geological time.

The role of tidal torques on the evolution of the system of Saturn's co-orbital satellites Janus and Epimetheus

NASA Astrophysics Data System (ADS)

Caudal, Gérard V.

2013-04-01

This paper discusses the effect of tides raised by Saturn on its co-orbital satellites Janus and Epimetheus, and its consequences on the long-term evolution of the co-orbital horseshoe pattern of those moons. This tidal effect is found to produce a loosening of the co-orbital lock of Janus and Epimetheus. The increase of the difference D between their semi-major axes under this process is estimated as 2.77 km/Myear, regardless of whether the moons are composed of monolithic or fractured ice. On the other hand, assuming that the outer edge of Saturn's A ring is permanently maintained by Janus and Epimetheus at their 7:6 resonance, Lissauer et al. [Lissauer, J.J., Goldreich, P., Tremaine S., 1985. Icarus 64, 425-434] have shown that the torques exerted on Janus and Epimetheus due to resonances with Saturn's rings would produce a tightening of the co-orbital lock. The rate of decrease of orbital difference D under that latter process depends upon the precise relative radial location of the A-ring outer edge as compared with Janus' lower orbit semi-major axis, which is quantified here by means of a parameter po characterizing the efficiency of the effect of Janus' ring resonance. Under the combined effects of those two processes, depending on the value of po relative to a critical value po ≈ 19%, the system will evolve toward either a transition from horseshoe to tadpole orbit, or to a destruction of the co-orbital lock, after a few tens of Myears. Most recent observations of the A ring's outer edge by Spitale and Porco [Spitale, J.N., Porco, C.C., 2009. The Astronomical Journal 138, 1520-1528] tend to indicate that the future evolution will be a net tightening of the co-orbital system, until a tadpole situation will be reached after about 15 Myears. From a study of the past history of the co-orbital system, it is shown that such a scenario is compatible with a capture from free orbits to co-orbital horseshoe pattern some 25 Myears ago.

Hopewell Beneficial CO2 Capture for Production of Fuels, Fertilizer and Energy

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

UOP; Honeywell Resins & Chemicals; Honeywell Process Solutions

2010-09-30

For Phase 1 of this project, the Hopewell team developed a detailed design for the Small Scale Pilot-Scale Algal CO2 Sequestration System. This pilot consisted of six (6) x 135 gallon cultivation tanks including systems for CO2 delivery and control, algal cultivation, and algal harvesting. A feed tank supplied Hopewell wastewater to the tanks and a receiver tank collected the effluent from the algal cultivation system. The effect of environmental parameters and nutrient loading on CO2 uptake and sequestration into biomass were determined. Additionally the cost of capturing CO2 from an industrial stack emission at both pilot and full-scale wasmore » determined. The engineering estimate evaluated Amine Guard technology for capture of pure CO2 and direct stack gas capture and compression. The study concluded that Amine Guard technology has lower lifecycle cost at commercial scale, although the cost of direct stack gas capture is lower at the pilot scale. Experiments conducted under high concentrations of dissolved CO2 did not demonstrate enhanced algae growth rate. This result suggests that the dissolved CO2 concentration at neutral pH was already above the limiting value. Even though dissolved CO2 did not show a positive effect on biomass growth, controlling its value at a constant set-point during daylight hours can be beneficial in an algae cultivation stage with high algae biomass concentration to maximize the rate of CO2 uptake. The limited enhancement of algal growth by CO2 addition to Hopewell wastewater was due at least in part to the high endogenous CO2 evolution from bacterial degradation of dissolved organic carbon present at high levels in the wastewater. It was found that the high level of bacterial activity was somewhat inhibitory to algal growth in the Hopewell wastewater. The project demonstrated that the Honeywell automation and control system, in combination with the accuracy of the online pH, dissolved O2, dissolved CO2, turbidity, Chlorophyll A and conductivity sensors is suitable for process control of algae cultivation in an open pond systems. This project concluded that the Hopewell wastewater is very suitable for algal cultivation but the potential for significant CO2 sequestration from the plant stack gas emissions was minimal due to the high endogenous CO2 generation in the wastewater from the organic wastewater content. Algae cultivation was found to be promising, however, for nitrogen remediation in the Hopewell wastewater.« less

Process-based modeling of silicate mineral weathering responses to increasing atmospheric CO2 and climate change

NASA Astrophysics Data System (ADS)

Banwart, Steven A.; Berg, Astrid; Beerling, David J.

2009-12-01

A mathematical model describes silicate mineral weathering processes in modern soils located in the boreal coniferous region of northern Europe. The process model results demonstrate a stabilizing biological feedback mechanism between atmospheric CO2 levels and silicate weathering rates as is generally postulated for atmospheric evolution. The process model feedback response agrees within a factor of 2 of that calculated by a weathering feedback function of the type generally employed in global geochemical carbon cycle models of the Earth's Phanerozoic CO2 history. Sensitivity analysis of parameter values in the process model provides insight into the key mechanisms that influence the strength of the biological feedback to weathering. First, the process model accounts for the alkalinity released by weathering, whereby its acceleration stabilizes pH at values that are higher than expected. Although the process model yields faster weathering with increasing temperature, because of activation energy effects on mineral dissolution kinetics at warmer temperature, the mineral dissolution rate laws utilized in the process model also result in lower dissolution rates at higher pH values. Hence, as dissolution rates increase under warmer conditions, more alkalinity is released by the weathering reaction, helping maintain higher pH values thus stabilizing the weathering rate. Second, the process model yields a relatively low sensitivity of soil pH to increasing plant productivity. This is due to more rapid decomposition of dissolved organic carbon (DOC) under warmer conditions. Because DOC fluxes strongly influence the soil water proton balance and pH, this increased decomposition rate dampens the feedback between productivity and weathering. The process model is most sensitive to parameters reflecting soil structure; depth, porosity, and water content. This suggests that the role of biota to influence these characteristics of the weathering profile is as important, if not more important, than the role of biota to influence mineral dissolution rates through changes in soil water chemistry. This process-modeling approach to quantify the biological weathering feedback to atmospheric CO2 demonstrates the potential for a far more mechanistic description of weathering feedback in simulations of the global geochemical carbon cycle.

Co-evolution of Massive Black Holes and Their Host Galaxies

NASA Astrophysics Data System (ADS)

Chen, Y. M.

2010-07-01

A scenario of co-evolution of supermassive black holes (SMBHs) and galaxies has been clearly conducted by the important evidence from observational results of quasar host galaxies and the relation between spheroid and SMBH mass. There are a plenty of unresolved problems and questions, some being basic, to be addressed in this scenario. The main goal of the present thesis is focusing on the mysterious scenario including growth of primordial black holes, cosmological evolution of spins and duty cycle of SMBHs, and interaction between the SMBH activity and star formation in galaxies from low to high redshifts. We review the main progress of this field over the past decade since the discovery of Magorrian relation and present comments on some questions in light of our view of points. The key questions to be addressed in this thesis work are: (1) how does the fast growth of primordial black holes influence their evolution? (2) what is the equation to describe the co-evolution of SMBHs and galaxies? (3) what is the mechanism to control the co-evolution? (4) how to transport the fueling gas from kpc scale to the center? It has been suggested that fast growth of primordial black holes via super-Eddington accretion is a promising way to form SMBHs in high redshift universe. Neutrino cooling has been employed and expedites the growth. We consider the Compton heating of the surroundings of the primordial black holes. We find that the realistic accretion rate is only a few percent of the Eddington rate, and the accretion is episodic. It implies that the fast growth via super-Eddington is not feasible. These conclusions have been confirmed by the detailed numerical simulations of Milosavljevic et al. (2008). The difficulties of the fast growth via accretion of baryon particles make the formation of SMBHs elusive in high redshift universe. We developed a new formulation to calculate the duty cycle of SMBHs based on the Soltan argument. We show it can be expressed by the mass density ratio of active SMBHs to the total. This not only makes the calculation of the duty cycle independent of the assumption of cosmological evolution of Eddington ratios, but also allows us to set a totally new equation - the so-called η-equation to describe the co-evolution of SMBHs and galaxies. Applying the equations to SDSS (Sloan Digital Sky Survey) and other related survey data, we find that: (1) cosmological evolution of the duty cycle tightly follows the history of star formation rate (SFR) density in z<2 universe; (2) they just show opposite trends in higher redshift universe; (3) the radiative efficiency dramatically decreases with z, showing η≈0.3 at z =2 and down to η≈0.05 at z =0. It shows for the first time a history of random accretion of SMBH growth from high to low redshift universe. Chapter 3 is devoted to develop a new method to estimate the specific star formation rates (SSFR) for DEEP2 data. Using the series of Balmer absorption lines in rest-frame 3750~4150 Å, we develop a new method to estimate the SSFR. Applying this new method to both SDSS and DEEP2 data, we find the SSFR derived from Balmer absorption lines is consistent with that from emission lines at local universe, while there is a 100.3~100.4 discrepancy at z&≈1. This result implies the initial mass function changes with redshift, and it tends to form more massive stars at higher redshift. We pay much attention to the interaction between AGN and star formation in Chapter 4 through investigations of the Seyfert galaxies and type II AGNs. We obtain the SFR in about 50 Seyfert galaxies and compare with the SFR predicted by Kennicutt-Schmidt's law. We find that they are lower than the predicted by a factor of 10~100, clearly showing the evidence of suppressing the star formation in the 100 pc region around nuclei. 10848 type II AGNs are selected from SDSS data for the study of starburst and AGN connection. We find the young stars are playing an important role in triggering SMBH activities. A very tight correlation Λ≅SSFR1.5 between the Eddington ratio λ and SSFR has been found in the sample. This nonlinear relation stresses the role of supernova explosion, which could excite strong turbulent viscosity to transport the angular momentum of the fueling gas to the SMBHs. We set up a modified model by including the role of supernova explosion to account for the starburst-AGN connection. Indeed, we find that the model can be nicely consistent with the correlation. In this thesis, we demonstrate a self-adjusted system of galaxies and SMBHs - the SMBHs are triggered via star formation, which would get suppressed by SMBH activities. As a summary of the present thesis, we draw a conclusion that we poorly understand the issues as to formation of SMBHs, evolution of galaxies and SMBHs. There are a plenty of issues to be addressed in future. The solved questions are much less than the bringing out ones.

Evolution of organic matter fractions after application of co-compost of sewage sludge with pruning waste to four Mediterranean agricultural soils. A soil microcosm experiment.

PubMed

Pérez-Lomas, A L; Delgado, G; Párraga, J; Delgado, R; Almendros, G; Aranda, V

2010-10-01

The effect of co-compost application from sewage sludge and pruning waste, on quality and quantity of soil organic carbon (SOC) in four Mediterranean agricultural soils (South Spain), was studied in soil microcosm conditions. Control soil samples (no co-compost addition) and soils treated with co-composts to a rate equivalent of 140 Mg ha(-1) were incubated for 90 days at two temperatures: 5 and 35 degrees C. The significances of incubation temperature and the addition of co-compost, on the evolution of the different fractions of SOC, were studied using a 2(3) factorial design. The co-compost amendment increased the amounts of humic fractions: humic acids (HA) (1.9 times), fulvic acids (FA) (3.3 times), humin (1.5 times), as well as the free organic matter (1.4 times) and free lipids (21.8 times). Incubation of the soils enhanced its biological activity mainly in the amended soils and at 35 degrees C, leading to progressive SOC mineralization and humification, concomitant to the preferential accumulation of HA. The incubation results show large differences depending on temperature and soil types. This fact allows us to select suitable organic amendment for the soil when a rapid increase in nutrients through mineralization is preferred, or in cases intending the stabilization and preservation of the SOC through a process of humification. In soils with HA of more than 5 E(4)/E(6) ratio, the incubation temperature increased rates of mineralization and humification, whereas lower temperatures limited the extent of both processes. In these soils the addition of co-compost in spring or summer is the most recommendable. In soils with HA of lower E(4)/E(6) ratio (<5), the higher temperature favoured mineralization but not humification, whereas the low temperature maintained the SOC levels and even increased the HA/FA ratio. In these soils the moment of addition of organic amendment should be decided depending on the effect intended. On the other hand, the lower the SOC content in the original soil, the greater are the changes observed in the SOC after amendment with co-compost. The results suggest that proper recommendations for optimum organic matter evolution after soil amendment is possible after considering a small set of characteristics of soil and the corresponding soil organic matter fractions, in particular HA. (c) 2010 Elsevier Ltd. All rights reserved.

Plate tectonics, habitability and life

NASA Astrophysics Data System (ADS)

Spohn, Tilman; Breuer, Doris

2016-04-01

The role of plate tectonics in defining habitability of terrestrial planets is being increasingly discussed (e.g., Elkins-Tanton, 2015). Plate tectonics is a significantly evolved concept with a large variety of aspects. In the present context, cycling of material between near surface and mantle reservoirs is most important. But increased heat transport through mixing of cold lithosphere with the deep interior and formation of continental crust may also matter. An alternative mechanism of material cycling between these reservoirs is hot-spot volcanism combined with crust delamination. Hot-spot volcanism will transport volatiles to the atmosphere while delamination will mix crust, possibly altered by sedimentation and chemical reactions, with the mantle. The mechanism works as long as the stagnant lithosphere plate has not grown thicker than the crust and as long as volcanic material is added onto the crust. Thermal evolution studies suggest that the mechanism could work for the first 1-2 Ga of planetary evolution. The efficiency of the mechanism is limited by the ratio of extrusive to intrusive volcanism, which is thought to be less than 0.25. Plate tectonics would certainly have an advantage by working even for more evolved planets. A simple, most-used concept of habitability requires the thermodynamic stability of liquid water on the surface of a planet. Cycling of CO2between the atmosphere, oceans and interior through subduction and surface volcanism is an important element of the carbonate-silicate cycle, a thermostat feedback cycle that will keep the atmosphere from entering into a runaway greenhouse. Calculations for a model Earth lacking plate tectonics but degassing CO2, N, and H2O to form a surface ocean and a secondary atmosphere (Tosi et al, 2016) suggest that liquid water can be maintained on the surface for 4.5Ga. The model planet would then qualify as habitable. It is conceivable that the CO2 buffering capability of its ocean together with silicate weathering of possible land surfaces and a biosphere could set up a CO2 sink that would further stabilize the temperature. As long as the planet keeps degassing CO2 at a sufficient rate, CO2 recycling through the mantle may not be required. However, this would require a sufficiently oxidized planet early on. If not sufficiently oxidized during accretion and core formation, oxidization of the planet would require cycling of matter between surface and interior reservoirs. Oxidization of an initially reduced Earth interior with the help of plate tectonics has been cited as a possible mechanism to allow the building up of oxygen in the terrestrial atmosphere around 2.3Ga b.p. (e.g., Catling and Claire, 2005), a pre-requisite for more evolved eukaryotic life. The oxidization would diminish a sink in the oxygen budget of the atmosphere by lowering the rate of outgassing of chemically reducing gases from the interior. Clearly, plate tectonics is a mechanism more potent of keeping a planet habitable and allow evolution of the biosphere than alternative concepts such as crust delamination. Catling, DC, Claire DW (2005), EPSL, 237, 1-20 Elkins-Tanton, L (2015) AGU Fall Meeting Abstract Tosi, N et al. (2016) EGU Abstract

Large-Scale Structure of the Molecular Gas in Taurus Revealed by High Spatial Dynamic Range Spectral Line Mapping

NASA Technical Reports Server (NTRS)

Goldsmith, Paul F.

2008-01-01

Viewgraph topics include: optical image of Taurus; dust extinction in IR has provided a new tool for probing cloud morphology; observations of the gas can contribute critical information on gas temperature, gas column density and distribution, mass, and kinematics; the Taurus molecular cloud complex; average spectra in each mask region; mas 2 data; dealing with mask 1 data; behavior of mask 1 pixels; distribution of CO column densities; conversion to H2 column density; variable CO/H2 ratio with values much less than 10(exp -4) at low N indicated by UV results; histogram of N(H2) distribution; H2 column density distribution in Taurus; cumulative distribution of mass and area; lower CO fractional abundance in mask 0 and 1 regions greatly increases mass determined in the analysis; masses determined with variable X(CO) and including diffuse regions agrees well with the found from L(CO); distribution of young stars as a function of molecular column density; star formation efficiency; star formation rate and gas depletion; and enlarged images of some of the regions with numerous young stars. Additional slides examine the origin of the Taurus molecular cloud, evolution from HI gas, kinematics as a clue to its origin, and its relationship to star formation.

Biodegradation of carbofuran and furathiocarb in soil: effect of pretreatment and microbial growth responses to carbofuran

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

Henry, K.M.

The rate of degradation of carbofuran was measured in Norfolk loamy sand and Lynchburg sandy loam soils with no known history of pesticide treatment. Degradation was measured by trapping /sup 14/CO/sub 2/ evolved from /sup 14/C-carbonyl carbofuran applied to soil in flasks. Loamy sand soil pretreated with 9 ..mu..g x g/sup -1/ carbofuran completely degraded a second or third application of 9 ..mu..g x g/sup -1/ within 1-3 days, but <5% was degraded in soil treated for the first time. Nitrogen, applied as 100 ..mu..g x g/sup -1/ in NH/sub 4/NO/sub 3/, very slightly increased the rate of degradation ofmore » 9 ..mu..g x g/sup -1/ carbofuran in the pretreated soils. The rate of degradation of carbofuran in the pretreated soils can be described by 1st order kinetics. However, in the soil pretreated with 9 ..mu..g x g/sup -1/ carbofuran, the rate of degradation of an 8 ng x g/sup -1/ treatment was biphasic, with only 65% rapidly degraded within 2 days. This /sup 14/CO/sub 2/ evolution curve was best described by a two-compartment model for the degradation of low levels of organics in soil.« less

Xenon-ion-induced and thermal mixing of Co/Si bilayers and their interplay

NASA Astrophysics Data System (ADS)

Novaković, M.; Zhang, K.; Popović, M.; Bibić, N.; Hofsäss, H.; Lieb, K. P.

2011-05-01

Studies on ion-irradiated transition-metal/silicon bilayers demonstrate that interface mixing and silicide phase formation depend sensitively on the ion and film parameters, including the structure of the metal/Si interface. Thin Co layers e-gun evaporated to a thickness of 50 nm on Si(1 0 0) wafers were bombarded at room temperature with 400-keV Xe + ions at fluences of up to 3 × 10 16 cm -2. We used either crystalline or pre-amorphized Si wafers the latter ones prepared by 1.0-keV Ar-ion implantation. The as-deposited or Xe-ion-irradiated samples were then isochronally annealed at temperatures up to 700 °C. Changes of the bilayer structures induced by ion irradiation and/or annealing were investigated with RBS, XRD and HRTEM. The mixing rate for the Co/c-Si couples, Δ σ2/ Φ = 3.0(4) nm 4, is higher than the value expected for ballistic mixing and about half the value typical for spike mixing. Mixing of pre-amorphized Si is much weaker relative to crystalline Si wafers, contrary to previous results obtained for Fe/Si bilayers. Annealing of irradiated samples produces very similar interdiffusion and phase formation patterns above 400 °C as in the non-irradiated Co/Si bilayers: the phase evolution follows the sequence Co 2Si → CoSi → CoSi 2.

Mantle redox evolution and the oxidation state of the Archean atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.; Eggler, D. H.; Raeburn, S. P.

1993-01-01

Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.

Sol-flame synthesis of cobalt-doped TiO2 nanowires with enhanced electrocatalytic activity for oxygen evolution reaction.

PubMed

Cai, Lili; Cho, In Sun; Logar, Manca; Mehta, Apurva; He, Jiajun; Lee, Chi Hwan; Rao, Pratap M; Feng, Yunzhe; Wilcox, Jennifer; Prinz, Fritz B; Zheng, Xiaolin

2014-06-28

Doping nanowires (NWs) is of crucial importance for a range of applications due to the unique properties arising from both impurities' incorporation and nanoscale dimensions. However, existing doping methods face the challenge of simultaneous control over the morphology, crystallinity, dopant distribution and concentration at the nanometer scale. Here, we present a controllable and reliable method, which combines versatile solution phase chemistry and rapid flame annealing process (sol-flame), to dope TiO2 NWs with cobalt (Co). The sol-flame doping method not only preserves the morphology and crystallinity of the TiO2 NWs, but also allows fine control over the Co dopant profile by varying the concentration of Co precursor solution. Characterizations of the TiO2:Co NWs show that Co dopants exhibit 2+ oxidation state and substitutionally occupy Ti sites in the TiO2 lattice. The Co dopant concentration significantly affects the oxygen evolution reaction (OER) activity of TiO2:Co NWs, and the TiO2:Co NWs with 12 at% of Co on the surface show the highest OER activity with a 0.76 V reduction of the overpotential with respect to undoped TiO2 NWs. This enhancement of OER activity for TiO2:Co NWs is attributed to both improved surface charge transfer kinetics and increased bulk conductivity.

Atmospheric carbon dioxide: a driver of photosynthetic eukaryote evolution for over a billion years?

PubMed Central

Beerling, David J.

2012-01-01

Exciting evidence from diverse fields, including physiology, evolutionary biology, palaeontology, geosciences and molecular genetics, is providing an increasingly secure basis for robustly formulating and evaluating hypotheses concerning the role of atmospheric carbon dioxide (CO2) in the evolution of photosynthetic eukaryotes. Such studies span over a billion years of evolutionary change, from the origins of eukaryotic algae through to the evolution of our present-day terrestrial floras, and have relevance for plant and ecosystem responses to future global CO2 increases. The papers in this issue reflect the breadth and depth of approaches being adopted to address this issue. They reveal new discoveries pointing to deep evidence for the role of CO2 in shaping evolutionary changes in plants and ecosystems, and establish an exciting cross-disciplinary research agenda for uncovering new insights into feedbacks between biology and the Earth system. PMID:22232760

Atmospheric carbon dioxide: a driver of photosynthetic eukaryote evolution for over a billion years?

PubMed

Beerling, David J

2012-02-19

Exciting evidence from diverse fields, including physiology, evolutionary biology, palaeontology, geosciences and molecular genetics, is providing an increasingly secure basis for robustly formulating and evaluating hypotheses concerning the role of atmospheric carbon dioxide (CO(2)) in the evolution of photosynthetic eukaryotes. Such studies span over a billion years of evolutionary change, from the origins of eukaryotic algae through to the evolution of our present-day terrestrial floras, and have relevance for plant and ecosystem responses to future global CO(2) increases. The papers in this issue reflect the breadth and depth of approaches being adopted to address this issue. They reveal new discoveries pointing to deep evidence for the role of CO(2) in shaping evolutionary changes in plants and ecosystems, and establish an exciting cross-disciplinary research agenda for uncovering new insights into feedbacks between biology and the Earth system.

Intense pulsed light and laser treatment regimen improves scar evolution after cleft lip repair surgery.

PubMed

Peng, Lihong; Tang, Shijie; Li, Qin

2018-06-19

To observe the effects of intense pulsed light (IPL) and lattice CO 2 laser treatment on scar evolution following cleft lip repair. Fifty cleft lip repair patients were enrolled in this study. Twenty-five patients used conventional approach with scar cream massage combined with silica gel products after operation. While other 25 patients which received IPL and lattice CO 2 laser treatments. The treatments commenced 1 week after removal of stitches and observation of scar hyperplasia. Scar evolution was evaluated with the Vancouver scar scale (VSS) by postoperative photographs. Relative to the conventional approach, the laser treatments showed improved scar softening and flattening. These differences were reflected in the groups' significantly different VSS scores. Intense pulsed light combined with lattice CO 2 laser treatment can improve cleft lip surgery scar pliability and appearance, while alleviating children from having to endure the pain of scar massage. © 2018 Wiley Periodicals, Inc.

Characterisation of the magmatic signature in gas emissions from Turrialba Volcano, Costa Rica

NASA Astrophysics Data System (ADS)

Moussallam, Y.; Peters, N.; Ramírez, C.; Oppenheimer, C.; Aiuppa, A.; Giudice, G.

2014-12-01

The equilibrium composition of volcanic gases with their magma is often overprinted by interaction with a shallow hydrothermal system. Identifying the magmatic signature of volcanic gases is critical to relate their composition to properties of the magma (temperature, fO2, gas-melt segregation depth). We report measurements of the chemical composition and flux of the major gas species emitted from Turrialba Volcano during March 2013. Measurements were made of two vents in the summit region, one of which opened in 2010 and the other in 2012. We determined an average SO2 flux of 5.2 ± 1.9 kg s-1 using scanning ultraviolet spectroscopy, and molar proportions of H2O, CO2, SO2, HCl, CO and H2 gases of 94.16, 4.03, 1.56, 0.23, 0.003 and 0.009% respectively by open-path Fourier transform infrared (FTIR) spectrometry and a multi-species gas-sensing system. Together, these data imply fluxes of 88, 8, 0.44, 5 × 10-3 and 1 × 10-3 kg s-1 for H2O, CO2, HCl, CO and H2 respectively. Although H2S was detected, its concentration could not be resolved. HF was not detected. The chemical signature of the gas from both vents was found to be broadly similar. Following the opening of the 2010 and 2012 vents we found limited to negligible interaction of the magmatic gas with the hydrothermal system has occurred and the gas composition of the volcanic plume is broadly representative of equilibrium with the magma. The time evolution of the gas composition, the continuous emission of large quantities of SO2, and the physical evolution of the summit area with new vent openings and more frequent eruptions all point towards a continuous drying of the hydrothermal system at Turrialba's summit at an apparently increasing rate.

Preliminary conceptual model for mineral evolution in Yucca Mountain

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

Duffy, C.J.

1993-12-01

A model is presented for mineral alteration in Yucca Mountain, Nevada, that suggests that the mineral transformations observed there are primarily controlled by the activity of aqueous silica. The rate of these reactions is related to the rate of evolution of the metastable silica polymorphs opal-CT and cristobalite assuming that a{sub SiO{sub 2(aq)}} is fixed at the equilibrium solubility of the most soluble silica polymorph present. The rate equations accurately predict the present depths of disappearance of opal-CT and cristobalite. The rate equations have also been used to predict the extent of future mineral alteration that may result from emplacementmore » of a high-level nuclear waste repository in Yucca Mountain. Relatively small changes in mineralogy are predicted, but these predictions are based on the assumption that emplacement of a repository would not increase the pH of water in Yucca Mountain nor increase its carbonate content. Such changes may significantly increase mineral alteration. Some of the reactions currently occurring in Yucca Mountain consume H{sup +} and CO{sub 3}{sup 2{minus}}. Combining reaction rate models for these reactions with water chemistry data may make it possible to estimate water flux through the basal vitrophyre of the Topopah Spring Member and to help confirm the direction and rate of flow of groundwater in Yucca Mountain.« less

The Red Queen in mitochondria: cyto-nuclear co-evolution, hybrid breakdown and human disease

PubMed Central

Chou, Jui-Yu; Leu, Jun-Yi

2015-01-01

Cyto-nuclear incompatibility, a specific form of Dobzhansky-Muller incompatibility caused by incompatible alleles between mitochondrial and nuclear genomes, has been suggested to play a critical role during speciation. Several features of the mitochondrial genome (mtDNA), including high mutation rate, dynamic genomic structure, and uniparental inheritance, make mtDNA more likely to accumulate mutations in the population. Once mtDNA has changed, the nuclear genome needs to play catch-up due to the intimate interactions between these two genomes. In two populations, if cyto-nuclear co-evolution is driven in different directions, it may eventually lead to hybrid incompatibility. Although cyto-nuclear incompatibility has been observed in a wide range of organisms, it remains unclear what type of mutations drives the co-evolution. Currently, evidence supporting adaptive mutations in mtDNA remains limited. On the other hand, it has been known that some mutations allow mtDNA to propagate more efficiently but compromise the host fitness (described as selfish mtDNA). Arms races between such selfish mtDNA and host nuclear genomes can accelerate cyto-nuclear co-evolution and lead to a phenomenon called the Red Queen Effect. Here, we discuss how the Red Queen Effect may contribute to the frequent observation of cyto-nuclear incompatibility and be the underlying driving force of some human mitochondrial diseases. PMID:26042149

Ab initio molecular dynamics simulations reveal localization and time evolution dynamics of an excess electron in heterogeneous CO2-H2O systems.

PubMed

Liu, Ping; Zhao, Jing; Liu, Jinxiang; Zhang, Meng; Bu, Yuxiang

2014-01-28

In view of the important implications of excess electrons (EEs) interacting with CO2-H2O clusters in many fields, using ab initio molecular dynamics simulation technique, we reveal the structures and dynamics of an EE associated with its localization and subsequent time evolution in heterogeneous CO2-H2O mixed media. Our results indicate that although hydration can increase the electron-binding ability of a CO2 molecule, it only plays an assisting role. Instead, it is the bending vibrations that play the major role in localizing the EE. Due to enhanced attraction of CO2, an EE can stably reside in the empty, low-lying π(*) orbital of a CO2 molecule via a localization process arising from its initial binding state. The localization is completed within a few tens of femtoseconds. After EE trapping, the ∠OCO angle of the core CO2 (-) oscillates in the range of 127°∼142°, with an oscillation period of about 48 fs. The corresponding vertical detachment energy of the EE is about 4.0 eV, which indicates extreme stability of such a CO2-bound solvated EE in [CO2(H2O)n](-) systems. Interestingly, hydration occurs not only on the O atoms of the core CO2 (-) through formation of O⋯H-O H-bond(s), but also on the C atom, through formation of a C⋯H-O H-bond. In the latter binding mode, the EE cloud exhibits considerable penetration to the solvent water molecules, and its IR characteristic peak is relatively red-shifted compared with the former. Hydration on the C site can increase the EE distribution at the C atom and thus reduce the C⋯H distance in the C⋯H-O H-bonds, and vice versa. The number of water molecules associated with the CO2 (-) anion in the first hydration shell is about 4∼7. No dimer-core (C2O4 (-)) and core-switching were observed in the double CO2 aqueous media. This work provides molecular dynamics insights into the localization and time evolution dynamics of an EE in heterogeneous CO2-H2O media.

Stellar populations dominated by massive stars in dusty starburst galaxies across cosmic time

NASA Astrophysics Data System (ADS)

Zhang, Zhi-Yu; Romano, D.; Ivison, R. J.; Papadopoulos, Padelis P.; Matteucci, F.

2018-06-01

All measurements of cosmic star formation must assume an initial distribution of stellar masses—the stellar initial mass function—in order to extrapolate from the star-formation rate measured for typically rare, massive stars (of more than eight solar masses) to the total star-formation rate across the full stellar mass spectrum1. The shape of the stellar initial mass function in various galaxy populations underpins our understanding of the formation and evolution of galaxies across cosmic time2. Classical determinations of the stellar initial mass function in local galaxies are traditionally made at ultraviolet, optical and near-infrared wavelengths, which cannot be probed in dust-obscured galaxies2,3, especially distant starbursts, whose apparent star-formation rates are hundreds to thousands of times higher than in the Milky Way, selected at submillimetre (rest-frame far-infrared) wavelengths4,5. The 13C/18O isotope abundance ratio in the cold molecular gas—which can be probed via the rotational transitions of the 13CO and C18O isotopologues—is a very sensitive index of the stellar initial mass function, with its determination immune to the pernicious effects of dust. Here we report observations of 13CO and C18O emission for a sample of four dust-enshrouded starbursts at redshifts of approximately two to three, and find unambiguous evidence for a top-heavy stellar initial mass function in all of them. A low 13CO/C18O ratio for all our targets—alongside a well tested, detailed chemical evolution model benchmarked on the Milky Way6—implies that there are considerably more massive stars in starburst events than in ordinary star-forming spiral galaxies. This can bring these extraordinary starbursts closer to the `main sequence' of star-forming galaxies7, although such main-sequence galaxies may not be immune to changes in initial stellar mass function, depending on their star-formation densities.

Stellar populations dominated by massive stars in dusty starburst galaxies across cosmic time.

PubMed

Zhang, Zhi-Yu; Romano, D; Ivison, R J; Papadopoulos, Padelis P; Matteucci, F

2018-06-01

All measurements of cosmic star formation must assume an initial distribution of stellar masses-the stellar initial mass function-in order to extrapolate from the star-formation rate measured for typically rare, massive stars (of more than eight solar masses) to the total star-formation rate across the full stellar mass spectrum 1 . The shape of the stellar initial mass function in various galaxy populations underpins our understanding of the formation and evolution of galaxies across cosmic time 2 . Classical determinations of the stellar initial mass function in local galaxies are traditionally made at ultraviolet, optical and near-infrared wavelengths, which cannot be probed in dust-obscured galaxies 2,3 , especially distant starbursts, whose apparent star-formation rates are hundreds to thousands of times higher than in the Milky Way, selected at submillimetre (rest-frame far-infrared) wavelengths 4,5 . The 13 C/ 18 O isotope abundance ratio in the cold molecular gas-which can be probed via the rotational transitions of the 13 CO and C 18 O isotopologues-is a very sensitive index of the stellar initial mass function, with its determination immune to the pernicious effects of dust. Here we report observations of 13 CO and C 18 O emission for a sample of four dust-enshrouded starbursts at redshifts of approximately two to three, and find unambiguous evidence for a top-heavy stellar initial mass function in all of them. A low 13 CO/C 18 O ratio for all our targets-alongside a well tested, detailed chemical evolution model benchmarked on the Milky Way 6 -implies that there are considerably more massive stars in starburst events than in ordinary star-forming spiral galaxies. This can bring these extraordinary starbursts closer to the 'main sequence' of star-forming galaxies 7 , although such main-sequence galaxies may not be immune to changes in initial stellar mass function, depending on their star-formation densities.

Beyond aridification: multiple explanations for the elevated diversification of cacti in the New World Succulent Biome.

PubMed

Hernández-Hernández, Tania; Brown, Joseph W; Schlumpberger, Boris O; Eguiarte, Luis E; Magallón, Susana

2014-06-01

Succulent plants are widely distributed, reaching their highest diversity in arid and semi-arid regions. Their origin and diversification is thought to be associated with a global expansion of aridity. We test this hypothesis by investigating the tempo and pattern of Cactaceae diversification. Our results contribute to the understanding of the evolution of New World Succulent Biomes. We use the most taxonomically complete dataset currently available for Cactaceae. We estimate divergence times and utilize Bayesian and maximum likelihood methods that account for nonrandom taxonomic sampling, possible extinction scenarios and phylogenetic uncertainty to analyze diversification rates, and evolution of growth form and pollination syndrome. Cactaceae originated shortly after the Eocene-Oligocene global drop in CO2 , and radiation of its richest genera coincided with the expansion of aridity in North America during the late Miocene. A significant correlation between growth form and pollination syndrome was found, as well as a clear state dependence between diversification rate, and pollination and growth-form evolution. This study suggests a complex picture underlying the diversification of Cactaceae. It not only responded to the availability of new niches resulting from aridification, but also to the correlated evolution of novel growth forms and reproductive strategies. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Middle cerebral artery occlusion in Macaca fascicularis: acute and chronic stroke evolution.

PubMed

D'Arceuil, Helen E; Duggan, Michael; He, Julian; Pryor, Johnny; de Crespigny, Alex

2006-04-01

An intravascular stroke model designed for magnetic resonance imaging was developed in Macaca fascicularis (M. fascicularis) to characterize serial stroke lesion evolution. This model produces a range of stroke lesion sizes which closely mimics human stroke evolution. This paper describes the care of animals undergoing this stroke procedure, the range of outcomes we experienced and the cause of mortality in this model. Anesthesia was induced with atropine and ketamine and maintained with isoflurane or propofol. Non-invasive blood pressure, oxygen saturation, heart rate, respiration rate, temperature and end tidal CO2 were monitored continuously. The stroke was created by occluding a distal branch of the middle cerebral artery. During catheter placement animals were heparinized and vasospasm was minimized using verapamil. Anesthetic induction and maintenance were smooth. Animals with small strokes showed very rapid recovery, were able to ambulate and self-feed within 2 hours of recovery. Animals with strokes of >or=4% of the hemispheric volume required lengthy observation during recovery and parenteral nutrition. Large strokes resulted in significant brain edema, herniation and brainstem compression. Intracerebral hemorrhage and or subarachnoid hemorrhage coupled with a stroke of any size was acutely fatal. In the absence of an effective acute stroke therapy, the spectrum of outcomes seen in our primate model is very similar to that observed in human stroke patients.

Long Time Evolution of Sequestered CO2 in Porous Media

NASA Astrophysics Data System (ADS)

Cohen, Y.; Rothman, D.

2013-12-01

CO2 sequestration is important for mitigating climate change and reducing atmospheric CO2 concentration. However, a complete physical picture able to predict both the pattern formation and the structure developing within the porous medium is lacking. We propose a theoretical model that couples transport, reaction, and the intricate geometry of the rock, in order to study the long time evolution of carbon in the brine-rock environment. As CO2 is injected into a brine-rock environment, it becomes initially trapped, and isolated bubbles are formed. Within the high CO2 phase, minerals dissolve and migrate from high concentration to low concentration regions, along with other carbonate species. The change in the concentrations at the interface moves the system out of equilibrium, drives up the saturation level, and leads to mineral precipitation. We argue that mineral precipitation in a small boundary layer may lead to lower diffusivity, slower kinetics, and eventually to a mechanical trapping of the CO2 bubbles. We investigate the reactive transport model and study the conditions that cause the mechanical separation of these two reactive fluids in porous media.

Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials

NASA Astrophysics Data System (ADS)

Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos; Roelofs, Mark G.; Peterson, Darin L.; Duff, James P.; Deibler, Dean T.; Wray, L. Andrew; Yang, Wanli

2017-08-01

The mixed transition-metal layered compound, LiNi0.5Mn0.3Co0.2O2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni2+, Ni3+ and Ni4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Additionally, about 20% of Ni2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« less

Paleobotany and Global Change: Important Lessons for Species to Biomes from Vegetation Responses to Past Global Change.

PubMed

McElwain, Jennifer C

2018-04-29

Human carbon use during the next century will lead to atmospheric carbon dioxide concentrations (pCO 2 ) that have been unprecedented for the past 50-100+ million years according to fossil plant-based CO 2 estimates. The paleobotanical record of plants offers key insights into vegetation responses to past global change, including suitable analogs for Earth's climatic future. Past global warming events have resulted in transient poleward migration at rates that are equivalent to the lowest climate velocities required for current taxa to keep pace with climate change. Paleobiome reconstructions suggest that the current tundra biome is the biome most threatened by global warming. The common occurrence of paleoforests at high polar latitudes when pCO 2 was above 500 ppm suggests that the advance of woody shrub and tree taxa into tundra environments may be inevitable. Fossil pollen studies demonstrate the resilience of wet tropical forests to global change up to 700 ppm CO 2 , contrary to modeled predictions of the future. The paleobotanical record also demonstrates a high capacity for functional trait evolution as an additional strategy to migration and maintenance of a species' climate envelope in response to global change.

An ultrafine platinum-cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution.

PubMed

Wang, Ziqiang; Ren, Xiang; Luo, Yonglan; Wang, Liang; Cui, Guanwei; Xie, Fengyu; Wang, Hongjing; Xie, Ying; Sun, Xuping

2018-06-22

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Glucose respiration in the intact chloroplast of Chlamydomonas reinhardtii

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

Changguo Chen; Gibbs, M.

1991-01-01

Chloroplastic respiration was monitored by measuring {sup 14}CO{sub 2} from {sup 14}C glucose in the darkened Chlamydomonas reinhardtii F-60 chloroplast, The patterns of {sup 14}CO{sub 2} evolution from labeled glucose in the absence and presence of the inhibitors iodoacetamide, glycolate-2-phosphate, and phosphoenolypyruvate were those expected from the oxidative pentose phosphate cycle and glycolysis. The K{sub m} for glucose was 56 micromolar and for MgATP was 200 micromolar. Release of {sup 14}CO{sub 2} was inhibited by phloretin and inorganic phosphate. Comparing the inhibition of CO{sub 2} evolution generated by pH 7.5 with respect to pH 8.2 (optimum) in chloroplasts given C-1,more » C-2, and C-6 labeled glucose indicated that a suboptimum pH affects the recycling of the pentose phosphate intermediates to a greater extent than CO{sub 2} evolution from C-1 of glucose. Respiratory inhibition by pH 7.5 in the darkened chloroplast was alleviated by NH{sub 4}Cl and KCl (stromal alkalating agents), iodoacetamide (an inhibitor of glyceraldehyde 3-phosphate dehydrogenase), or phosphoenolypyruvate (an inhibitor of phosphofructokinase). It is concluded that the site which primarily mediates respiration in the darkened Chlamydomonas chloroplast is the fructose-1,6-bisphosphatase/phosphofructokinase junction. The respiratory pathways described here can account for the total oxidation of a hexose to Co{sub 2} and for interactions between carbohydrate metabolism and the oxyhydrogen reaction in algal cells adapted to a hydrogen metabolism.« less

Towards Greenland Glaciation: cumulative or abrupt transition?

NASA Astrophysics Data System (ADS)

Ramstein, Gilles; Tan, Ning; Ladant, Jean-baptiste; Dumas, Christophe; Contoux, Camille

2017-04-01

During the mid-Pliocene warming period (3-3.3 Ma BP), the global annual mean temperatures inferred by data and model studies were 2-3° warmer than pre-industrial values. Accordingly, Greenland ice sheet volume is supposed to reach at the most, only half of that of present-day [Haywood et al. 2010]. Around 2.7-2.6 Ma BP, just ˜ 500 kyr after the warming peak of mid-Pliocene, the Greenland ice sheet has reached its full size [Lunt et al. 2008]. A crucial question concerns the evolution of the Greenland ice sheet from half to full size during the 3 - 2.5 Ma period. Data show a decreasing trend of atmospheric CO2 concentration from 3 Ma to 2.5 Ma [Seki et al.2010; Bartoli et al. 2011; Martinez et al. 2015]. However, a recent study [Contoux et al. 2015] suggests that a lowering of CO2 is not sufficient to initiate a perennial glaciation on Greenland and must be combined with low summer insolation to preserve the ice sheet during insolation maxima. This suggests rather a cumulative process than an abrupt event. In order to diagnose the evolution of the ice sheet build-up, we carry on, for the first time, a transient simulation of climate and ice sheet evolutions from 3 Ma to 2.5 Ma. This strategy enables us to investigate the waxing and waning of the ice sheet during several orbital cycles. We use a tri-dimensional interpolation method designed by Ladant et al. (2014), which allows the evolution of CO2 concentration and of orbital parameters, and the evolution of the Greenland ice sheet size to be taken into account. By interpolating climatic snapshot simulations ran with various possible combinations of CO2, orbits and ice sheet sizes, we can build a continuous climatic forcing that is then used to provide 500 kyrs-long ice sheet simulations. With such a tool, we may offer a physically based answer to different CO2 reconstructions scenarios and analyse which one is the most consistent with Greenland ice sheet buildup.

Simulation of climate, ice sheets and CO2 evolution during the last four glacial cycles with an Earth system model of intermediate complexity

NASA Astrophysics Data System (ADS)

Ganopolski, Andrey; Brovkin, Victor

2017-11-01

In spite of significant progress in paleoclimate reconstructions and modelling of different aspects of the past glacial cycles, the mechanisms which transform regional and seasonal variations in solar insolation into long-term and global-scale glacial-interglacial cycles are still not fully understood - in particular, in relation to CO2 variability. Here using the Earth system model of intermediate complexity CLIMBER-2 we performed simulations of the co-evolution of climate, ice sheets, and carbon cycle over the last 400 000 years using the orbital forcing as the only external forcing. The model simulates temporal dynamics of CO2, global ice volume, and other climate system characteristics in good agreement with paleoclimate reconstructions. These results provide strong support for the idea that long and strongly asymmetric glacial cycles of the late Quaternary represent a direct but strongly nonlinear response of the Northern Hemisphere ice sheets to orbital forcing. This response is strongly amplified and globalised by the carbon cycle feedbacks. Using simulations performed with the model in different configurations, we also analyse the role of individual processes and sensitivity to the choice of model parameters. While many features of simulated glacial cycles are rather robust, some details of CO2 evolution, especially during glacial terminations, are sensitive to the choice of model parameters. Specifically, we found two major regimes of CO2 changes during terminations: in the first one, when the recovery of the Atlantic meridional overturning circulation (AMOC) occurs only at the end of the termination, a pronounced overshoot in CO2 concentration occurs at the beginning of the interglacial and CO2 remains almost constant during the interglacial or even declines towards the end, resembling Eemian CO2 dynamics. However, if the recovery of the AMOC occurs in the middle of the glacial termination, CO2 concentration continues to rise during the interglacial, similar to the Holocene. We also discuss the potential contribution of the brine rejection mechanism for the CO2 and carbon isotopes in the atmosphere and the ocean during the past glacial termination.

Carbon Chemistry in Transitional Clouds from the GOT C+ Survey of CII 158 micron Emission in the Galactic Plane

NASA Astrophysics Data System (ADS)

Langer, W. D.; Velusamy, T.; Pineda, J.; Willacy, K.; Goldsmith, P. F.

2011-05-01

In understanding the lifecycle and chemistry of the interstellar gas, the transition from diffuse atomic to molecular gas clouds is a very important stage. The evolution of carbon from C+ to C0 and CO is a fundamental part of this transition, and C+ along with its carbon chemistry is a key diagnostic. Until now our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the dense molecular H2 phase traced by CO. However, we have generally been missing an important layer in diffuse and transition clouds, which is denoted by the warm "dark gas'', that is mostly H2 and little HI and CO, and is best traced with C+. Here, we discuss the chemistry in the transition from C+ to C0 and CO in these clouds as understood by a survey of the CII 1.9 THz (158 micron) line from a sparse survey of the inner galaxy over about 40 degrees in longitude as part of the Galactic Observations of Terahertz C+ (GOT C+) program, a Herschel Space Observatory Open Time Key Program to study interstellar clouds by sampling ionized carbon. Using the first results from GOT C+ along 11 LOSs, in a sample of 53 transition clouds, Velusamy, Langer et al. (A&A 521, L18, 2010) detected an excess of CII intensities indicative of a thick H2 layer (a significant warm H2, "dark gas'' component) around the 12CO core. Here we present a much larger, statistically significant sample of a few hundred diffuse and transition clouds traced by CII, along with auxiliary HI and CO data in the inner Galaxy between l=-30° and +30°. Our new and more extensive sample of transition clouds is used to elucidate the time dependent physical and carbon chemical evolution of diffuse to transition clouds, and transition layers. We consider the C+ to CO conversion pathways such as H++ O and C+ + H2 chemistry for CO production to constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse transition clouds.

Effects of elevated CO2 concentrations on denitrifying and nitrifying popualtions at terrestrial CO2 leakeage analogous sites

NASA Astrophysics Data System (ADS)

Christine, Dictor Marie; Catherine, Joulian; Valerie, Laperche; Stephanie, Coulon; Dominique, Breeze

2010-05-01

CO2 capture and geological storage (CCS) is recognized to be an important option for carbon abatement in Europe. One of the risks of CCS is the leakage from storage site. A laboratory was conducted on soil samples sampled near-surface from a CO2 leakage analogous site (Latera, Italy) in order to evaluate the impact of an elevated soil CO2 concentration on terrestrial bacterial ecosystems form near surface terrestrial environments and to determine a potential bacterial indicator of CO2 leakage from storage site. Surveys were conducted along a 50m long transect across the vent centre, providing a spectrum of CO2 flux rates, soil gas concentrations and compositions (Beaubien et al., 2007). A bacterial diversity studies, performed by CE-SSCP technique, on a soil profile with increasing CO2 soil concentrations (from 0.3% to 100%) showed that a change on bacterial diversity was noted when CO2 concentration was above 50 % of CO2. From this result, 3 soil samples were taken at 70 cm depth in 3 distinct zones (background soil CO2 content, soil CO2 content of 20% and soil CO2 content of 50%). Then theses soil samples were incubated under closed jars flushed with different air atmospheres (20, 50 and 90 % of CO2) during 18 months. At initial, 3, 6, 12 and 18 months, some soil samples were collected in order to estimate the denitrifying, nitrifying activities as a function of CO2 concentration content and times. Theses enzymatic activities were chosen because one occurs under anaerobic conditions (denitrification) and the other occurs under aerobic conditions (nitrification). Both of them were involved in the nitrogen cycle and are major actors of soil function and groundwater quality preservation. Metabolic diversity using BIOLOG Ecoplates was determined on every soil samples. Physico-chemical parameters (e.g. pH, bulk chemistry, mineralogy) were analyzed to have some information about the evolution of the soil during the incubation with increasing soil CO2 concentrations. Statistical analyses were performed to correlate microbiological measures and physico-chemical parameters. For the soil sampled in a zone with background CO2 content, incubation under an atmosphere with 20% of CO2, induce a sharp decrease of denitrifying activity after 6 months of incubation and only after 3 months with an atmosphere of 50% of CO2. On the contrary, concerning the soil sampled in a zone with 25.5% of CO2, incubation with an atmosphere of 50% has no effect on denitrifying activity and moreover this activity was stimulated with an atmosphere of 90% of CO2.Last, with the soil sampled in an area with 65.8% of CO2, denitrifying activity was negatively impacted from the 3th month of incubation with 90% CO2.and the activity was 2 fold lower after 12th of incubation. Concerning the nitrifying activity, soil sampled in an area with background CO2 content, this one remains little affected by increasing CO2 incubation. At initial times, soil sampled in the areas with 25.5 and 65.8 % of CO2 showed low level of nitrifying activities and further CO2 incubations have no effect on these activities. At the end, denitrifying activities seems to be more sensitive to CO2 concentrations evolution in the soil. More studies need to be done as incubation with lower CO2 content (< 10%) in order to determine the threshold of CO2 that can affect the near-surface bacterial activities and identify a possible candidate of CO2 leakage from deep reservoirs.

Shelf-life extension of fresh Tuber aestivum and Tuber melanosporum truffles by modified atmosphere packaging with microperforated films.

PubMed

Rivera, Carmen Susana; Blanco, Domingo; Salvador, María Luisa; Venturini, María Eugenia

2010-05-01

The aim of this study was to design a modified atmosphere packaging suitable for Tuber melanosporum and Tuber aestivum truffles that extend their shelf life and their availability as a fresh product. Their respiration rates were determined by O(2) depletion and CO(2) formation in closed systems performed at different temperatures: 4, 10, and 23 degrees C. The results were fitted by exponential equations and derivatives of these equations were used to obtain the experimental respiration rates. Our results revealed high respiration rates in both species of truffles and respiratory quotients (RQ) higher than 1 in all the cases studied. A linear dependence of respiration rate, both R(O2) and R(CO2), on O(2) concentration was revealed. A mathematical model was used to predict the evolution of the gaseous composition at 4 degrees C in the interior of polypropylene trays (250 mL) heat sealed with 4 microperforated films of different transmission rates. A microperforated film with 2 holes (90 x 50 microm) was selected to produce an internal atmosphere of 15%CO(2)/7%O(2) at 4 degrees C. The predicted atmosphere composition was confirmed by the experimental results. The quality and microbiological characteristics of fresh truffles, packaged in these conditions, revealed that the microbial counts of pseudomonads and Enterobacteriaceae were decreased, the weight loss was reduced, the typical hard texture was maintained, and the development of mycelium growth was delayed, enabling good scores for aroma and flavor, and therefore prolonging the shelf life of T. melanosporum and T. aestivum truffles to 28 and 21 d, respectively. Practical Application: This study describes the benefits of using MAP with microperforated films in the postharvest storage of Tuber melanosporum and Tuber aestivum fresh truffles. The shelf life of T. aestivum is prolonged to 21 d and of T. melanosporum to beyond 28 d increasing the possibilities for a foreign market.

Submesoscale CO2 variability across an upwelling front off Peru

NASA Astrophysics Data System (ADS)

Köhn, Eike E.; Thomsen, Sören; Arévalo-Martínez, Damian L.; Kanzow, Torsten

2017-12-01

As a major source for atmospheric CO2, the Peruvian upwelling region exhibits strong variability in surface fCO2 on short spatial and temporal scales. Understanding the physical processes driving the strong variability is of fundamental importance for constraining the effect of marine emissions from upwelling regions on the global CO2 budget. In this study, a frontal decay on length scales of 𝒪(10 km) was observed off the Peruvian coast following a pronounced decrease in down-frontal (equatorward) wind speed with a time lag of 9 h. Simultaneously, the sea-to-air flux of CO2 on the inshore (cold) side of the front dropped from up to 80 to 10 mmol m-2 day-1, while the offshore (warm) side of the front was constantly outgassing at a rate of 10-20 mmol m-2 day-1. Based on repeated ship transects the decay of the front was observed to occur in two phases. The first phase was characterized by a development of coherent surface temperature anomalies which gained in amplitude over 6-9 h. The second phase was characterized by a disappearance of the surface temperature front within 6 h. Submesoscale mixed-layer instabilities were present but seem too slow to completely remove the temperature gradient in this short time period. Dynamics such as a pressure-driven gravity current appear to be a likely mechanism behind the evolution of the front.

Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

PubMed

Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

2015-04-07

Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude.

Bifunctional bamboo-like CoSe2 arrays for high-performance asymmetric supercapacitor and electrocatalytic oxygen evolution.

PubMed

Chen, Tian; Li, Songzhan; Gui, Pengbin; Wen, Jian; Fu, Xuemei; Fang, Guojia

2018-05-18

Bifunctional bamboo-like CoSe 2 arrays are synthesized by thermal annealing of Co(CO 3 ) 0.5 OH grown on carbon cloth in Se atmosphere. The CoSe 2 arrays obtained have excellent electrical conductivity, larger electrochemical active surface areas, and can directly serve as a binder-free electrode for supercapacitors and the oxygen evolution reaction (OER). When tested as a supercapacitor electrode, the CoSe 2 delivers a higher specific capacitance (544.6 F g -1 at current density of 1 mA cm -2 ) compared with CoO (308.2 F g -1 ) or Co 3 O 4 (201.4 F g -1 ). In addition, the CoSe 2 electrode possesses excellent cycling stability. An asymmetric supercapacitor (ASC) is also assembled based on bamboo-like CoSe 2 as a positive electrode and active carbon as a negative electrode in a 3.0 M KOH aqueous electrolyte. Owing to the unique stucture and good electrochemical performance of bamboo-like CoSe 2 , the as-assembled ACS can achieve a maximum operating voltage window of 1.7 V, a high energy density of 20.2 Wh kg -1 at a power density of 144.1 W kg -1 , and an outstanding cyclic stability. As the catalyst for the OER, the CoSe 2 exhibits a lower potential of 1.55 V (versus RHE) at current density of 10 mA cm -2 , a smaller Tafel slope of 62.5 mV dec -1 and an also outstanding stability.

Bifunctional bamboo-like CoSe2 arrays for high-performance asymmetric supercapacitor and electrocatalytic oxygen evolution

NASA Astrophysics Data System (ADS)

Chen, Tian; Li, Songzhan; Gui, Pengbin; Wen, Jian; Fu, Xuemei; Fang, Guojia

2018-05-01

Bifunctional bamboo-like CoSe2 arrays are synthesized by thermal annealing of Co(CO3)0.5OH grown on carbon cloth in Se atmosphere. The CoSe2 arrays obtained have excellent electrical conductivity, larger electrochemical active surface areas, and can directly serve as a binder-free electrode for supercapacitors and the oxygen evolution reaction (OER). When tested as a supercapacitor electrode, the CoSe2 delivers a higher specific capacitance (544.6 F g‑1 at current density of 1 mA cm‑2) compared with CoO (308.2 F g‑1) or Co3O4 (201.4 F g‑1). In addition, the CoSe2 electrode possesses excellent cycling stability. An asymmetric supercapacitor (ASC) is also assembled based on bamboo-like CoSe2 as a positive electrode and active carbon as a negative electrode in a 3.0 M KOH aqueous electrolyte. Owing to the unique stucture and good electrochemical performance of bamboo-like CoSe2, the as-assembled ACS can achieve a maximum operating voltage window of 1.7 V, a high energy density of 20.2 Wh kg‑1 at a power density of 144.1 W kg‑1, and an outstanding cyclic stability. As the catalyst for the OER, the CoSe2 exhibits a lower potential of 1.55 V (versus RHE) at current density of 10 mA cm‑2, a smaller Tafel slope of 62.5 mV dec‑1 and an also outstanding stability.

The evolving star formation rate: M⋆ relation and sSFR since z ≃ 5 from the VUDS spectroscopic survey

NASA Astrophysics Data System (ADS)

Tasca, L. A. M.; Le Fèvre, O.; Hathi, N. P.; Schaerer, D.; Ilbert, O.; Zamorani, G.; Lemaux, B. C.; Cassata, P.; Garilli, B.; Le Brun, V.; Maccagni, D.; Pentericci, L.; Thomas, R.; Vanzella, E.; Zucca, E.; Amorin, R.; Bardelli, S.; Cassarà, L. P.; Castellano, M.; Cimatti, A.; Cucciati, O.; Durkalec, A.; Fontana, A.; Giavalisco, M.; Grazian, A.; Paltani, S.; Ribeiro, B.; Scodeggio, M.; Sommariva, V.; Talia, M.; Tresse, L.; Vergani, D.; Capak, P.; Charlot, S.; Contini, T.; de la Torre, S.; Dunlop, J.; Fotopoulou, S.; Koekemoer, A.; López-Sanjuan, C.; Mellier, Y.; Pforr, J.; Salvato, M.; Scoville, N.; Taniguchi, Y.; Wang, P. W.

2015-09-01

We study the evolution of the star formation rate (SFR) - stellar mass (M⋆) relation and specific star formation rate (sSFR) of star-forming galaxies (SFGs) since a redshift z ≃ 5.5 using 2435 (4531) galaxies with highly reliable spectroscopic redshifts in the VIMOS Ultra-Deep Survey (VUDS). It is the first time that these relations can be followed over such a large redshift range from a single homogeneously selected sample of galaxies with spectroscopic redshifts. The log (SFR) - log (M⋆) relation for SFGs remains roughly linear all the way up to z = 5, but the SFR steadily increases at fixed mass with increasing redshift. We find that for stellar masses M⋆ ≥ 3.2 × 109M⊙ the SFR increases by a factor of ~13 between z = 0.4 and z = 2.3. Weextend this relation up to z = 5, finding an additional increase in SFR by a factor of 1.7 from z = 2.3 to z = 4.8 for masses M⋆ ≥ 1010M⊙. We observe a turn-off in the SFR-M⋆ relation at the highest mass end up to a redshift z ~ 3.5. We interpret this turn-off as the signature of a strong on-going quenching mechanism and rapid mass growth. The sSFR increases strongly up to z ~ 2, but it grows much less rapidly in 2

Respiration-to-DNA ratio reflects physiological state of microorganisms in root-free and rhizosphere soil

NASA Astrophysics Data System (ADS)

Blagodatskaya, E.; Blagodatsky, S.; Kuzyakov, Y.

2009-04-01

The double-stranded DNA (dsDNA) content in soil can serve as a measure of microbial biomass under near steady-state conditions and quantitatively reflect the exponential microbial growth initiated by substrate addition. The yield of respired CO2 per microbial biomass unit (expressed as DNA content) could be a valuable physiological indicator reflecting state of soil microbial community. Therefore, investigations combining both analyses of DNA content and respiration of soil microorganisms under steady-state and during periods of rapid growth are needed. We studied the relationship between CO2 evolution and microbial dsDNA content in native and glucose-amended samples of root-free and rhizosphere soil under Beta vulgaris (Cambisol, loamy sand from the field experiment of the Institute of Agroecology FAL, Braunschweig, Germany). Quantity of dsDNA was determined by direct DNA isolation from soil with mechanic and enzymatic disruption of microbial cell walls with following spectrofluorimetric detection with PicoGreen (Blagodatskaya et al., 2003). Microbial biomass and the kinetic parameters of microbial growth were estimated by dynamics of the CO2 emission from soil amended with glucose and nutrients (Blagodatsky et al., 2000). The CO2 production rate was measured hourly at 22оС using an automated infrared-gas analyzer system. The overall increase in microbial biomass, DNA content, maximal specific growth rate and therefore, in the fraction of microorganisms with r-strategy were observed in rhizosphere as compared to bulk soil. The rhizosphere effect for microbial respiration, biomass and specific growth rate was more pronounced for plots with half-rate of N fertilizer compared to full N addition. The DNA content was significantly lower in bulk compared to rhizosphere soil both before and during microbial growth initiated by glucose amendment. Addition of glucose to the soil strongly increased the amount of CO2 respired per DNA unit. Without substrate addition the VCO2-to-total DNA ratios were lower than 0.1 µg CO2-C µg-1 total DNA h-1 whereas during exponential microbial growth these values increased consistently and exceeded 1 µg CO2-C µg-1 DNA h-1. Thus, the VCO2-to-total DNA ratio strongly changes along with the physiological state of soil microorganisms and can be used as valuable physiological parameter. In growing microorganisms the quantity of CO2 evolved per unit of newly formed DNA was identical in rhizosphere and root free soil and averaged for 13.5 ± 1.1 µg CO2-C µg-1 newly formed DNA. The CO2 yield per unit of newly formed DNA allows the estimation of microbial growth efficiency and validation of specific growth rates obtained during kinetic analysis of respiration curves. The study was supported by European Commission (Marie Curie IIF program, project MICROSOM) and by Alexander von Humboldt Foundation. References: Blagodatskaya EV, Blagodatskii SA, Anderson TH. 2003. Quantitative Isolation of Microbial DNA from Different Types of Soils of Natural and Agricultural Ecosystems. Microbiology 72(6):744-749. Blagodatsky SA, Heinemeyer O, Richter J. 2000. Estimating the active and total soil microbial biomass by kinetic respiration analysis. Biology and Fertility of Soils 32(1):73-81.

Single crystalline Co3O4 nanocrystals exposed with different crystal planes for Li-O2 batteries.

PubMed

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-08-29

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}.

Calcium metaborate as a cathode additive to improve the high-temperature properties of nickel hydroxide electrodes for nickel-metal hydride batteries

NASA Astrophysics Data System (ADS)

Li, Jing; Shangguan, Enbo; Guo, Dan; Li, Quanmin; Chang, Zhaorong; Yuan, Xiao-Zi; Wang, Haijiang

2014-10-01

In this paper, a novel additive, calcium metaborate (CMB), is proposed to improve the high-temperature characteristics of the nickel electrodes for nickel-metal hydride batteries. As a soluble calcium salt, CMB can easily and uniformly be dispersed in the nickel electrodes. The effects of CMB on the nickel electrode are investigated via a combination of cyclability, capacity retention, electrochemical impedance spectroscopy, scanning electron microscope and X-ray diffraction. Compared with conventional nickel electrodes, the electrode containing 0.5 wt.% CMB exhibits superior electrode properties including enhanced discharge capacity, improved high-rate discharge ability and excellent cycle stability at an elevated temperature (70 °C). The improved cell performance of the nickel electrode containing CMB additives can be attributable to the increased oxygen evolution overvoltage and slower oxygen evolution rate. Compared with insoluble calcium salts, such as Ca(OH)2, CaCO3, and CaF2, CMB is more effective as a cathode additive to improve the high-temperature performance of Ni-MH batteries.

The late Miocene 'paradox' of the CO2 climate sensitivity (Invited)

NASA Astrophysics Data System (ADS)

Zhang, Y.; Pagani, M.

2013-12-01

Ancient climates provide opportunities for studying the impact of CO2 change on global temperatures. While advances in CO2-reconstruction techniques are yielding a clearer picture of the Cenozoic history of CO2 (Beerling and Royer, 2011), the late Miocene (~12-5 Ma) remains enigmatic. For example, recent sea-surface temperature reconstructions from 12-5 Ma have shown that mid-latitude and equatorial regions of the Pacific cooled 6°C (LaRiviere et al., 2012) and 2°C (Zhang et al., 2013), respectively. This cooling trend was probably initiated at the mid-Miocene climate transition (14 Ma), and continued into the Plio-Pleistocene. However, existing compilation of late Miocene - Pliocene CO2 records show little variability, with some indicating a rise in CO2 concurrent with global cooling. Here we present four continuous alkenone-based CO2 records using Pacific sediment samples (ODP Sites 769, 806, 850 and 1143), from late Miocene to Pliocene. Compound-specific carbon isotope measurements show a broad decrease in alkenone δ13C values in all four sites, suggesting increasing pCO2 levels in the late Miocene. Decreasing ocean temperature and increasing pCO2 in the late Miocene appears to challenge a leading climatic role for CO2 during this time. Alternatively, alkenone-CO2 estimates are flawed in the late Miocene because factors other than CO2, such as algal growth rate, cell geometry, and carbon-fixation pathways, can influence carbon isotopic fractionation during algae growth. We explore the uncertainty of the alkenone-CO2 methodology and assess the potential influence that non-CO2 variables have in producing spurious CO2 estimates and trends. Beerling, D.J., Royer, D.L., 2011. Convergent Cenozoic CO2 history. Nat. Geosci. 4, 418-420. LaRiviere, J.P., Ravelo, A.C., Crimmins, A., Dekens, P.S., Ford, H.L., Lyle, M., Wara, M.W., 2012. Late Miocene decoupling of oceanic warmth and atmospheric carbon dioxide forcing. Nature 486, 97-100. Zhang, Y.G., Pagani, M., Liu, Z., 2013. Temperature evolution of the equatorial Pacific since late Miocene and the ancient El Nino. In Preperation.

PHYSICAL EFFECTS OCCURRING DURING GENERATION AND AMPLIFICATION OF LASER RADIATION: Dynamics of population of the A3∑u+ nitrogen metastable state in a self-sustained volume discharge of a pulsed CO2 laser

NASA Astrophysics Data System (ADS)

Apollonov, V. V.; Baĭtsur, G. G.; Ermachenko, A. V.; Raspopov, N. A.; Sviridenkov, É. A.; Semenov, S. K.; Firsov, K. N.

1989-02-01

Intracavity laser spectroscopy was used to study the dynamics of population of the ν = 2-8 vibrational levels of the A3∑u+ state in order to establish the possible influence of multistage ionization on the evolution of instability in a self-sustained volume discharge in CO2 laser active mixtures. The populations of the nitrogen vibrational levels Nν were calculated taking into account the real output pulse profile of a dye laser. It was found that multistage ionization can only influence the duration of stable operation of a self-sustained volume discharge by increasing the rate of growth of the spark channel in the discharge gap. This is why the addition of readily ionized substances to the gas that reduce the electron energy and therefore lower Nν can substantially improve the stability of the volume discharge and increase the active volume and output energy of a CO2 laser.

Evolution of lung breathing from a lungless primitive vertebrate.

PubMed

Hoffman, M; Taylor, B E; Harris, M B

2016-04-01

Air breathing was critical to the terrestrial radiation and evolution of tetrapods and arose in fish. The vertebrate lung originated from a progenitor structure present in primitive boney fish. The origin of the neural substrates, which are sensitive to metabolically produced CO2 and which rhythmically activate respiratory muscles to match lung ventilation to metabolic demand, is enigmatic. We have found that a distinct periodic centrally generated rhythm, described as "cough" and occurring in lamprey in vivo and in vitro, is modulated by central sensitivity to CO2. This suggests that elements critical for the evolution of breathing in tetrapods, were present in the most basal vertebrate ancestors prior to the evolution of the lung. We propose that the evolution of breathing in all vertebrates occurred through exaptations derived from these critical basal elements. Copyright © 2015 Elsevier B.V. All rights reserved.

Foundational errors in the Neutral and Nearly-Neutral theories of evolution in relation to the Synthetic Theory: is a new evolutionary paradigm necessary?

PubMed

Valenzuela, Carlos Y

2013-01-01

The Neutral Theory of Evolution (NTE) proposes mutation and random genetic drift as the most important evolutionary factors. The most conspicuous feature of evolution is the genomic stability during paleontological eras and lack of variation among taxa; 98% or more of nucleotide sites are monomorphic within a species. NTE explains this homology by random fixation of neutral bases and negative selection (purifying selection) that does not contribute either to evolution or polymorphisms. Purifying selection is insufficient to account for this evolutionary feature and the Nearly-Neutral Theory of Evolution (N-NTE) included negative selection with coefficients as low as mutation rate. These NTE and N-NTE propositions are thermodynamically (tendency to random distributions, second law), biotically (recurrent mutation), logically and mathematically (resilient equilibria instead of fixation by drift) untenable. Recurrent forward and backward mutation and random fluctuations of base frequencies alone in a site make life organization and fixations impossible. Drift is not a directional evolutionary factor, but a directional tendency of matter-energy processes (second law) which threatens the biotic organization. Drift cannot drive evolution. In a site, the mutation rates among bases and selection coefficients determine the resilient equilibrium frequency of bases that genetic drift cannot change. The expected neutral random interaction among nucleotides is zero; however, huge interactions and periodicities were found between bases of dinucleotides separated by 1, 2... and more than 1,000 sites. Every base is co-adapted with the whole genome. Neutralists found that neutral evolution is independent of population size (N); thus neutral evolution should be independent of drift, because drift effect is dependent upon N. Also, chromosome size and shape as well as protein size are far from random.

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution.

PubMed

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy-carbon core-shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10-30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2-6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Photocatalytic degradation of E. coliform in water.

PubMed

Sun, Darren Delai; Tay, Joo Hwa; Tan, Koh Min

2003-08-01

This study aims to further investigate the total mineralization of the bacteria to the extent of death and cell-mass inactivation using a TiO2-Fe2O3 membrane photocatalytic oxidation reactor. Experimental results clearly indicated that dissolved oxygen (DO), hydraulic retention time (HRT) and concentration of the model bacteria (Escherichia coliform) affected the removal efficiency. It was found that the ultimate removal efficiency was 99% at DO level of 21.34 mg/l, HRT at 60s and high concentration of E. coli at 10(9)CFU/ml. The morphologic studies also showed that E. coliform could be further mineralized into CO2 and H2O. Dissolved organic carbon, pH and gas chromatograph analysis had justified most importantly the evolution of CO2. Experimental results revealed that the photomineralization rate of E. coliform followed pseudo-first-order kinetics by the role of DO. The derived empirical models were found consistent with the proposed reaction pathways of a combined UV breakdown on mass cell and a dual-site Langmuir-Hinshelwood mechanism where the rate-controlling step is the surface interaction between the adsorbed cleavage bacterial cells and hydroxyl radicals.

Fitness cost of reassortment in human influenza.

PubMed

Villa, Mara; Lässig, Michael

2017-11-01

Reassortment, which is the exchange of genome sequence between viruses co-infecting a host cell, plays an important role in the evolution of segmented viruses. In the human influenza virus, reassortment happens most frequently between co-existing variants within the same lineage. This process breaks genetic linkage and fitness correlations between viral genome segments, but the resulting net effect on viral fitness has remained unclear. In this paper, we determine rate and average selective effect of reassortment processes in the human influenza lineage A/H3N2. For the surface proteins hemagglutinin and neuraminidase, reassortant variants with a mean distance of at least 3 nucleotides to their parent strains get established at a rate of about 10-2 in units of the neutral point mutation rate. Our inference is based on a new method to map reassortment events from joint genealogies of multiple genome segments, which is tested by extensive simulations. We show that intra-lineage reassortment processes are, on average, under substantial negative selection that increases in strength with increasing sequence distance between the parent strains. The deleterious effects of reassortment manifest themselves in two ways: there are fewer reassortment events than expected from a null model of neutral reassortment, and reassortant strains have fewer descendants than their non-reassortant counterparts. Our results suggest that influenza evolves under ubiquitous epistasis across proteins, which produces fitness barriers against reassortment even between co-circulating strains within one lineage.

Coupled thermal–hydrological–mechanical modeling of CO 2 -enhanced coalbed methane recovery

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

Ma, Tianran; Rutqvist, Jonny; Oldenburg, Curtis M.

CO 2 -enhanced coalbed methane recovery, also known as CO 2 -ECBM, is a potential win-win approach for enhanced methane production while simultaneously sequestering injected anthropogenic CO 2 to decrease CO 2 emissions into the atmosphere. Here, CO 2 -ECBM is simulated using a coupled thermal–hydrological–mechanical (THM) numerical model that considers multiphase (gas and water) flow and solubility, multicomponent (CO 2 and CH 4 ) diffusion and adsorption, heat transfer and coal deformation. The coupled model is based on the TOUGH-FLAC simulator, which is applied here for the first time to model CO 2 -ECBM. The capacity of the simulatormore » for modeling methane production is verified by a code-to-code comparison with the general-purpose finite-element solver COMSOL. Then, the TOUGH-FLAC simulator is applied in an isothermal simulation to study the variations in permeability evolution during a CO 2 -ECBM operation while considering four different stress-dependent permeability models that have been implemented into the simulator. Finally, the TOUGH-FLAC simulator is applied in non-isothermal simulations to model THM responses during a CO 2 -ECBM operation.Our simulations show that the permeability evolution, mechanical stress, and deformation are all affected by changes in pressure, temperature and adsorption swelling, with adsorption swelling having the largest effect. The calculated stress changes do not induce any mechanical failure in the coal seam, except near the injection well in one case of a very unfavorable stress field.« less

Coupled thermal–hydrological–mechanical modeling of CO 2 -enhanced coalbed methane recovery

DOE PAGES

Ma, Tianran; Rutqvist, Jonny; Oldenburg, Curtis M.; ...

2017-05-22

CO 2 -enhanced coalbed methane recovery, also known as CO 2 -ECBM, is a potential win-win approach for enhanced methane production while simultaneously sequestering injected anthropogenic CO 2 to decrease CO 2 emissions into the atmosphere. Here, CO 2 -ECBM is simulated using a coupled thermal–hydrological–mechanical (THM) numerical model that considers multiphase (gas and water) flow and solubility, multicomponent (CO 2 and CH 4 ) diffusion and adsorption, heat transfer and coal deformation. The coupled model is based on the TOUGH-FLAC simulator, which is applied here for the first time to model CO 2 -ECBM. The capacity of the simulatormore » for modeling methane production is verified by a code-to-code comparison with the general-purpose finite-element solver COMSOL. Then, the TOUGH-FLAC simulator is applied in an isothermal simulation to study the variations in permeability evolution during a CO 2 -ECBM operation while considering four different stress-dependent permeability models that have been implemented into the simulator. Finally, the TOUGH-FLAC simulator is applied in non-isothermal simulations to model THM responses during a CO 2 -ECBM operation.Our simulations show that the permeability evolution, mechanical stress, and deformation are all affected by changes in pressure, temperature and adsorption swelling, with adsorption swelling having the largest effect. The calculated stress changes do not induce any mechanical failure in the coal seam, except near the injection well in one case of a very unfavorable stress field.« less

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

2018-01-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

Photocatalysis using a Wide Range of the Visible Light Spectrum: Hydrogen Evolution from Doped AgGaS2.

PubMed

Yamato, Kohei; Iwase, Akihide; Kudo, Akihiko

2015-09-07

Doping of nickel into AgGaS2 yields a new absorption band, at a wavelength longer than the intrinsic absorption band of the AgGaS2 host. The doped nickel forms an electron donor level in a forbidden band of AgGaS2 . The nickel-doped AgGaS2 with rhodium co-catalyst shows photocatalytic activity for sacrificial H2 evolution under the light of up to 760 nm due to the transition from the electron donor level consisting of Ni(2+) to the conduction band of AgGaS2 . Apparent quantum yields for the sacrificial H2 evolution at 540-620 nm are about 1 %. Moreover, the nickel-doped AgGa0.75 In0.25 S2 also responds to near-IR light, up to 900 nm. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of homogeneous electrocatalysts by cyclic voltammetry.

PubMed

Rountree, Eric S; McCarthy, Brian D; Eisenhart, Thomas T; Dempsey, Jillian L

2014-10-06

The pursuit of solar fuels has motivated extensive research on molecular electrocatalysts capable of evolving hydrogen from protic solutions, reducing CO2, and oxidizing water. Determining accurate figures of merit for these catalysts requires the careful and appropriate application of electroanalytical techniques. This Viewpoint first briefly presents the fundamentals of cyclic voltammetry and highlights practical experimental considerations before focusing on the application of cyclic voltammetry for the characterization of electrocatalysts. Key metrics for comparing catalysts, including the overpotential (η), potential for catalysis (E(cat)), observed rate constant (k(obs)), and potential-dependent turnover frequency, are discussed. The cyclic voltammetric responses for a general electrocatalytic one-electron reduction of a substrate are presented along with methods to extract figures of merit from these data. The extension of this analysis to more complex electrocatalytic schemes, such as those responsible for H2 evolution and CO2 reduction, is then discussed.

One-pot Synthesis of CdS Irregular Nanospheres Hybridized with Oxygen-Incorporated Defect-Rich MoS2 Ultrathin Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Zhang, Shouwei; Yang, Hongcen; Gao, Huihui; Cao, Ruya; Huang, Jinzhao; Xu, Xijin

2017-07-19

Robust and highly active photocatalysts, CdS@MoS 2 , for hydrogen evolution were successfully fabricated by one-step growth of oxygen-incorporated defect-rich MoS 2 ultrathin nanosheets on the surfaces of CdS with irregular fissures. Under optimized experimental conditions, the CdS@MoS 2 displayed a quantum yield of ∼24.2% at 420 nm and the maximum H 2 generation rate of ∼17203.7 umol/g/h using Na 2 S-Na 2 SO 3 as sacrificial agents (λ ≥ 420 nm), which is ∼47.3 and 14.7 times higher than CdS (∼363.8 μmol/g/h) and 3 wt % Pt/CdS (∼1173.2 μmol/g/h), respectively, and far exceeds all previous hydrogen evolution reaction photocatalysts with MoS 2 as co-catalysts using Na 2 S-Na 2 SO 3 as sacrificial agents. Large volumes of hydrogen bubbles were generated within only 2 s as the photocatalysis started, as demonstrated by the photocatalytic video. The high hydrogen evolution activity is attributed to several merits: (1) the intimate heterojunctions formed between the MoS 2 and CdS can effectively enhance the charge transfer ability and retard the recombination of electron-hole pairs; and (2) the defects in the MoS 2 provide additional active S atoms on the exposed edge sites, and the incorporation of O reduces the energy barrier for H 2 evolution and increases the electric conductivity of the MoS 2 . Considering its low cost and high efficiency, this highly efficient hybrid photocatalysts would have great potential in energy-generation and environment-restoration fields.

The effect of a confining unit on the geochemical evolution of ground water in the Upper Floridan aquifer system

USGS Publications Warehouse

Wicks, C.M.; Herman, J.S.

1994-01-01

In west-central Florida, sections of the Upper Floridan aquifer system range in character from confined to leaky to unconfined. The confining unit is the Hawthorn Formation, a clay-rich sequence. The presence or absence of the Hawthorn Formation affects the geochemical evolution of the ground water in the Upper Floridan aquifer system. Mass-balance and mass-transfer models suggest that, in unconfined areas, the geochemical reactions are dolomite dissolution, ion exchange (Mg for Na, K), sulfate reduction, calcite dissolution, and CO2 exchange. In the areas in which the Hawthorn Formation is leaky, the evolution of the ground water is accounted for by ion exchange, sulfate reduction, calcite dissolution, and CO2 exchange. In the confined areas, no ion exchange and only limited sulfate reduction occur, and the chemical character of the ground water is consistent with dolomite and gypsum dissolution, calcite precipitation, and CO2 ingassing. The Hawthorn Formation acts both as a physical barrier to the transport of CO2 and organic matter and as a source of ion-exchange sites, but the carbonate-mineral reactions are largely unaffected by the extent of confinement of the Upper Floridan aquifer. ?? 1994.

Synthetic Active Site Model of the [NiFeSe] Hydrogenase

PubMed Central

Wombwell, Claire; Reisner, Erwin

2015-01-01

A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe(‘S2Se2’)(CO)3] (H2‘S2Se2’=1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni(‘S2Se2’)] with [Fe(CO)3bda] (bda=benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe(‘S2Se2’)(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe(‘S2Se2’)(CO)3] with the previously reported thiolate analogue [NiFe(‘S4’)(CO)3] (H2‘S4’=H2xbsms=1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe(‘S2Se2’)(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe(‘S2Se2’)(CO)3] and [NiFe(‘S4’)(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. PMID:25847470

Evolution of the Active Phase of CoMo/Al2O3 Catalysts under Industrial Conditions: a High-Pressure MES Study

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

Dugulan, A.I.; Overweg, A.R.; Craje, M.W.J.

2005-04-26

The behavior of CoMo/Al2O3 catalysts sulfided in H2S/H2 gas mixture, under industrial conditions, was investigated using Moessbauer emission spectroscopy (MES). An intermediate Co-Mo phase is formed after increasing the sulfidation pressure to 4 MPa, favoring the Co-Mo-S phase formation. An increase in the quadrupole splitting value of the Co-sulfide species after treatment at 573 K is proposed as a prerequisite for the formation of ideal Co-Mo-S structures.

Photosynthesis of Scenedesmus obliquus in outdoor open thin-layer cascade system in high and low CO2 in Belgium.

PubMed

de Marchin, Thomas; Erpicum, Michel; Franck, Fabrice

2015-12-10

Two outdoor open thin-layer cascade systems operated as batch cultures with the alga Scenedesmus obliquus were used to compare the productivity and photosynthetic acclimations in control and CO2 supplemented cultures in relation with the outdoor light irradiance. We found that the culture productivity was limited by CO2 availability. In the CO2 supplemented culture, we obtained a productivity of up to 24gdwm(-2)day(-1) and found a photosynthetic efficiency (value based on the PAR solar radiation energy) of up to 5%. In the CO2 limited culture, we obtained a productivity of up to 10gdwm(-2)day(-1) while the photosynthetic efficiency was up to 3.3% and decreased to 2.1% when the integrated daily PAR increased. Fluorescence and oxygen evolution measurements showed that ETR and oxygen evolution light saturation curves, as well as light-dependent O2 uptake were similar in algal samples from both cultures when the CO2 limitation was removed. In contrast, we found that CO2 limitation conducted to a decreased PSII photochemical efficiency and an increased light-induced heat-dissipation in the control culture compared to the CO2 supplemented culture. These features are in line with a lower light use efficiency and may therefore contribute to the lower productivity observed in absence of CO2 supplementation in outdoor mass cultures of S. obliquus. Copyright © 2015 Elsevier B.V. All rights reserved.

Future ocean hypercapnia driven by anthropogenic amplification of the natural CO2 cycle

NASA Astrophysics Data System (ADS)

McNeil, B.

2016-02-01

Elevated carbon dioxide concentrations in seawater (hypercapnia) can induce neurological, physiological and behavioural deficiencies in marine animals. Prediction of the onset and evolution of hypercapnia in the ocean requires a good understanding of annual oceanic carbon dioxide variability, but relevant global observational data are sparse. Here we diagnose global ocean patterns of monthly carbon variability based on observations that allow us to examine the evolution of surface ocean CO2 levels over the entire annual cycle under increasing atmospheric CO2 concentrations. We find that some oceanic regions undergo an up to 10-fold amplification of the natural cycle of CO2 by 2100, if atmospheric carbon dioxide concentrations continue to rise throughout this century (RCP8.5). Projections from a suite of Earth System Climate Models are broadly consistent with the findings from our data based approach. Our predicted amplification in the annual CO2 cycle displays distinct global patterns that may expose major fisheries in the Southern, Pacific and North Atlantic Oceans to high CO2 events many decades earlier than expected from average atmospheric CO2 concentrations. We suggest that these ocean 'CO2 hotspots' evolve as a combination of the strong seasonal dynamics of CO2 and the long-term effective storage of anthropogenic CO2 that lowers the buffer capacity in those regions, causing a non-linear CO2 amplification over the annual cycle. The onset of ocean hypercapnia events (pCO2 >1000 µatm) is forecast for atmospheric CO2 concentrations that exceed 650 ppm, with hypercapnia spreading to up to one half of the surface ocean by the year 2100 under a high-emissions scenario (RCP8.5) with potential implications for fisheries over the coming century.

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

PubMed

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

The Class 0 Protostar BHR71: Herschel Observations and Dust Continuum Models

NASA Astrophysics Data System (ADS)

Yang, Yao-Lun; Evans, Neal J., II; Green, Joel D.; Dunham, Michael M.; Jørgensen, Jes K.

2017-02-01

We use Herschel spectrophotometry of BHR71, an embedded Class 0 protostar, to provide new constraints on its physical properties. We detect 645 (non-unique) spectral lines among all spatial pixels. At least 61 different spectral lines originate from the central region. A CO rotational diagram analysis shows four excitation temperature components, 43, 197, 397, and 1057 K. Low-J CO lines trace the outflow while the high-J CO lines are centered on the infrared source. The low-excitation emission lines of {{{H}}}2{{O}} trace the large-scale outflow, while the high-excitation emission lines trace a small-scale distribution around the equatorial plane. We model the envelope structure using the dust radiative transfer code, hyperion, incorporating rotational collapse, an outer static envelope, outflow cavity, and disk. The evolution of a rotating collapsing envelope can be constrained by the far-infrared/millimeter spectral energy distribution along with the azimuthally averaged radial intensity profile, and the structure of the outflow cavity plays a critical role at shorter wavelengths. Emission at 20-40 μm requires a cavity with a constant-density inner region and a power-law density outer region. The best-fit model has an envelope mass of 19 {M}⊙ inside a radius of 0.315 pc and a central luminosity of 18.8 {L}⊙ . The time since collapse began is 24,630-44,000 years, most likely around 36,000 years. The corresponding mass infall rate in the envelope (1.2 × 10-5 {M}⊙ {{yr}}-1) is comparable to the stellar mass accretion rate, while the mass-loss rate estimated from the CO outflow is 20% of the stellar mass accretion rate. We find no evidence for episodic accretion.

Cost sharing and hospitalizations for ambulatory care sensitive conditions.

PubMed

Arrieta, Alejandro; García-Prado, Ariadna

2015-01-01

During the last decade, Chile's private health sector has experienced a dramatic increase in hospitalization rates, growing at four times the rate of ambulatory visits. Such evolution has raised concern among policy-makers. We studied the effect of ambulatory and hospital co-insurance rates on hospitalizations for ambulatory care sensitive conditions (ACSC) among individuals with private insurance in Chile. We used a large administrative dataset of private insurance claims for the period 2007-8 and a final sample of 2,792,662 individuals to estimate a structural model of two equations. The first equation was for ambulatory visits and the second for future hospitalizations for ACSC. We estimated the system by Two Stage Least Squares (2SLS) corrected by heteroskedasticity via Generalized Method of Moments (GMM) estimation. Results show that increased ambulatory visits reduced the probability of future hospitalizations, and increased ambulatory co-insurance decreased ambulatory visits for the adult population (19-65 years-old). Both findings indicate the need to reduce ambulatory co-insurance as a way to reduce hospitalizations for ACSC. Results also showed that increasing hospital co-insurance does have a statistically significant reduction on hospitalizations for the adult group, while it does not seem to have a significant effect on hospitalizations for the children (1-18 years-old) group. This paper's contribution is twofold: first, it shows how the level of co-insurance can be a determinant in avoiding unnecessary hospitalizations for certain conditions; second, it highlights the relevance for policy-making of using data on ACSC to improve the efficiency of health systems by promoting ambulatory care as well as population health. Copyright © 2014 Elsevier Ltd. All rights reserved.

Co-existence of Distinct Prion Types Enables Conformational Evolution of Human PrPSc by Competitive Selection*

PubMed Central

Haldiman, Tracy; Kim, Chae; Cohen, Yvonne; Chen, Wei; Blevins, Janis; Qing, Liuting; Cohen, Mark L.; Langeveld, Jan; Telling, Glenn C.; Kong, Qingzhong; Safar, Jiri G.

2013-01-01

The unique phenotypic characteristics of mammalian prions are thought to be encoded in the conformation of pathogenic prion proteins (PrPSc). The molecular mechanism responsible for the adaptation, mutation, and evolution of prions observed in cloned cells and upon crossing the species barrier remains unsolved. Using biophysical techniques and conformation-dependent immunoassays in tandem, we isolated two distinct populations of PrPSc particles with different conformational stabilities and aggregate sizes, which frequently co-exist in the most common human prion disease, sporadic Creutzfeldt-Jakob disease. The protein misfolding cyclic amplification replicates each of the PrPSc particle types independently and leads to the competitive selection of those with lower initial conformational stability. In serial propagation with a nonglycosylated mutant PrPC substrate, the dominant PrPSc conformers are subject to further evolution by natural selection of the subpopulation with the highest replication rate due to its lowest stability. Cumulatively, the data show that sporadic Creutzfeldt-Jakob disease PrPSc is not a single conformational entity but a dynamic collection of two distinct populations of particles. This implies the co-existence of different prions, whose adaptation and evolution are governed by the selection of progressively less stable, faster replicating PrPSc conformers. PMID:23974118

Dynamic Evolution of Cement Composition and Transport Properties under Conditions Relevant to Geological Carbon Sequestration

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

Brunet, Jean-Patrick Leopold; Li, Li; Karpyn, Zuleima T

2013-08-01

Assessing the possibility of CO{sub 2} leakage is one of the major challenges for geological carbon sequestration. Injected CO{sub 2} can react with wellbore cement, which can potentially change cement composition and transport properties. In this work, we develop a reactive transport model based on experimental observations to understand and predict the property evolution of cement in direct contact with CO{sub 2}-saturated brine under diffusion-controlled conditions. The model reproduced the observed zones of portlandite depletion and calcite formation. Cement alteration is initially fast and slows down at later times. This work also quantified the role of initial cement properties, inmore » particular the ratio of the initial portlandite content to porosity (defined here as φ), in determining the evolution of cement properties. Portlandite-rich cement with large φ values results in a localized “sharp” reactive diffusive front characterized by calcite precipitation, leading to significant porosity reduction, which eventually clogs the pore space and prevents further acid penetration. Severe degradation occurs at the cement–brine interface with large φ values. This alteration increases effective permeability by orders of magnitude for fluids that preferentially flow through the degraded zone. The significant porosity decrease in the calcite zone also leads to orders of magnitude decrease in effective permeability, where fluids flow through the low-permeability calcite zone. The developed reactive transport model provides a valuable tool to link cement–CO{sub 2} reactions with the evolution of porosity and permeability. It can be used to quantify and predict long-term wellbore cement behavior and can facilitate the risk assessment associated with geological CO{sub 2} sequestration.« less

Rubisco Catalytic Properties and Temperature Response in Crops1

PubMed Central

2016-01-01

Rubisco catalytic traits and their thermal dependence are two major factors limiting the CO2 assimilation potential of plants. In this study, we present the profile of Rubisco kinetics for 20 crop species at three different temperatures. The results largely confirmed the existence of significant variation in the Rubisco kinetics among species. Although some of the species tended to present Rubisco with higher thermal sensitivity (e.g. Oryza sativa) than others (e.g. Lactuca sativa), interspecific differences depended on the kinetic parameter. Comparing the temperature response of the different kinetic parameters, the Rubisco Km for CO2 presented higher energy of activation than the maximum carboxylation rate and the CO2 compensation point in the absence of mitochondrial respiration. The analysis of the Rubisco large subunit sequence revealed the existence of some sites under adaptive evolution in branches with specific kinetic traits. Because Rubisco kinetics and their temperature dependency were species specific, they largely affected the assimilation potential of Rubisco from the different crops, especially under those conditions (i.e. low CO2 availability at the site of carboxylation and high temperature) inducing Rubisco-limited photosynthesis. As an example, at 25°C, Rubisco from Hordeum vulgare and Glycine max presented, respectively, the highest and lowest potential for CO2 assimilation at both high and low chloroplastic CO2 concentrations. In our opinion, this information is relevant to improve photosynthesis models and should be considered in future attempts to design more efficient Rubiscos. PMID:27329223

Rubisco Catalytic Properties and Temperature Response in Crops.

PubMed

Hermida-Carrera, Carmen; Kapralov, Maxim V; Galmés, Jeroni

2016-08-01

Rubisco catalytic traits and their thermal dependence are two major factors limiting the CO2 assimilation potential of plants. In this study, we present the profile of Rubisco kinetics for 20 crop species at three different temperatures. The results largely confirmed the existence of significant variation in the Rubisco kinetics among species. Although some of the species tended to present Rubisco with higher thermal sensitivity (e.g. Oryza sativa) than others (e.g. Lactuca sativa), interspecific differences depended on the kinetic parameter. Comparing the temperature response of the different kinetic parameters, the Rubisco Km for CO2 presented higher energy of activation than the maximum carboxylation rate and the CO2 compensation point in the absence of mitochondrial respiration. The analysis of the Rubisco large subunit sequence revealed the existence of some sites under adaptive evolution in branches with specific kinetic traits. Because Rubisco kinetics and their temperature dependency were species specific, they largely affected the assimilation potential of Rubisco from the different crops, especially under those conditions (i.e. low CO2 availability at the site of carboxylation and high temperature) inducing Rubisco-limited photosynthesis. As an example, at 25°C, Rubisco from Hordeum vulgare and Glycine max presented, respectively, the highest and lowest potential for CO2 assimilation at both high and low chloroplastic CO2 concentrations. In our opinion, this information is relevant to improve photosynthesis models and should be considered in future attempts to design more efficient Rubiscos. © 2016 American Society of Plant Biologists. All Rights Reserved.

Sublethal streptomycin concentrations and lytic bacteriophage together promote resistance evolution.

PubMed

Cairns, Johannes; Becks, Lutz; Jalasvuori, Matti; Hiltunen, Teppo

2017-01-19

Sub-minimum inhibiting concentrations (sub-MICs) of antibiotics frequently occur in natural environments owing to wide-spread antibiotic leakage by human action. Even though the concentrations are very low, these sub-MICs have recently been shown to alter bacterial populations by selecting for antibiotic resistance and increasing the rate of adaptive evolution. However, studies are lacking on how these effects reverberate into key ecological interactions, such as bacteria-phage interactions. Previously, co-selection of bacteria by phages and antibiotic concentrations exceeding MICs has been hypothesized to decrease the rate of resistance evolution because of fitness costs associated with resistance mutations. By contrast, here we show that sub-MICs of the antibiotic streptomycin (Sm) increased the rate of phage resistance evolution, as well as causing extinction of the phage. Notably, Sm and the phage in combination also enhanced the evolution of Sm resistance compared with Sm alone. These observations demonstrate the potential of sub-MICs of antibiotics to impact key ecological interactions in microbial communities with evolutionary outcomes that can radically differ from those associated with high concentrations. Our findings also contribute to the understanding of ecological and evolutionary factors essential for the management of the antibiotic resistance problem.This article is part of the themed issue 'Human influences on evolution, and the ecological and societal consequences'. © 2016 The Author(s).

Sublethal streptomycin concentrations and lytic bacteriophage together promote resistance evolution

PubMed Central

2017-01-01

Sub-minimum inhibiting concentrations (sub-MICs) of antibiotics frequently occur in natural environments owing to wide-spread antibiotic leakage by human action. Even though the concentrations are very low, these sub-MICs have recently been shown to alter bacterial populations by selecting for antibiotic resistance and increasing the rate of adaptive evolution. However, studies are lacking on how these effects reverberate into key ecological interactions, such as bacteria–phage interactions. Previously, co-selection of bacteria by phages and antibiotic concentrations exceeding MICs has been hypothesized to decrease the rate of resistance evolution because of fitness costs associated with resistance mutations. By contrast, here we show that sub-MICs of the antibiotic streptomycin (Sm) increased the rate of phage resistance evolution, as well as causing extinction of the phage. Notably, Sm and the phage in combination also enhanced the evolution of Sm resistance compared with Sm alone. These observations demonstrate the potential of sub-MICs of antibiotics to impact key ecological interactions in microbial communities with evolutionary outcomes that can radically differ from those associated with high concentrations. Our findings also contribute to the understanding of ecological and evolutionary factors essential for the management of the antibiotic resistance problem. This article is part of the themed issue ‘Human influences on evolution, and the ecological and societal consequences’. PMID:27920385

Evolution of H2O, CO, and CO2 production in Comet C/2009 P1 Garradd during the 2011-2012 apparition

NASA Astrophysics Data System (ADS)

McKay, Adam J.; Cochran, Anita L.; DiSanti, Michael A.; Villanueva, Geronimo; Russo, Neil Dello; Vervack, Ronald J.; Morgenthaler, Jeffrey P.; Harris, Walter M.; Chanover, Nancy J.

2015-04-01

We present analysis of high spectral resolution NIR spectra of CO and H2O in Comet C/2009 P1 (Garradd) taken during its 2011-2012 apparition with the CSHELL instrument on NASA's Infrared Telescope Facility (IRTF). We also present analysis of observations of atomic oxygen in Comet Garradd obtained with the ARCES echelle spectrometer mounted on the ARC 3.5-m telescope at Apache Point Observatory and the Tull Coude spectrograph on the Harlan J. Smith 2.7-m telescope at McDonald Observatory. The observations of atomic oxygen serve as a proxy for H2O and CO2. We confirm the high CO abundance in Comet Garradd and the asymmetry in the CO/H2O ratio with respect to perihelion reported by previous studies. From the oxygen observations, we infer that the CO2/H2O ratio decreased as the comet moved towards the Sun, which is expected based on current sublimation models. We also infer that the CO2/H2O ratio was higher pre-perihelion than post-perihelion. We observe evidence for the icy grain source of H2O reported by several studies pre-perihelion, and argue that this source is significantly less abundant post-perihelion. Since H2O, CO2, and CO are the primary ices in comets, they drive the activity. We use our measurements of these important volatiles in an attempt to explain the evolution of Garradd's activity over the apparition.

Directed evolution of an ultrastable carbonic anhydrase for highly efficient carbon capture from flue gas

DOE PAGES

Alvizo, Oscar; Nguyen, Luan J.; Savile, Christopher K.; ...

2014-11-03

Carbonic anhydrase (CA) is one of nature’s fastest enzymes and can dramatically improve the economics of carbon capture under demanding environments such as coal-fired power plants. The use of CA to accelerate carbon capture is limited by the enzyme’s sensitivity to the harsh process conditions. Using directed evolution, the properties of a β-class CA from Desulfovibrio vulgaris were dramatically enhanced. Iterative rounds of library design, library generation, and high-throughput screening identified highly stable CA variants that tolerate temperatures of up to 107 °C in the presence of 4.2 M alkaline amine solvent at pH >10.0. This increase in thermostability andmore » alkali tolerance translates to a 4,000,000-fold improvement over the natural enzyme. In conclusion, at pilot scale, the evolved catalyst enhanced the rate of CO2 absorption 25-fold compared with the noncatalyzed reaction.« less

Directed evolution of an ultrastable carbonic anhydrase for highly efficient carbon capture from flue gas

PubMed Central

Alvizo, Oscar; Nguyen, Luan J.; Savile, Christopher K.; Bresson, Jamie A.; Lakhapatri, Satish L.; Solis, Earl O. P.; Fox, Richard J.; Broering, James M.; Benoit, Michael R.; Zimmerman, Sabrina A.; Novick, Scott J.; Liang, Jack; Lalonde, James J.

2014-01-01

Carbonic anhydrase (CA) is one of nature’s fastest enzymes and can dramatically improve the economics of carbon capture under demanding environments such as coal-fired power plants. The use of CA to accelerate carbon capture is limited by the enzyme’s sensitivity to the harsh process conditions. Using directed evolution, the properties of a β-class CA from Desulfovibrio vulgaris were dramatically enhanced. Iterative rounds of library design, library generation, and high-throughput screening identified highly stable CA variants that tolerate temperatures of up to 107 °C in the presence of 4.2 M alkaline amine solvent at pH >10.0. This increase in thermostability and alkali tolerance translates to a 4,000,000-fold improvement over the natural enzyme. At pilot scale, the evolved catalyst enhanced the rate of CO2 absorption 25-fold compared with the noncatalyzed reaction. PMID:25368146

Modeling CO 2 ice clouds with a Mars Global Climate Model

NASA Astrophysics Data System (ADS)

Audouard, Joachim; Määttänen, Anni; Listowski, Constantino; Millour, Ehouarn; Forget, Francois; Spiga, Aymeric

2016-10-01

Since the first claimed detection of CO2 ice clouds by the Mariner campaign (Herr and Pimentel, 1970), more recent observations and modelling works have put new constraints concerning their altitude, region, time and mechanisms of formation (Clancy and Sandor, 1998; Montmessin et al., 2007; Colaprete et al., 2008; Määttänen et al., 2010; Vincendon et al., 2011; Spiga et al. 2012; Listowski et al. 2014). CO2 clouds are observed at the poles at low altitudes (< 20 km) during the winter and at high altitudes (60-110 km) in the equatorial regions during the first half of the year. However, Martian CO2 clouds's variability and dynamics remain somehow elusive.Towards an understanding of Martian CO2 clouds and especially of their precise radiative impact on the climate throughout the history of the planet, including their formation and evolution in a Global Climate Model (GCM) is necessary.Adapting the CO2 clouds microphysics modeling work of Listowski et al. (2013; 2014), we aim at implementing a complete CO2 clouds scheme in the GCM of the Laboratoire de Météorologie Dynamique (LMD, Forget et al., 1999). It covers CO2 microphysics, growth, evolution and dynamics with a methodology inspired from the water ice clouds scheme recently included in the LMD GCM (Navarro et al., 2014).Two main factors control the formation and evolution of CO2 clouds in the Martian atmosphere: sufficient supersaturation of CO2 is needed and condensation nuclei must be available. Topography-induced gravity-waves (GW) are expected to propagate to the upper atmosphere where they produce cold pockets of supersaturated CO2 (Spiga et al., 2012), thus allowing the formation of clouds provided enough condensation nuclei are present. Such supersaturations have been observed by various instruments, in situ (Schofield et al., 1997) and from orbit (Montmessin et al., 2006, 2011; Forget et al., 2009).Using a GW-induced temperature profile and the 1-D version of the GCM, we simulate the formation of CO2 clouds in the mesosphere and investigate the sensitivity of our microphysics scheme. First results and steps towards the integration in the 3-D GCM will be presented and discussed at the conference.This work is funded by the Laboratory of Excellence ESEP.

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

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

Development of Inorganic Nanomaterials as Photocatalysts for the Water Splitting Reaction

NASA Astrophysics Data System (ADS)

Frame, Fredrick Andrew

The photochemical water splitting reaction is of great interest for converting solar energy into usable fuels. This dissertation focuses on the development of inorganic nanoparticle catalysts for solar energy driven conversion of water into hydrogen and oxygen. The results from these selected studies have allowed greater insight into nanoparticle chemistry and the role of nanoparticles in photochemical conversion of water in to hydrogen and oxygen. Chapter 2 shows that CdSe nanoribbons have photocatalytic activity for hydrogen production from water in the presence of Na2S/Na2SO 3 as sacrificial electron donors in both UV and visible light. Quantum confinement of this material leads to an extended bandgap of 2.7 eV and enables the photocatalytic activity of this material. We report on the photocatalytic H2 evolution, and its dependence on platinum co-catalysts, the concentration of the electron donor, and the wavelength of incident radiation. Transient absorption measurements reveal decay of the excited state on multiple timescales, and an increase of lifetimes of trapped electrons due to the sacrificial electron donors. In chapter 3, we explore the catalytic activity of citrate-capped CdSe quantum dots. We show that the process is indeed catalytic for these dots in aqueous 0.1 M Na2S:Na2SO3, but not in pure water. Furthermore, optical spectroscopy was used to report electronic transitions in the dots and electron microscopy was used to obtain morphology of the catalyst. Interestingly, an increasing catalytic rate is noted for undialyzed catalyst. Dynamic light scattering experiments show an increased hydrodynamic radius in the case of undialyzed CdSe dots in donor solution. In chapter 4 we show that CdSe:MoS2 nanoparticle composites with improved catalytic activity can be assembled from CdSe and MoS2 nanoparticle building units. We report on the photocatalytic H 2 evolution, quantum efficiency using LED irriadiation, and its dependence on the co-catalyst loading. Furthermore, optical spectroscopy, cyclic voltammetry, and electron microscopy were used to obtain morphology, optical properties, and electronic structure of the catalysts. In chapter 5, illumination with visible light (lambda > 400 nm) photoconverts a red V2O5 gel in aqueous methanol solution into a green VO2 gel. The presence of V(4+) in the green VO2 gel is supported by Electron Energy Loss Spectra. High-resolution electron micrographs, powder X-ray diffraction, and selective area electron diffraction (SAED) data show that the crystalline structure of the V2O5 gel is retained upon reduction. After attachment of colloidal Pt nanoparticles, H2 evolution proceeds catalytically on the VO2 gel. The Pt nanoparticles reduce the H2 evolution overpotential. However, the activity of the new photocatalyst remains limited by the VO2 conduction band edge just below the proton reduction potential. Chapter 6 studies the ability of IrO2 to evolve oxygen from aqueous solutions under UV irradiation. We show that visible illumination (lambda > 400 nm) of iridium dioxide (IrO2) nanocrystals capped in succinic acid in aqueous sodium persulfate solution leads to catalytic oxygen evolution. While the majority of catalytic hydrogen evolution comes from UV light, the process can still be driven with visible light. Morphology, optical properties, surface photovoltage measurements, and oxygen evolution rates are discussed.

Experimentally investigate ionospheric depletion chemicals in artificially created ionosphere

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

Liu Yu; Cao Jinxiang; Wang Jian

2012-09-15

A new approach for investigating ionosphere chemical depletion in the laboratory is introduced. Air glow discharge plasma closely resembling the ionosphere in both composition and chemical reactions is used as the artificially created ionosphere. The ionospheric depletion experiment is accomplished by releasing chemicals such as SF{sub 6}, CCl{sub 2}F{sub 2}, and CO{sub 2} into the model discharge. The evolution of the electron density is investigated by varying the plasma pressure and input power. It is found that the negative ion (SF{sub 6}{sup -}, CCl{sub 2}F{sub 2}{sup -}) intermediary species provide larger reduction of the electron density than the positive ionmore » (CO{sub 2}{sup +}) intermediary species. The negative ion intermediary species are also more efficient in producing ionospheric holes because of their fast reaction rates. Airglow enhancement attributed to SF{sub 6} and CO{sub 2} releases agrees well with the published data. Compared to the traditional methods, the new scheme is simpler to use, both in the release of chemicals and in the electron density measurements. It is therefore more efficient for investigating the release of chemicals in the ionosphere.« less

Evolution of CAM and C4 carbon-concentrating mechanisms

USGS Publications Warehouse

Keeley, Jon E.; Rundel, Philip W.

2003-01-01

Mechanisms for concentrating carbon around the Rubisco enzyme, which drives the carbon-reducing steps in photosynthesis, are widespread in plants; in vascular plants they are known as crassulacean acid metabolism (CAM) and C4 photosynthesis. CAM is common in desert succulents, tropical epiphytes, and aquatic plants and is characterized by nighttime fixation of CO2. The proximal selective factor driving the evolution of this CO2-concentrating pathway is low daytime CO2, which results from the unusual reverse stomatal behavior of terrestrial CAM species or from patterns of ambient CO2 availability for aquatic CAM species. In terrestrials the ultimate selective factor is water stress that has selected for increased water use efficiency. In aquatics the ultimate selective factor is diel fluctuations in CO2 availability for palustrine species and extreme oligotrophic conditions for lacustrine species. C4 photosynthesis is based on similar biochemistry but carboxylation steps are spatially separated in the leaf rather than temporally as in CAM. This biochemical pathway is most commonly associated with a specialized leaf anatomy known as Kranz anatomy; however, there are exceptions. The ultimate selective factor driving the evolution of this pathway is excessively high photorespiration that inhibits normal C3 photosynthesis under high light and high temperature in both terrestrial and aquatic habitats. CAM is an ancient pathway that likely has been present since the Paleozoic era in aquatic species from shallow-water palustrine habitats. While atmospheric CO2 levels have undoubtedly affected the evolution of terrestrial plant carbon-concentrating mechanisms, there is reason to believe that past atmospheric changes have not played as important a selective role in the aquatic milieu since palustrine habitats today are not generally carbon sinks, and the selective factors driving aquatic CAM are autogenic. Terrestrial CAM, in contrast, is of increasing selective value under extreme water deficits, and undoubtedly, high Mesozoic CO2 levels reduced the amount of landscape perceived by plants as water limited. Late Tertiary and Quaternary reductions in atmospheric CO2, coupled with increasing seasonality, were probably times of substantial species radiation and ecological expansion for CAM plants. C4 photosynthesis occurs in only about half as many families as CAM, and three-fourths of C4 species are either grasses or sedges. Molecular phylogenies indicate C4 is a more recent innovation than CAM and that it originated in the mid-Tertiary, 20–30 Ma, although some data support an earlier origin. While the timing of the origin of C4 remains controversial, the nearly explosive increase in C4 species is clearly documented in the late Miocene, 4–7 Ma. Increasing seasonality has been widely suggested as an important climatic stimulus for this C4 expansion. Alternatively, based on models of photosynthetic quantum yield at different temperatures and CO2 concentration, it has been hypothesized that the late Miocene C4 expansion resulted from declining atmospheric CO2 levels. This model is most appropriate for explaining the transition from C3 grasslands to C4 grasslands but by itself may not be sufficient to explain the more likely scenario of a late Miocene transition from C3 woodland/ savanna to C4 grasslands. A largely unexplored hypothesis is that climatic changes in late Miocene altered disturbance regimes, in particular the incidence of fires, which today are often associated with maintenance of C4 grasslands. Oceanic charcoal sediments that appear to represent Aeolian deposits from continental wildfires follow a strikingly similar pattern of explosive increase in late Miocene. Climate, CO2, and disturbance are not mutually exclusive explanations and probably all acted in concert to promote the expansion of C4 grasslands. More recently, late Quaternary changes in CO2 may have been responsible for driving major changes in the landscape distribution of C4 species. The theory is sound; however, many of the studies cited in support of this model are open to alternative interpretations, and none has eliminated climatic factors as important selective agents. CAM and C4 evolution required coupling of biochemical pathways with structural changes in photosynthetic tissues, succulence in CAM and Kranz in C4. This was apparently accomplished by piecemeal evolution beginning with mechanisms for recapturing respiratory CO2, although this need not have been so in aquatic CAM species. It has been proposed that the extreme rarity of both pathways in the same plant results from biochemical and structural incompatibilities (Sage 2002). Equally important is the fact that the selective environments are quite different, with CAM evolution thriving on stressful sites inhospitable to C3 species whereas C4 evolution has selected for rapid growth capable of outcompeting associated C3 plants.

Understanding and controlling morphology evolution via DIO plasticization in PffBT4T-2OD/PC71BM devices

PubMed Central

Zhang, Yiwei; Parnell, Andrew J.; Pontecchiani, Fabio; Cooper, Joshaniel F. K.; Thompson, Richard L.; Jones, Richard A. L.; King, Stephen M.; Lidzey, David G.; Bernardo, Gabriel

2017-01-01

We demonstrate that the inclusion of a small amount of the co-solvent 1,8-diiodooctane in the preparation of a bulk-heterojunction photovoltaic device increases its power conversion efficiency by 20%, through a mechanism of transient plasticisation. We follow the removal of 1,8-diiodooctane directly after spin-coating using ellipsometry and ion beam analysis, while using small angle neutron scattering to characterise the morphological nanostructure evolution of the film. In PffBT4T-2OD/PC71BM devices, the power conversion efficiency increases from 7.2% to above 8.7% as a result of the coarsening of the phase domains. This coarsening process is assisted by thermal annealing and the slow evaporation of 1,8-diiodooctane, which we suggest, acts as a plasticiser to promote molecular mobility. Our results show that 1,8-diiodooctane can be completely removed from the film by a thermal annealing process at temperatures ≤100 °C and that there is an interplay between the evaporation rate of 1,8-diiodooctane and the rate of domain coarsening in the plasticized film which helps elucidate the mechanism by which additives improve device efficiency. PMID:28287164

The SILCC (SImulating the LifeCycle of molecular Clouds) project - I. Chemical evolution of the supernova-driven ISM

NASA Astrophysics Data System (ADS)

Walch, S.; Girichidis, P.; Naab, T.; Gatto, A.; Glover, S. C. O.; Wünsch, R.; Klessen, R. S.; Clark, P. C.; Peters, T.; Derigs, D.; Baczynski, C.

2015-11-01

The SILCC (SImulating the Life-Cycle of molecular Clouds) project aims to self-consistently understand the small-scale structure of the interstellar medium (ISM) and its link to galaxy evolution. We simulate the evolution of the multiphase ISM in a (500 pc)2 × ±5 kpc region of a galactic disc, with a gas surface density of Σ _{_GAS} = 10 M_{⊙} pc^{-2}. The FLASH 4 simulations include an external potential, self-gravity, magnetic fields, heating and radiative cooling, time-dependent chemistry of H2 and CO considering (self-) shielding, and supernova (SN) feedback but omit shear due to galactic rotation. We explore SN explosions at different rates in high-density regions (peak), in random locations with a Gaussian distribution in the vertical direction (random), in a combination of both (mixed), or clustered in space and time (clus/clus2). Only models with self-gravity and a significant fraction of SNe that explode in low-density gas are in agreement with observations. Without self-gravity and in models with peak driving the formation of H2 is strongly suppressed. For decreasing SN rates, the H2 mass fraction increases significantly from <10 per cent for high SN rates, i.e. 0.5 dex above Kennicutt-Schmidt, to 70-85 per cent for low SN rates, i.e. 0.5 dex below KS. For an intermediate SN rate, clustered driving results in slightly more H2 than random driving due to the more coherent compression of the gas in larger bubbles. Magnetic fields have little impact on the final disc structure but affect the dense gas (n ≳ 10 cm-3) and delay H2 formation. Most of the volume is filled with hot gas (˜80 per cent within ±150 pc). For all but peak driving a vertically expanding warm component of atomic hydrogen indicates a fountain flow. We highlight that individual chemical species populate different ISM phases and cannot be accurately modelled with temperature-/density-based phase cut-offs.

Consumer co-evolution as an important component of the eco-evolutionary feedback.

PubMed

Hiltunen, Teppo; Becks, Lutz

2014-10-22

Rapid evolution in ecologically relevant traits has recently been recognized to significantly alter the interaction between consumers and their resources, a key interaction in all ecological communities. While these eco-evolutionary dynamics have been shown to occur when prey populations are evolving, little is known about the role of predator evolution and co-evolution between predator and prey in this context. Here, we investigate the role of consumer co-evolution for eco-evolutionary feedback in bacteria-ciliate microcosm experiments by manipulating the initial trait variation in the predator populations. With co-evolved predators, prey evolve anti-predatory defences faster, trait values are more variable, and predator and prey population sizes are larger at the end of the experiment compared with the non-co-evolved predators. Most importantly, differences in predator traits results in a shift from evolution driving ecology, to ecology driving evolution. Thus we demonstrate that predator co-evolution has important effects on eco-evolutionary dynamics.

High-rate composting of barley dregs with sewage sludge in a pilot scale bioreactor.

PubMed

Lu, Li-An; Kumar, Mathava; Tsai, Jen-Chieh; Lin, Jih-Gaw

2008-05-01

The feasibility of high-rate composting of barley dregs and sewage sludge was examined using a pilot scale bioreactor. A central composite design (CCD) was used to optimize the mix ratio of barley dregs/sewage sludge and moisture content. The performance of the bioreactor was monitored as a function of carbon decomposition rate (CDR) and total volatile solids (TVS) loss rate. The optimum range of mix ratio and moisture content was found to be 35-40% and 55-60%, respectively. High CO2 evolution rate (CER) and TVS loss rate were observed after 3 days of the composting and the compost was matured/stable after 7 days. Cardinal temperature model with inflection (CTMI) was used to analyze the compost stability with respect to CER as a parameter of composting efficiency. After examining the phytotoxicity, the compost can be promoted for land application.

Co-ordination of NDH and Cup proteins in CO2 uptake in cyanobacterium Synechocystis sp. PCC 6803.

PubMed

Han, Xunling; Sun, Nan; Xu, Min; Mi, Hualing

2017-06-01

High and low affinity CO2-uptake systems containing CupA (NDH-1MS) and CupB (NDH-1MS'), respectively, have been identified in Synechocystis sp. PCC 6803, but it is yet unknown how the complexes function in CO2 uptake. In this work, we found that deletion of cupB significantly lowered the growth of cells, and deletion of both cupA and cupB seriously suppressed the growth below pH 7.0 even under 3% CO2. The rate of photosynthetic oxygen evolution was decreased slightly by deletion of cupA but significantly by deletion of cupB and more severely by deletion of both cupA and cupB, especially in response to changed pH conditions under 3% CO2. Furthermore, we found that assembly of CupB into NDH-1MS' was dependent on NdhD4 and NdhF4. NDH-1MS' was not affected in the NDH-1MS-degradation mutant and NDH-1MS was not affected in the NDH-1MS'-degradation mutants, indicating the existence of independent CO2-uptake systems under high CO2 conditions. The light-induced proton gradient across thylakoid membranes was significantly inhibited in ndhD-deletion mutants, suggesting that NdhDs functions in proton pumping. The carbonic anhydrase activity was suppressed partly in the cupA- or cupB-deletion mutant but severely in the mutant with both cupA and cupB deletion, indicating that CupA and CupB function in conversion of CO2 to HCO3-. In turn, deletion of cup genes lowered the transthylakoid membrane proton gradient and deletion of ndhDs decreased the CO2 hydration. Our results suggest that NDH-1M provides an alkaline region to activate Cup proteins involved in CO2 uptake. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Co-evolution of somatic variation in primary and metastatic colorectal cancer may expand biopsy indications in the molecular era.

PubMed

Kim, Richard; Schell, Michael J; Teer, Jamie K; Greenawalt, Danielle M; Yang, Mingli; Yeatman, Timothy J

2015-01-01

Metastasis is thought to be a clonal event whereby a single cell initiates the development of a new tumor at a distant site. However the degree to which primary and metastatic tumors differ on a molecular level remains unclear. To further evaluate these concepts, we used next generation sequencing (NGS) to assess the molecular composition of paired primary and metastatic colorectal cancer tissue specimens. 468 colorectal tumor samples from a large personalized medicine initiative were assessed by targeted gene sequencing of 1,321 individual genes. Eighteen patients produced genomic profiles for 17 paired primary:metastatic (and 2 metastatic:metastatic) specimens. An average of 33.3 mutations/tumor were concordant (shared) between matched samples, including common well-known genes (APC, KRAS, TP53). An average of 2.3 mutations/tumor were discordant (unshared) among paired sites. KRAS mutational status was always concordant. The overall concordance rate for mutations was 93.5%; however, nearly all (18/19 (94.7%)) paired tumors showed at least one mutational discordance. Mutations were seen in: TTN, the largest gene (5 discordant pairs), ADAMTS20, APC, MACF1, RASA1, TP53, and WNT2 (2 discordant pairs), SMAD2, SMAD3, SMAD4, FBXW7, and 66 others (1 discordant pair). Whereas primary and metastatic tumors displayed little variance overall, co-evolution produced incremental mutations in both. These results suggest that while biopsy of the primary tumor alone is likely sufficient in the chemotherapy-naïve patient, additional biopsies of primary or metastatic disease may be necessary to precisely tailor therapy following chemotherapy resistance or insensitivity in order to adequately account for tumor evolution.

Co-Evolution of Somatic Variation in Primary and Metastatic Colorectal Cancer May Expand Biopsy Indications in the Molecular Era

PubMed Central

Kim, Richard; Schell, Michael J.; Teer, Jamie K.; Greenawalt, Danielle M.; Yang, Mingli; Yeatman, Timothy J.

2015-01-01

Introduction Metastasis is thought to be a clonal event whereby a single cell initiates the development of a new tumor at a distant site. However the degree to which primary and metastatic tumors differ on a molecular level remains unclear. To further evaluate these concepts, we used next generation sequencing (NGS) to assess the molecular composition of paired primary and metastatic colorectal cancer tissue specimens. Methods 468 colorectal tumor samples from a large personalized medicine initiative were assessed by targeted gene sequencing of 1,321 individual genes. Eighteen patients produced genomic profiles for 17 paired primary:metastatic (and 2 metastatic:metastatic) specimens. Results An average of 33.3 mutations/tumor were concordant (shared) between matched samples, including common well-known genes (APC, KRAS, TP53). An average of 2.3 mutations/tumor were discordant (unshared) among paired sites. KRAS mutational status was always concordant. The overall concordance rate for mutations was 93.5%; however, nearly all (18/19 (94.7%)) paired tumors showed at least one mutational discordance. Mutations were seen in: TTN, the largest gene (5 discordant pairs), ADAMTS20, APC, MACF1, RASA1, TP53, and WNT2 (2 discordant pairs), SMAD2, SMAD3, SMAD4, FBXW7, and 66 others (1 discordant pair). Conclusions Whereas primary and metastatic tumors displayed little variance overall, co-evolution produced incremental mutations in both. These results suggest that while biopsy of the primary tumor alone is likely sufficient in the chemotherapy-naïve patient, additional biopsies of primary or metastatic disease may be necessary to precisely tailor therapy following chemotherapy resistance or insensitivity in order to adequately account for tumor evolution. PMID:25974029

Structure Evolution and Multiferroic Properties in Cobalt Doped Bi4NdTi3Fe1-xCoxO15-Bi3NdTi2Fe1-xCoxO12-δ Intergrowth Aurivillius Compounds

PubMed Central

Zhang, D. L.; Huang, W. C.; Chen, Z. W.; Zhao, W. B.; Feng, L.; Li, M.; Yin, Y. W.; Dong, S. N.; Li, X. G.

2017-01-01

Here, we report the structure evolution, magnetic and ferroelectric properties in Co-doped 4- and 3-layered intergrowth Aurivillius compounds Bi4NdTi3Fe1-xCoxO15-Bi3NdTi2Fe1-xCoxO12-δ. The compounds suffer a structure evolution from the parent 4-layered phase (Bi4NdTi3FeO15) to 3-layered phase (Bi3NdTi2CoO12-δ) with increasing cobalt doping level from 0 to 1. Meanwhile the remanent magnetization and polarization show opposite variation tendencies against the doping level, and the sample with x = 0.3 has the largest remanent magnetization and the smallest polarization. It is believed that the Co concentration dependent magnetic properties are related to the population of the Fe3+ -O-Co3+ bonds, while the suppressed ferroelectric polarization is due to the enhanced leakage current caused by the increasing Co concentration. Furthermore, the samples (x = 0.1–0.7) with ferromagnetism show magnetoelectric coupling effects at room temperature. The results indicate that it is an effective method to create new multiferroic materials through modifying natural superlattices. PMID:28272495

Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces.

PubMed

Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine A

2016-11-23

A detailed understanding of the electrochemical reduction of CO 2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO 2 (1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO 2 reduction reaction (CO2RR) based on thermodynamic analysis. We aim to specify the requirements for CO2RR catalysts to establish adsorbate scaling relations and use these to derive activity volcanoes. Computational results show that the OH* binding free energy is a good descriptor of the thermodynamic limitations and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits their suitability. We determine the ideal binding free energy for H* and OH* to facilitate selective CO2RR over H 2 /CO evolution to be ΔG B [H]>0.5 eV and -0.5 eV<ΔG B [OH]<0.1 eV. The Re-containing overlayers considered in this work display excellent promise for selectivity, although they are active at a highly reducing potential. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Measurement for Correlation of Co-evolution Relationship of Subsequences in Protein.

PubMed

Gao, Hongyun; Yu, Xiaoqing; Dou, Yongchao; Wang, Jun

2015-12-01

Many computational tools have been developed to measure the protein residues co-evolution. Most of them only focus on co-evolution for pairwise residues in a protein sequence. However, number of residues participate in co-evolution might be multiple. And some co-evolved residues are clustered in several distinct regions in primary structure. Therefore, the co-evolution among the adjacent residues and the correlation between the distinct regions offer insights into function and evolution of the protein and residues. Subsequence is used to represent the adjacent multiple residues in one distinct region. In the paper, co-evolution relationship in each subsequence is represented by mutual information matrix (MIM). Then, Pearson's correlation coefficient: R value is developed to measure the similarity correlation of two MIMs. MSAs from Catalytic Data Base (Catalytic Site Atlas, CSA) are used for testing. R value characterizes a specific class of residues. In contrast to individual pairwise co-evolved residues, adjacent residues without high individual MI values are found since the co-evolved relationship among them is similar to that among another set of adjacent residues. These subsequences possess some flexibility in the composition of side chains, such as the catalyzed environment.

Soil CO2 flux in response to elevated atmospheric CO2 and nitrogen fertilization: patterns and methods

Treesearch

James M. Vose; Katherine J. Elliott; D.W. Johnson

1995-01-01

The evolution of carbon dioxide (CO2) from soils is due to the metabolic activity of roots, mycorrhizae, and soil micro- and macro-organisms. Although precise estimates of carbon (C) recycled to the atmosphere from belowground sources are unavailable, Musselman and Fox (1991) propose that the belowground contribution exceeds 100 Pg y-1...

Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

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

Enrique Iglesia; Akio Ishikawa; Manual Ojeda

2007-09-30

A detailed study of the catalyst composition, preparation and activation protocol of Fe-based catalysts for the Fischer-Tropsch Synthesis (FTS) have been carried out in this project. We have studied the effects of different promoters on the catalytic performance of Fe-based catalysts. Specifically, we have focused on how their sequence of addition dramatically influences the performance of these materials in the Fischer-Tropsch synthesis. The resulting procedures have been optimized to improve further upon the already unprecedented rates and C{sub 5+} selectivities of the Fe-based catalysts that we have developed as part of this project. Selectivity to C{sub 5+} hydrocarbon was closemore » to 90 % (CO{sub 2}-free basis) and CO conversion rate was about 6.7 mol h{sup -1} g-at Fe{sup -1} at 2.14 MPa, 508 K and with substoichiometric synthesis gas; these rates were larger than any reported previously for Fe-based FTS catalysts at these conditions. We also tested the stability of Fe-based catalysts during FTS reaction (10 days); as a result, the high hydrocarbon formation rates were maintained during 10 days, though the gradual deactivation was observed. Our investigation has also focused on the evaluation of Fe-based catalysts with hydrogen-poor synthesis gas streams (H{sub 2}/CO=1). We have observed that the Fe-based catalysts prepared in this project display also a high hydrocarbon synthesis rate with substoichiometric synthesis gas (H{sub 2}/CO=1) stream, which is a less desirable reactant mixture than stoichiometric synthesis gas (H{sub 2}/CO=2). We have improved the catalyst preparation protocols and achieved the highest FTS reaction rates and selectivities so far reported at the low temperatures required for selectivity and stability. Also, we have characterized the catalyst structural change and active phases formed, and their catalytic behavior during the activation process to evaluate their influences on FTS reaction. The efforts of this project led to (i) structural evolution of Fe-Zn oxide promoted with K and Cu, and (ii) evaluation of hydrocarbon and CH{sub 4} formation rates during activation procedures at various temperature and H{sub 2}/CO ratios. On the basis of the obtained results, we suggest that lower reactor temperature can be sufficient to activate catalysts and lead to the high FTS performance. In this project, we have also carried out a detailed kinetic and mechanistic study of the Fischer-Tropsch Synthesis with Fe-based catalysts. We have proposed a reaction mechanism with two CO activation pathways: unassisted and H-assisted. Both routes lead to the formation of the same surface monomers (CH{sub 2}). However, the oxygen removal mechanism is different. In the H-assisted route, oxygen is removed exclusively as water, while oxygen is rejected as carbon dioxide in the unassisted CO dissociation. The validity of the mechanism here proposed has been found to be in agreement with the experimental observation and with theoretical calculations over a Fe(110) surface. Also, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that the use of D{sub 2} instead of H{sub 2} leads to higher hydrocarbons formation rates (inverse kinetic isotopic effect). On the contrary, primary carbon dioxide formation is not influenced. These experimental observations can be explained by two CO activation pathways. We have also explored the catalytic performance of Co-based catalysts prepared by using inverse micelles techniques. We have studied several methods in order to terminate the silanol groups on SiO{sub 2} support including impregnation, urea homogeneous deposition-precipitation, or zirconium (IV) ethoxide titration. Although hydroxyl groups on the SiO{sub 2} surface are difficult to be stoichiometrically titrated by ZrO{sub 2}, a requirement to prevent the formation of strongly-interacting Co oxide species on SiO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion leading to a marked increase in the number of accessible Co sites. Inverse micelle method allowed the synthesis of small Co clusters on SiO{sub 2}, but the required surfactant removal steps led to the re-oxidation of Co metal clusters and to the formation of difficult to reduce CoO{sub x} species.« less

Non-equilibrium plasma kinetics of reacting CO: an improved state to state approach

NASA Astrophysics Data System (ADS)

Pietanza, L. D.; Colonna, G.; Capitelli, M.

2017-12-01

Non-equilibrium plasma kinetics of reacting CO for conditions typically met in microwave discharges have been developed based on the coupling of excited state kinetics and the Boltzmann equation for the electron energy distribution function (EEDF). Particular attention is given to the insertion in the vibrational kinetics of a complete set of electron molecule resonant processes linking the whole vibrational ladder of the CO molecule, as well as to the role of Boudouard reaction, i.e. the process of forming CO2 by two vibrationally excited CO molecules, in shaping the vibrational distribution of CO and promoting reaction channels assisted by vibrational excitation (pure vibrational mechanisms, PVM). PVM mechanisms can become competitive with electron impact dissociation processes (DEM) in the activation of CO. A case study reproducing the conditions of a microwave discharge has been considered following the coupled kinetics also in the post discharge conditions. Results include the evolution of EEDF in discharge and post discharge conditions highlighting the role of superelastic vibrational and electronic collisions in shaping the EEDF. Moreover, PVM rate coefficients and DEM ones are studied as a function of gas temperature, showing a non-Arrhenius behavior, i.e. the rate coefficients increase with decreasing gas temperature as a result of a vibrational-vibrational (V-V) pumping up mechanism able to form plateaux in the vibrational distribution function. The accuracy of the results is discussed in particular in connection to the present knowledge of the activation energy of the Boudouard process.

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

The Paleo-ecology of C4 Evolution

NASA Astrophysics Data System (ADS)

Sage, R. F.; Khoshravesh, R.

2014-12-01

Molecular clock analysis of extant plant lineages consistently place the earliest appearance of the C4 photosynthetic pathway in the mid-to-late Oligocene, coincident with a decline in atmospheric CO2 and a spread of dry environments. Most of the approximately 70 known lineages of C4 photosynthesis, however, evolved over the subsequent 23 million years since the Oligocene. Examination of living C3-C4 intermediate species, and close C3 relatives of modern C4 lineages, indicate that the C4 pathway evolved in regions of high heat and episodic drought and/or salinity, usually in the drier ends of the monsoon belts of the subtropics. Soils associated with transitional species are typically sandy, rocky, or salinized, and have low vegetation density, which in combination with high air temperature allows for high surface heat loads that warm leaves to near 45°C. Under such conditions in low CO2 atmospheres, the rate of photorespiration is very high and would greatly impair C3 photosynthesis and establish conditions favoring C4 evolution. However, studies with modern taxa do not address whether the extreme habitats proposed to facilitate C4 evolution were actually present at the time when the C4 pathway evolved in any given lineage. Here, we examine the paleo-record to evaluate the environmental conditions present in the C4 centres of origin when the respective transitions from C3 to C4 photosynthesis are estimated to have occurred.

Non-sensitized selective photochemical reduction of CO2 to CO under visible light with an iron molecular catalyst.

PubMed

Rao, Heng; Bonin, Julien; Robert, Marc

2017-03-02

A substituted tetraphenyl iron porphyrin, bearing positively charged trimethylammonio groups at the para position of each phenyl ring, demonstrates its ability as a homogeneous molecular catalyst to selectively reduce CO 2 to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.

Tracking Co(I) Intermediate in operando in Photocatalytic Hydrogen Evolution by X-ray transient Absorption Spectroscopy and DFT Calculation

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

Li, Zhi-Jun; Zhan, Fei; Xiao, Hongyan

X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [RuII(bpy)3]Cl2·6H2O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([CoII(DPABpy) Cl]Cl) as the pre-catalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 ± 0.03 Å. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand π back-bonding greatly stabilizes the penta-coordinated Co(I) intermediate, whichmore » provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure– function relationship of cobalt-based molecular catalysts.« less

Environmental fate and effects of granular pesta formulation from strains of Pseudomonas aeruginosa C1501 and Lasiodiplodia pseudotheobromae C1136 on soil activity and weeds.

PubMed

Adetunji, Charles Oluwaseun; Oloke, Julius Kola; Osemwegie, Osarenkhoe Omorefosa

2018-03-01

This work investigated the effect of variably formulated pesta granules containing wild and UV mutated Pseudomonas aeruginosa and Lasiodiplodia pseudotheobromae on the rate of CO 2 evolution, organic carbon content, enzymatic activity (acidic and alkaline phosphatase, dehydrogenases, urease and protease) and representative soil microorganisms in the soils using different assay techniques. After the 35th day period of experiment, the pesta granule formulation BH4 showed the best evolution of CO 2 (824 ± 6.2 mg CO 2 kg -1 soil hr -1 ) as against control treatment (689 ± 3.7 mg CO 2 kg -1 soil hr -1 ). Enzymes activities, organic carbon content of 3.8% on the 15th day of study and stable representation of microorganisms that include actinomycetes, fungi, heterogenous as well as soil nitrogen-mediatory bacteria were equally at their maximum level BH4 treatments. The phytotoxic assay showed no inhibitory effect on Solanum lycopersicum seeds and seedlings compared to the observed growth inhibition on the tested weeds (Amaranthus hybridus and Echinocholoa crus-galli) which corresponds with positive control glyphosate treatment. The glyphosate treated soil had the least critical results on parameters investigated during the study. The order of bioherbicidal activity is BH4>BH2>BH6>BH3>BH1>BH5>positive control. Results from this study confirmed the target efficacy of variably formulated pesta granules which is sustainable, cheap, ecologically suitable and recent. This is in addition to recognizing the microbial-derived formulations as characteristically potent alternative to chemical herbicides utility in agrosystems practice. Further study of the underlining factor responsible for the bioherbicidal performances of the variably formulated pesta granules and field trials are critical for their future commercialization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Feature co-localization landscape of the human genome

PubMed Central

Ng, Siu-Kin; Hu, Taobo; Long, Xi; Chan, Cheuk-Hin; Tsang, Shui-Ying; Xue, Hong

2016-01-01

Although feature co-localizations could serve as useful guide-posts to genome architecture, a comprehensive and quantitative feature co-localization map of the human genome has been lacking. Herein we show that, in contrast to the conventional bipartite division of genomic sequences into genic and inter-genic regions, pairwise co-localizations of forty-two genomic features in the twenty-two autosomes based on 50-kb to 2,000-kb sequence windows indicate a tripartite zonal architecture comprising Genic zones enriched with gene-related features and Alu-elements; Proximal zones enriched with MIR- and L2-elements, transcription-factor-binding-sites (TFBSs), and conserved-indels (CIDs); and Distal zones enriched with L1-elements. Co-localizations between single-nucleotide-polymorphisms (SNPs) and copy-number-variations (CNVs) reveal a fraction of sequence windows displaying steeply enhanced levels of SNPs, CNVs and recombination rates that point to active adaptive evolution in such pathways as immune response, sensory perceptions, and cognition. The strongest positive co-localization observed between TFBSs and CIDs suggests a regulatory role of CIDs in cooperation with TFBSs. The positive co-localizations of cancer somatic CNVs (CNVT) with all Proximal zone and most Genic zone features, in contrast to the distinctly more restricted co-localizations exhibited by germline CNVs (CNVG), reveal disparate distributions of CNVTs and CNVGs indicative of dissimilarity in their underlying mechanisms. PMID:26854351

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

PubMed

Chen, Ziliang; Wu, Renbing; Liu, Yang; Ha, Yuan; Guo, Yanhui; Sun, Dalin; Liu, Miao; Fang, Fang

2018-06-10

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm -2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H 2 SO 4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative Planetary Mineralogy: Co, Ni Systematics in Chromite from Planetary Basalts

NASA Technical Reports Server (NTRS)

Karner, J. M.; Shearer, C. K.; Papike, J. J.; Righter,K.

2005-01-01

Spinel is a minor but important phase in planetary basalts because its variable composition often reflects basalt petrogenesis. For example, complicated zoning trends in spinel can give clues to melt evolution [1], and V concentrations in chromite lend insight into magma oxygen fugacity (fO2) conditions [2]. Nickel and Co are two elements that are commonly used as a measure of melt fractionation, and their partitioning between olivine and melt is fairly well understood. Less clear is their partitioning into spinel, although [3] has explored Ni and Co systematics in experimental charges. This study documents Ni and Co behavior in early crystallizing spinel (chromite) from several planetary basalts in an attempt to compare our results with [3], and also gain insight into basalt evolution on the three planets.

Abundances of Volatile - Bearing Species from Evolved Gas Analysis of Samples from the Rocknest Aeolian Bedform in Gale Crater

NASA Technical Reports Server (NTRS)

Archer, P. D., Jr.; Franc, H. B.; Sutter, B.; McAdam, A.; Ming, D. W.; Morris, R. V.; Mahaffy, P. R.

2013-01-01

The Sample Analysis at Mars (SAM) instrument suite on board the Mars Science Laboratory (MSL) recently ran four samples from an aeolian bedform named Rocknest. SAM detected the evolution of H2O, CO2, O2, and SO2, indicative of the presence of multiple volatile bearing species (Fig 1). The Rocknest bedform is a windblown deposit selected as representative of both the windblown material in Gale crater as well as the globally-distributed martian dust. Four samples of Rocknest material were analyzed by SAM, all from the fifth scoop taken at this location. The material delivered to SAM passed through a 150 m sieve and is assumed to have been well mixed during the sample acquisition/preparation/handoff process. SAM heated the Rocknest samples to approx.835 C at a ramp rate of 35 C/min with a He carrier gas flow rate of apprx.1.5 standard cubic centimeters per minute and at an oven pressure of 30 mbar [1]. Evolved gases were detected by a quadrupole mass spectrometer (QMS). This abstract presents the molar abundances of H2O, CO2, O2, and SO2 as well as their concentration in rocknest samples using an estimated sample mass.

Evolution of carbon sinks in a changing climate.

PubMed

Fung, Inez Y; Doney, Scott C; Lindsay, Keith; John, Jasmin

2005-08-09

Climate change is expected to influence the capacities of the land and oceans to act as repositories for anthropogenic CO2 and hence provide a feedback to climate change. A series of experiments with the National Center for Atmospheric Research-Climate System Model 1 coupled carbon-climate model shows that carbon sink strengths vary with the rate of fossil fuel emissions, so that carbon storage capacities of the land and oceans decrease and climate warming accelerates with faster CO2 emissions. Furthermore, there is a positive feedback between the carbon and climate systems, so that climate warming acts to increase the airborne fraction of anthropogenic CO2 and amplify the climate change itself. Globally, the amplification is small at the end of the 21st century in this model because of its low transient climate response and the near-cancellation between large regional changes in the hydrologic and ecosystem responses. Analysis of our results in the context of comparable models suggests that destabilization of the tropical land sink is qualitatively robust, although its degree is uncertain.

Evolution of carbon sinks in a changing climate

PubMed Central

Fung, Inez Y.; Doney, Scott C.; Lindsay, Keith; John, Jasmin

2005-01-01

Climate change is expected to influence the capacities of the land and oceans to act as repositories for anthropogenic CO2 and hence provide a feedback to climate change. A series of experiments with the National Center for Atmospheric Research–Climate System Model 1 coupled carbon–climate model shows that carbon sink strengths vary with the rate of fossil fuel emissions, so that carbon storage capacities of the land and oceans decrease and climate warming accelerates with faster CO2 emissions. Furthermore, there is a positive feedback between the carbon and climate systems, so that climate warming acts to increase the airborne fraction of anthropogenic CO2 and amplify the climate change itself. Globally, the amplification is small at the end of the 21st century in this model because of its low transient climate response and the near-cancellation between large regional changes in the hydrologic and ecosystem responses. Analysis of our results in the context of comparable models suggests that destabilization of the tropical land sink is qualitatively robust, although its degree is uncertain. PMID:16061800

A non-classical phase diagram for virus-bacterial co-evolution mediated by CRISPR

NASA Astrophysics Data System (ADS)

Han, Pu; Deem, Michael

CRISPR is a newly discovered prokaryotic immune system. Bacteria and archaea with this system incorporate genetic material from invading viruses into their genomes, providing protection against future infection by similar viruses. Due to the cost of CRISPR, bacteria can lose the acquired immunity. We will show an intriguing phase diagram of the virus extinction probability, which when the rate of losing the acquired immunity is small, is more complex than that of the classic predator-prey model. As the CRISPR incorporates genetic material, viruses are under pressure to evolve to escape the recognition by CRISPR, and this co-evolution leads to a non-trivial phase structure that cannot be explained by the classical predator-prey model.

MONTE CARLO POPULATION SYNTHESIS OF POST-COMMON-ENVELOPE WHITE DWARF BINARIES AND TYPE Ia SUPERNOVA RATE

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

Ablimit, Iminhaji; Maeda, Keiichi; Li, Xiang-Dong

Binary population synthesis (BPS) studies provide a comprehensive way to understand the evolution of binaries and their end products. Close white dwarf (WD) binaries have crucial characteristics for examining the influence of unresolved physical parameters on binary evolution. In this paper, we perform Monte Carlo BPS simulations, investigating the population of WD/main-sequence (WD/MS) binaries and double WD binaries using a publicly available binary star evolution code under 37 different assumptions for key physical processes and binary initial conditions. We considered different combinations of the binding energy parameter ( λ {sub g}: considering gravitational energy only; λ {sub b}: considering bothmore » gravitational energy and internal energy; and λ {sub e}: considering gravitational energy, internal energy, and entropy of the envelope, with values derived from the MESA code), CE efficiency, critical mass ratio, initial primary mass function, and metallicity. We find that a larger number of post-CE WD/MS binaries in tight orbits are formed when the binding energy parameters are set by λ {sub e} than in those cases where other prescriptions are adopted. We also determine the effects of the other input parameters on the orbital periods and mass distributions of post-CE WD/MS binaries. As they contain at least one CO WD, double WD systems that evolved from WD/MS binaries may explode as type Ia supernovae (SNe Ia) via merging. In this work, we also investigate the frequency of two WD mergers and compare it to the SNe Ia rate. The calculated Galactic SNe Ia rate with λ = λ {sub e} is comparable to the observed SNe Ia rate, ∼8.2 × 10{sup 5} yr{sup 1} – ∼4 × 10{sup 3} yr{sup 1} depending on the other BPS parameters, if a DD system does not require a mass ratio higher than ∼0.8 to become an SNe Ia. On the other hand, a violent merger scenario, which requires the combined mass of two CO WDs ≥ 1.6 M {sub ⊙} and a mass ratio >0.8, results in a much lower SNe Ia rate than is observed.« less

Transition-metal redox evolution in LiNi 0.5Mn 0.3Co 0.2O 2 electrodes at high potentials

DOE PAGES

Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos; ...

2017-06-12

The mixed transition-metal layered compound, LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here in this paper, we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni 4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained belowmore » 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni 2+, Ni 3+ and Ni 4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Furthermore, about 20% of Ni 2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.« less

Future ocean hypercapnia driven by anthropogenic amplification of the natural CO2 cycle.

PubMed

McNeil, Ben I; Sasse, Tristan P

2016-01-21

High carbon dioxide (CO2) concentrations in sea-water (ocean hypercapnia) can induce neurological, physiological and behavioural deficiencies in marine animals. Prediction of the onset and evolution of hypercapnia in the ocean requires a good understanding of annual variations in oceanic CO2 concentration, but there is a lack of relevant global observational data. Here we identify global ocean patterns of monthly variability in carbon concentration using observations that allow us to examine the evolution of surface-ocean CO2 levels over the entire annual cycle under increasing atmospheric CO2 concentrations. We predict that the present-day amplitude of the natural oscillations in oceanic CO2 concentration will be amplified by up to tenfold in some regions by 2100, if atmospheric CO2 concentrations continue to rise throughout this century (according to the RCP8.5 scenario of the Intergovernmental Panel on Climate Change). The findings from our data are broadly consistent with projections from Earth system climate models. Our predicted amplification of the annual CO2 cycle displays distinct global patterns that may expose major fisheries in the Southern, Pacific and North Atlantic oceans to hypercapnia many decades earlier than is expected from average atmospheric CO2 concentrations. We suggest that these ocean 'CO2 hotspots' evolve as a combination of the strong seasonal dynamics of CO2 concentration and the long-term effective storage of anthropogenic CO2 in the oceans that lowers the buffer capacity in these regions, causing a nonlinear amplification of CO2 concentration over the annual cycle. The onset of ocean hypercapnia (when the partial pressure of CO2 in sea-water exceeds 1,000 micro-atmospheres) is forecast for atmospheric CO2 concentrations that exceed 650 parts per million, with hypercapnia expected in up to half the surface ocean by 2100, assuming a high-emissions scenario (RCP8.5). Such extensive ocean hypercapnia has detrimental implications for fisheries during the twenty-first century.

Future ocean hypercapnia driven by anthropogenic amplification of the natural CO2 cycle

NASA Astrophysics Data System (ADS)

McNeil, Ben I.; Sasse, Tristan P.

2016-01-01

High carbon dioxide (CO2) concentrations in sea-water (ocean hypercapnia) can induce neurological, physiological and behavioural deficiencies in marine animals. Prediction of the onset and evolution of hypercapnia in the ocean requires a good understanding of annual variations in oceanic CO2 concentration, but there is a lack of relevant global observational data. Here we identify global ocean patterns of monthly variability in carbon concentration using observations that allow us to examine the evolution of surface-ocean CO2 levels over the entire annual cycle under increasing atmospheric CO2 concentrations. We predict that the present-day amplitude of the natural oscillations in oceanic CO2 concentration will be amplified by up to tenfold in some regions by 2100, if atmospheric CO2 concentrations continue to rise throughout this century (according to the RCP8.5 scenario of the Intergovernmental Panel on Climate Change). The findings from our data are broadly consistent with projections from Earth system climate models. Our predicted amplification of the annual CO2 cycle displays distinct global patterns that may expose major fisheries in the Southern, Pacific and North Atlantic oceans to hypercapnia many decades earlier than is expected from average atmospheric CO2 concentrations. We suggest that these ocean ‘CO2 hotspots’ evolve as a combination of the strong seasonal dynamics of CO2 concentration and the long-term effective storage of anthropogenic CO2 in the oceans that lowers the buffer capacity in these regions, causing a nonlinear amplification of CO2 concentration over the annual cycle. The onset of ocean hypercapnia (when the partial pressure of CO2 in sea-water exceeds 1,000 micro-atmospheres) is forecast for atmospheric CO2 concentrations that exceed 650 parts per million, with hypercapnia expected in up to half the surface ocean by 2100, assuming a high-emissions scenario (RCP8.5). Such extensive ocean hypercapnia has detrimental implications for fisheries during the twenty-first century.

Plant adaptation or acclimation to rising CO2 ? Insight from first multigenerational RNA-Seq transcriptome.

PubMed

Watson-Lazowski, Alexander; Lin, Yunan; Miglietta, Franco; Edwards, Richard J; Chapman, Mark A; Taylor, Gail

2016-11-01

Atmospheric carbon dioxide (CO 2 ) directly determines the rate of plant photosynthesis and indirectly effects plant productivity and fitness and may therefore act as a selective pressure driving evolution, but evidence to support this contention is sparse. Using Plantago lanceolata L. seed collected from a naturally high CO 2 spring and adjacent ambient CO 2 control site, we investigated multigenerational response to future, elevated atmospheric CO 2 . Plants were grown in either ambient or elevated CO 2 (700 μmol mol -1 ), enabling for the first time, characterization of the functional and population genomics of plant acclimation and adaptation to elevated CO 2 . This revealed that spring and control plants differed significantly in phenotypic plasticity for traits underpinning fitness including above-ground biomass, leaf size, epidermal cell size and number and stomatal density and index. Gene expression responses to elevated CO 2 (acclimation) were modest [33-131 genes differentially expressed (DE)], whilst those between control and spring plants (adaptation) were considerably larger (689-853 DE genes). In contrast, population genomic analysis showed that genetic differentiation between spring and control plants was close to zero, with no fixed differences, suggesting that plants are adapted to their native CO 2 environment at the level of gene expression. An unusual phenotype of increased stomatal index in spring but not control plants in elevated CO 2 correlated with altered expression of stomatal patterning genes between spring and control plants for three loci (YODA, CDKB1;1 and SCRM2) and between ambient and elevated CO 2 for four loci (ER, YODA, MYB88 and BCA1). We propose that the two positive regulators of stomatal number (SCRM2) and CDKB1;1 when upregulated act as key controllers of stomatal adaptation to elevated CO 2 . Combined with significant transcriptome reprogramming of photosynthetic and dark respiration and enhanced growth in spring plants, we have identified the potential basis of plant adaptation to high CO 2 likely to occur over coming decades. © 2016 The Authors. Global Change Biology Published by John Wiley & Sons Ltd.

Active Galactic Nuclei with James Webb Space Telescope (JWST)

NASA Technical Reports Server (NTRS)

Rigby, Jane R.

2011-01-01

I'll discuss several ways in which JWST will probe the cosmic history of accretion onto supermassive black holes, and the co-evolution of host galaxies. Key investigations include: 1) Measurements of redshift, luminosity, and AGN fraction for obscured AGN candidates identified by other missions. 2) Measurements of AGN hosts at all redshifts, including stellar masses, morphology, interactions, and star formation rates. 3) Measurements of stellar mass and black hole mass in AGN at high redshift, to chart the early history of black hole and galaxy growth.

Observing the Electrochemical Oxidation of Co Metal at the Solid/Liquid Interface Using Ambient Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.; ...

2017-08-28

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

Design of active and stable Co-Mo-S x chalcogels as pH-universal catalyst for the hydrogen evolution reaction

DOE PAGES

Staszak-Jirkovský, Jakub; Malliakas, Christos D.; Lopes, Pietro P.; ...

2015-11-30

Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS 2 and MoS 2) and amorphous (CoS x and MoS x) hydrogen evolution catalysts. We propose that Co 2+ and Mo 4+ centers promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoS x materials are more active than MoSmore » x they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. Finally, by combining the higher activity of CoS x building blocks with the higher stability of MoS x units into a compact and robust CoMoS x structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.« less

The possible evolution and future of CO2-concentrating mechanisms.

PubMed

Raven, John A; Beardall, John; Sánchez-Baracaldo, Patricia

2017-06-01

CO2-concentrating mechanisms (CCMs), based either on active transport of inorganic carbon (biophysical CCMs) or on biochemistry involving supplementary carbon fixation into C4 acids (C4 and CAM), play a major role in global primary productivity. However, the ubiquitous CO2-fixing enzyme in autotrophs, Rubisco, evolved at a time when atmospheric CO2 levels were very much higher than today and O2 was very low and, as CO2 and O2 approached (by no means monotonically), today's levels, at some time subsequently many organisms evolved a CCM that increased the supply of CO2 and decreased Rubisco oxygenase activity. Given that CO2 levels and other environmental factors have altered considerably between when autotrophs evolved and the present day, and are predicted to continue to change into the future, we here examine the drivers for, and possible timing of, evolution of CCMs. CCMs probably evolved when CO2 fell to 2-16 times the present atmospheric level, depending on Rubisco kinetics. We also assess the effects of other key environmental factors such as temperature and nutrient levels on CCM activity and examine the evidence for evolutionary changes in CCM activity and related cellular processes as well as limitations on continuity of CCMs through environmental variations. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Degassing of basaltic magma: decompression experiments and implications for interpreting the textures of volcanic rocks

NASA Astrophysics Data System (ADS)

Le Gall, Nolwenn; Pichavant, Michel; Cai, Biao; Lee, Peter; Burton, Mike

2017-04-01

Decompression experiments were performed to simulate the ascent of basaltic magma, with the idea of approaching the textural features of volcanic rocks to provide insights into degassing processes. The experiments were conducted in an internally heated pressure vessel between NNO-1.4 and +0.9. H2O-only (4.9 wt%) and H2O-CO2-bearing (0.71-2.45 wt% H2O, 818-1094 ppm CO2) melts, prepared from Stromboli pumice, were synthesized at 1200°C and 200 MPa, continuously decompressed between 200 and 25 MPa at a rate of either 39 or 78 kPa/s (or 1.5 and 3 m/s, respectively), and rapidly quenched. Run products were characterized both texturally (by X-ray computed tomography and scanning electron microscopy) and chemically (by IR spectroscopy and electron microprobe analysis), and then compared with products from basaltic Plinian eruptions and Stromboli paroxysms (bubble textures, glass inclusions). The obtained results demonstrate that textures are controlled by the kinetics of nucleation, growth, coalescence and outgassing of the bubbles, as well as by fragmentation, which largely depend on the presence of CO2 in the melt and the achievement in chemical equilibrium. Textures of the H2O-only melts result from two nucleation events, the first at high pressure (200 < P < 150 MPa) and the second at low pressure (50 < P < 25 MPa), preceding fragmentation. Both events, restricted to narrow P intervals, are driven by melt H2O supersaturation. In contrast, textures of the H2O-CO2-bearing basaltic melts result from continuous bubble nucleation, which is driven by the generation of melts supersaturated in CO2. This persistent non-equilibrium degassing causes the bubbles to evolve through power law distributions, as small bubbles continue to form and grow. This is what is observed in Plinian products. From our results, the evolution to mixed power law-exponential distributions, as found in Stromboli products, is indicative of the prevalence of bubble coalescence and an evolution toward chemical equilibrium. In line with this, a strong correlation was found between experimental and natural bubble textures (bubble number densities, shapes, sizes and distributions), having implications for interpreting bubbles in volcanic rocks and quantifying magma ascent rates. Next step will be to perform in situ decompression experiments to simulate both degassing and crystallization of basaltic magma during ascent in the shallow volcanic conduit (P < 50 MPa), using synchrotron X-ray imaging. The obtained 4D (3D + time) data will help us refine our understanding of magma ascent processes. This experimental programme requires first technology adaptation and development, which is in progress.

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

Single Crystalline Co3O4 Nanocrystals Exposed with Different Crystal Planes for Li-O2 Batteries

PubMed Central

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-01-01

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}. PMID:25169737

Modeling the Time-dependent Changes in Electrical Conductivity of Basaltic Melts With Redox State

NASA Astrophysics Data System (ADS)

Pommier, A.; Gaillard, F.; Pichavant, M.

2008-12-01

The electrical conductivity σ is an efficient probe of mass transfer processes within silicate melts and magmas. Little attention has been given to the influence of redox state (fO2) on the melts conductivity. We present an experimental setup allowing electrical conductivity measurements for basaltic melts under variable fO2. We demonstrate a significant dependence of σ with fO2, allowing to characterize in situ the mechanisms and kinetics of redox changes in the melt. Experiments were conducted on basalts from Pu'u 'O'o, Hawaii, and Mt.Vesuvius, Italy. Measurements were performed cylindrical glass samples (OD: 6mm, ID: 1mm, L: 8mm) using an impedance spectrometer. Experiments were conducted in a 1atm vertical furnace, from 1200°C to 1400°C. Variable gas atmosphere (air, CO2 or CO-CO2 gas mixtures) were used, imposing ΔNNO from -1 to +7. Electrical conductivities were determined for the two melts at constant fO2, different T (constant fO2) and constant T, different fO2 (variable fO2) obtained by changing the gas composition. Isothermal reduction and oxidation cycles were performed. Glasses quenched from different T and fO2 conditions were analyzed by electron microprobe, the FeO concentration was determined by wet chemistry. In constant fO2 experiments, a small but detectable effect of fO2 on σ is evidenced. At 1300°C, the difference in the Kilauea sample conductivity between reduced (ΔNNO=-1) and oxidized (ΔNNO=+7) fO2 is <1(ohm.m)-1, the sample being more conductive when reduced. The temperature dependence of σ was fitted using Arrhenian equations, the activation energy Ea being 100kJ/mol. Sodium was identified as the main charge carrier in the melts. The fO2-effect on σ can thus be attributed to the influence of the Fe2+/Fe3+ ratio on sodium mobility. The fO2-dependence of σ was included in the model of Pommier et al.(2008), allowing the conductivity of natural melts to be calculated as a function of T, P, H2O, and fO2. Variable fO2 experiments confirmed the increase in σ when reducing the melt. At 1200°C, for both reduction-oxidation cycles, a stable value of σ following a change in fO2 is reached in 15hours, while 2hours are needed at 1400°C. The real-time changes in σ of basaltic melts following fO2 step changes were monitored. The time-dependent changes in σ are interpreted in terms of kinetics processes due to redox reequilibration between melt and gas. The evolution of σ with time can be fitted using a diffusion-limited process for reduction in CO-CO2 gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation in CO2. Reduction and oxidation rates are similar and increase with T. Oxidation-reduction rates calculated from the analysis of the conductivity evolution with time range from 10-9 to 10-8m2/s for the T range 1200-1400°C. These reaction rates are in agreement with typical alkali diffusion coefficients in basaltic melts. However, the high value of Ea (230kJ/mol) calculated from the T dependence of the oxidation-reduction rates agrees with the Ea for alkali-Earth elements. Furthermore, microprobe analyses document the existence of alkali-Earth cation fluxes during oxidations and reductions. Such cation migration probably occurs to charge-balance electron fluxes in the melt, in agreement with the study of Cooper et al. (1996). Our results suggest that the migration of alkali and alkali-Earth elements rate-limits the redox state changes in basaltic melts, and that redox mechanisms are not restricted to oxygen chemical diffusion. A discussion of chemical vs tracer oxygen diffusion studies is proposed.

Constraining the CO intensity mapping power spectrum at intermediate redshifts

NASA Astrophysics Data System (ADS)

Padmanabhan, Hamsa

2018-04-01

We compile available constraints on the carbon monoxide (CO) 1-0 luminosity functions and abundances at redshifts 0-3. This is used to develop a data driven halo model for the evolution of the CO galaxy abundances and clustering across intermediate redshifts. It is found that the recent constraints from the CO Power Spectrum Survey (z ˜ 3; Keating et al. 2016), when combined with existing observations of local galaxies (z ˜ 0; Keres, Yun & Young 2003), lead to predictions that are consistent with the results of smaller surveys at intermediate redshifts (z ˜ 1-2). We provide convenient fitting forms for the evolution of the CO luminosity-halo mass relation, and estimates of the mean and uncertainties in the CO power spectrum in the context of future intensity mapping experiments.

Evolution and phylogeographic dissemination of endemic porcine picornaviruses in Vietnam

PubMed Central

Lu, Lu; Van Dung, Nguyen; Bryant, Juliet E.; Carrique-Mas, Juan; Van Cuong, Nguyen; Anh, Pham Honh; Rabaa, Maia A.; Baker, Stephen; Simmonds, Peter; Woolhouse, Mark E.

2016-01-01

Members of the Picornaviridae are important and often zoonotic viruses responsible for a variety of human and animal diseases. However, the evolution and spatial dissemination of different picornaviruses circulating in domestic animals are not well studied. We examined the rate of evolution and time of origin of porcine enterovirus G (EV-G) and porcine kobuvirus species C lineages (PKV-C) circulating in pig farms in Vietnam and from other countries. We further explored the spatiotemporal spread of EV-G and PKV-C in Southwest Vietnam using phylogeographic models. Multiple types of EV-G are co-circulating in Vietnam. The two dominant EV-G types among isolates from Vietnam (G1 and G6) showed strong phylogenetic clustering. Three clades of PKV-C (PKV-C1-3) represent more recent introductions into Vietnam; PKV-C2 is closely related to PKV-C from Southwest China, indicating possible cross-border dissemination. In addition, high virus lineage migration rates were estimated within four districts in Dong Thap province in Vietnam for both EV-G types (G1, G6) and all PKV-C (C1-3) clades. We found that Chau Thanh district is a primary source of both EV-G and PKV-C clades, consistent with extensive pig trading in and out of the district. Understanding the evolution and spatial dissemination of endemic picornaviruses in pigs may inform future strategies for the surveillance and control of picornaviruses. PMID:27774295

Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

PubMed

Liu, Mengjia; Li, Jinghong

2016-01-27

The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations.

Combinatorial pathway optimization in Escherichia coli by directed co-evolution of rate-limiting enzymes and modular pathway engineering.

PubMed

Lv, Xiaomei; Gu, Jiali; Wang, Fan; Xie, Wenping; Liu, Min; Ye, Lidan; Yu, Hongwei

2016-12-01

Metabolic engineering of microorganisms for heterologous biosynthesis is a promising route to sustainable chemical production which attracts increasing research and industrial interest. However, the efficiency of microbial biosynthesis is often restricted by insufficient activity of pathway enzymes and unbalanced utilization of metabolic intermediates. This work presents a combinatorial strategy integrating modification of multiple rate-limiting enzymes and modular pathway engineering to simultaneously improve intra- and inter-pathway balance, which might be applicable for a range of products, using isoprene as an example product. For intra-module engineering within the methylerythritol-phosphate (MEP) pathway, directed co-evolution of DXS/DXR/IDI was performed adopting a lycopene-indicated high-throughput screening method developed herein, leading to 60% improvement of isoprene production. In addition, inter-module engineering between the upstream MEP pathway and the downstream isoprene-forming pathway was conducted via promoter manipulation, which further increased isoprene production by 2.94-fold compared to the recombinant strain with solely protein engineering and 4.7-fold compared to the control strain containing wild-type enzymes. These results demonstrated the potential of pathway optimization in isoprene overproduction as well as the effectiveness of combining metabolic regulation and protein engineering in improvement of microbial biosynthesis. Biotechnol. Bioeng. 2016;113: 2661-2669. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

MAVEN/IUVS Periapse Lyman-alpha Observations: Variability and Constraints on H and CO2 Abundance

NASA Astrophysics Data System (ADS)

Hughes, A. C. G.; Chaffin, M.; Mierkiewicz, E. J.; Chaufray, J. Y.; Deighan, J.; Schneider, N. M.; Thiemann, E.; Clarke, J. T.; Mayyasi, M.; Jain, S. K.; Crismani, M. M. J.; Stiepen, A.; Montmessin, F.; Epavier, F.; Stewart, I. F.; McClintock, B.; Holsclaw, G.; Jakosky, B. M.

2017-12-01

The abundance of spectroscopic and geomorphologic evidence demonstrating that liquid water once flowed on Mars raises significant questions regarding the history of Martian water and the evolution of the atmosphere into the current hyper-arid climate. Using data from the Imaging UltraViolet Spectrograph (IUVS) onboard the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft, we evaluate the hydrogen Lyman-alpha emission (121.6 nm) across multiple Martian years and solar zenith angles. We create altitude-intensity profiles of atmospheric hydrogen emission using periapse data from all MAVEN orbits to-date. Due to the optically thin emission of the UV-doublet scale height of mid-ultraviolet IUVS data, we are able to indirectly probe the temperature of the atmosphere. By combining mid-ultraviolet and far-ultraviolet IUVS data, we extract temperatures and densities of the upper atmosphere and fit the data using a radiative transfer forward model. Below 120 km, the H Lyman-alpha emission is absorbed by CO2, providing constraint on CO2 in the lower thermosphere. Fitting the altitude-intensity curves below 120 km altitude and comparing spatial and temporal variations of the profiles allows us to constrain CO2 abundances. The results of this work, in combination with other MAVEN findings, will provide better constraints on Martian H and CO2 densities and determining neutral temperatures, as well as a more thorough understanding of the evolution of the Martian atmosphere through time.

Toward explaining the Holocene carbon dioxide and carbon isotope records: Results from transient ocean carbon cycle-climate simulations

NASA Astrophysics Data System (ADS)

Menviel, L.; Joos, F.

2012-03-01

The Bern3D model was applied to quantify the mechanisms of carbon cycle changes during the Holocene (last 11,000 years). We rely on scenarios from the literature to prescribe the evolution of shallow water carbonate deposition and of land carbon inventory changes over the glacial termination (18,000 to 11,000 years ago) and the Holocene and modify these scenarios within uncertainties. Model results are consistent with Holocene records of atmospheric CO2 and δ13C as well as the spatiotemporal evolution of δ13C and carbonate ion concentration in the deep sea. Deposition of shallow water carbonate, carbonate compensation of land uptake during the glacial termination, land carbon uptake and release during the Holocene, and the response of the ocean-sediment system to marine changes during the termination contribute roughly equally to the reconstructed late Holocene pCO2 rise of 20 ppmv. The 5 ppmv early Holocene pCO2 decrease reflects terrestrial uptake largely compensated by carbonate deposition and ocean sediment responses. Additional small contributions arise from Holocene changes in sea surface temperature, ocean circulation, and export productivity. The Holocene pCO2 variations result from the subtle balance of forcings and processes acting on different timescales and partly in opposite direction as well as from memory effects associated with changes occurring during the termination. Different interglacial periods with different forcing histories are thus expected to yield different pCO2 evolutions as documented by ice cores.

Synthetic Active Site Model of the [NiFeSe] Hydrogenase.

PubMed

Wombwell, Claire; Reisner, Erwin

2015-05-26

A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe('S2Se2')(CO)3] (H2'S2Se2' = 1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni('S2Se2')] with [Fe(CO)3bda] (bda = benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe('S2Se2')(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe('S2Se2')(CO)3] with the previously reported thiolate analogue [NiFe('S4')(CO)3] (H2'S4' = H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe('S2Se2')(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe('S2Se2')(CO)3] and [NiFe('S4')(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

FeS2 /CoS2 Interface Nanosheets as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Li, Yuxuan; Yin, Jie; An, Li; Lu, Min; Sun, Ke; Zhao, Yong-Qin; Gao, Daqiang; Cheng, Fangyi; Xi, Pinxian

2018-05-28

Electrochemical water splitting to produce hydrogen and oxygen, as an important reaction for renewable energy storage, needs highly efficient and stable catalysts. Herein, FeS 2 /CoS 2 interface nanosheets (NSs) as efficient bifunctional electrocatalysts for overall water splitting are reported. The thickness and interface disordered structure with rich defects of FeS 2 /CoS 2 NSs are confirmed by atomic force microscopy and high-resolution transmission electron microscopy. Furthermore, extended X-ray absorption fine structure spectroscopy clarifies that FeS 2 /CoS 2 NSs with sulfur vacancies, which can further increase electrocatalytic performance. Benefiting from the interface nanosheets' structure with abundant defects, the FeS 2 /CoS 2 NSs show remarkable hydrogen evolution reaction (HER) performance with a low overpotential of 78.2 mV at 10 mA cm -2 and a superior stability for 80 h in 1.0 m KOH, and an overpotential of 302 mV at 100 mA cm -2 for the oxygen evolution reaction (OER). More importantly, the FeS 2 /CoS 2 NSs display excellent performance for overall water splitting with a voltage of 1.47 V to achieve current density of 10 mA cm -2 and maintain the activity for at least 21 h. The present work highlights the importance of engineering interface nanosheets with rich defects based on transition metal dichalcogenides for boosting the HER and OER performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The evolution of C/O in dwarf galaxies from Hubble Space Telescope FOS observations

NASA Technical Reports Server (NTRS)

Garnett, D. R.; Skillman, E. D.; Dufour, R. J.; Peimbert, M.; Torres-Peimbert, S.; Terlevich, R.; Terlevich, E.; Shields, G. A.

1995-01-01

We present UV observations of seven H II regions in low-luminosity dwarf irregular galaxies and the Magellanic Clouds obtained with the Faint Object Spectrograph (FOS) on the Hubble Space Telescope (HST) in order to measure the C/O abundance ratio in the interstellar medium (ISM) of those galaxies. We measure both O III 1666 A and C III 1909 A in our spectra, enabling us to determine C(+2)/O(+2) with relatively small uncertainties. The results from our HST observations show a continuous increase in C/O with increasing O/H, consistent with a power law having an index of 0.43 +/- 0.09 over the range -4.7 to -3.6 in log (O/H). One possible interpretation of this trend is that the most metal-poor galaxies are the youngest and dominated by the products of early enrichment by massive stars, while more metal-rich galaxies show increasing, delayed contributions of carbon from intermediate-mass stars. Our results also suggest that it may not be appropiate to combine abundances in irregular galaxies with those in spiral galaxies to study the evolution of chemical abundances. Our measured C/O ratios in the most metal-poor galaxies are consistent with predictions of nucleosynthesis from massive stars for Weaver & Woosley's best estimate for the 12C(alpha, gamma) 16O nuclear reaction rate, assuming negligible contanmination from carbon produced in intermediate-mass stars in these galaxies. We detect a weak N III 1750 A multiplet in SMC N88A and obtain interesting upper limits for two other objects. Our 2 sigma uppr limits on the 1750 A feature indicate that the N(+2)/O(+2) ratios in these objects are not significantly larger than the N(+)/O(+) ratios measured from optical spectra. This behavior is consistent with predictions of photionization models, although better detections of N III are needed to confirm the results.

Carbon dioxide emission rate of Kīlauea Volcano: Implications for primary magma and the summit reservoir

USGS Publications Warehouse

Gerlach, T.M.; McGee, K.A.; Elias, T.; Sutton, A.J.; Doukas, M.P.

2002-01-01

 We report a CO2 emission rate of 8500 metric tons per day (t d−1) for the summit of Kīlauea Volcano, several times larger than previous estimates. It is based on three sets of measurements over 4 years of synchronous SO2 emission rates and volcanic CO2/SO2concentration ratios for the summit correlation spectrometer (COSPEC) traverse. Volcanic CO2/SO2 for the traverse is representative of the global ratio for summit emissions. The summit CO2 emission rate is nearly constant, despite large temporal variations in summit CO2/SO2 and SO2 emission rates. Summit CO2 emissions comprise most of Kīlauea's total CO2 output (∼9000 t d−1). The bulk CO2 content of primary magma determined from CO2emission and magma supply rate data is ∼0.70 wt %. Most of the CO2 is present as exsolved vapor at summit reservoir depths, making the primary magma strongly buoyant. Turbulent mixing with resident reservoir magma, however, prevents frequent eruptions of buoyant primary magma in the summit region. CO2 emissions confirm that the magma supply enters the edifice through the summit reservoir. A persistent several hundred parts per million CO2 anomaly arises from the entry of magma into the summit reservoir beneath a square kilometer area east of Halemaumau pit crater. Since most of the CO2 in primary magma is degassed in the summit, the summit CO2 emission rate is an effective proxy for the magma supply rate. Both scrubbing of SO2 and solubility controls on CO2and S in basaltic melt cause high CO2/SO2 in summit emissions and spatially uncorrelated distributions of CO2 and SO2 in the summit plume.

Internucleotide correlations and nucleotide periodicity in Drosophila mtDNA: new evidence for panselective evolution.

PubMed

Valenzuela, Carlos Y

2010-01-01

Analysis for the homogeneity of the distribution of the second base of dinucleotides in relation to the first, whose bases are separated by 0, 1, 2,... 21 nucleotide sites, was performed with the VIH-1 genome (cDNA), the Drosophila mtDNA, the Drosophila Torso gene and the human p-globin gene. These four DNA segments showed highly significant heterogeneities of base distributions that cannot be accounted for by neutral or nearly neutral evolution or by the "neighbor influence" of nucleotides on mutation rates. High correlations are found in the bases of dinucleotides separated by 0, 1 and more number of sites. A periodicity of three consecutive significance values (measured by the x²9) was found only in Drosophila mtDNA. This periodicity may be due to an unknown structure or organization of mtDNA. This non-random distribution of the two bases of dinucleotides widespread throughout these DNA segments is rather compatible with panselective evolution and generalized internucleotide co-adaptation.

In Situ Fabrication of Hierarchically Branched TiO2 Nanostructures: Enhanced Performance in Photocatalytic H2 Evolution and Li-Ion Batteries.

PubMed

Yang, Guorui; Wang, Ling; Peng, Shengjie; Wang, Jianan; Ji, Dongxiao; Yan, Wei; Ramakrishna, Seeram

2017-12-01

1D branched TiO 2 nanomaterials play a significant role in efficient photocatalysis and high-performance lithium ion batteries. In contrast to the typical methods which generally have to employ epitaxial growth, the direct in situ growth of hierarchically branched TiO 2 nanofibers by a combination of the electrospinning technique and the alkali-hydrothermal process is presented in this work. Such the branched nanofibers exhibit improvement in terms of photocatalytic hydrogen evolution (0.41 mmol g -1 h -1 ), in comparison to the conventional TiO 2 nanofibers (0.11 mmol g -1 h -1 ) and P25 (0.082 mmol g -1 h -1 ). Furthermore, these nanofibers also deliver higher lithium specific capacity at different current densities, and the specific capacity at the rate of 2 C is as high as 201. 0 mAh g -1 , roughly two times higher than that of the pristine TiO 2 nanofibers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis.

PubMed

Valverde, Jose Manuel; Medina, Santiago

2017-03-15

This work reports an in situ XRD analysis of whether the calcination/carbonation behavior of natural limestone (CaCO 3 ) is affected by the addition of H 2 O to the calciner at a very low concentration under relevant Calcium-Looping (CaL) conditions for CO 2 capture in coal fired power plants (CFPP) and Thermochemical Energy Storage (TCES) in Concentrated Solar Power plants (CSP). Previous studies have demonstrated that the presence of steam in the calciner at a high concentration yields a significant increase in the reaction rate. However, a further undesired consequence is the serious deterioration of the CaO mechanical strength, which would lead to particle attrition and mass loss in any CaL process based on the use of circulating fluidized beds. The results presented in this manuscript on the time evolution of the wt% and crystallite size of the phases involved in the calcination/carbonation reactions indicate that the calcination rate is still notably increased by the presence of H 2 O at very low concentrations whereas the reactivity toward carbonation and crystal structure of the formed CaO are not essentially affected, which suggests that the CaO mechanical strength is not impaired. Thus, the benefit of using steam for calcination in the CaL process could be still retained while at the same time particle attrition would not be promoted.

Nature-Inspired 2D-Mosaic 3D-Gradient Mesoporous Framework: Bimetal Oxide Dual-Composite Strategy toward Ultrastable and High-Capacity Lithium Storage.

PubMed

Yu, Jia; Wang, Yanlei; Mou, Lihui; Fang, Daliang; Chen, Shimou; Zhang, Suojiang

2018-02-27

In allusion to traditional transition-metal oxide (TMO) anodes for lithium-ion batteries, which face severe volume variation and poor conductivity, herein a bimetal oxide dual-composite strategy based on two-dimensional (2D)-mosaic three-dimensional (3D)-gradient design is proposed. Inspired by natural mosaic dominance phenomena, Zn 1-x Co x O/ZnCo 2 O 4 2D-mosaic-hybrid mesoporous ultrathin nanosheets serve as building blocks to assemble into a 3D Zn-Co hierarchical framework. Moreover, a series of derivative frameworks with high evolution are controllably synthesized, based on which a facile one-pot synthesis process can be developed. From a component-composite perspective, both Zn 1-x Co x O and ZnCo 2 O 4 provide superior conductivity due to bimetal doping effect, which is verified by density functional theory calculations. From a structure-composite perspective, 2D-mosaic-hybrid mode gives rise to ladder-type buffering and electrochemical synergistic effect, thus realizing mutual stabilization and activation between the mosaic pair, especially for Zn 1-x Co x O with higher capacity yet higher expansion. Moreover, the inside-out Zn-Co concentration gradient in 3D framework and rich oxygen vacancies further greatly enhance Li storage capability and stability. As a result, a high reversible capacity (1010 mA h g -1 ) and areal capacity (1.48 mA h cm -2 ) are attained, while ultrastable cyclability is obtained during high-rate and long-term cycles, rending great potential of our 2D-mosaic 3D-gradient design together with facile synthesis.

Evolutionary dynamics of Hepatitis C virus in a chronic HIV co-infected patient and its correlation with the immune status.

PubMed

Culasso, Andrés Carlos Alberto; Monzani, María Cecilia; Baré, Patricia; Campos, Rodolfo Hector

2018-05-04

The HCV evolutionary dynamics play a key role in the infection onset, maintenance of chronicity, pathogenicity, and drug resistance variants fixation, and are thought to be one of the main caveats in the development of an effective vaccine. Previous studies in HCV/HIV co-infected patients suggest that a decline in the immune status is related with increases in the HCV intra-host genetic diversity. However, these findings are based on single point sequence diversity measures or coalescence analyses in several virus-host interactions. In this work, we describe the molecular evolution of HCV-E2 region in a single HIV-co-infected patient with two clearly defined immune conditions. The phylogenetic analysis of the HCV-1a sequences from the studied patient showed that he was co-infected with three different viral lineages. These lineages were not evenly detected throughout time. The sequence diversity and coalescence analyses of these lineages suggested the action of different evolutionary patterns in different immune conditions: a slow rate, drift-like process in an immunocompromised condition (low levels of CD4+ T lymphocytes); and a fast rate, variant-switch process in an immunocompetent condition (high levels of CD4+ T lymphocytes). Copyright © 2017. Published by Elsevier B.V.

Calculating the balance between atmospheric CO2 drawdown and organic carbon oxidation in subglacial hydrochemical systems

NASA Astrophysics Data System (ADS)

Graly, Joseph A.; Drever, James I.; Humphrey, Neil F.

2017-04-01

In order to constrain CO2 fluxes from biogeochemical processes in subglacial environments, we model the evolution of pH and alkalinity over a range of subglacial weathering conditions. We show that subglacial waters reach or exceed atmospheric pCO2 levels when atmospheric gases are able to partially access the subglacial environment. Subsequently, closed system oxidation of sulfides is capable of producing pCO2 levels well in excess of atmosphere levels without any input from the decay of organic matter. We compared this model to published pH and alkalinity measurements from 21 glaciers and ice sheets. Most subglacial waters are near atmospheric pCO2 values. The assumption of an initial period of open system weathering requires substantial organic carbon oxidation in only 4 of the 21 analyzed ice bodies. If the subglacial environment is assumed to be closed from any input of atmospheric gas, large organic carbon inputs are required in nearly all cases. These closed system assumptions imply that order of 10 g m-2 y-1 of organic carbon are removed from a typical subglacial environment—a rate too high to represent soil carbon built up over previous interglacial periods and far in excess of fluxes of surface deposited organic carbon. Partial open system input of atmospheric gases is therefore likely in most subglacial environments. The decay of organic carbon is still important to subglacial inorganic chemistry where substantial reserves of ancient organic carbon are found in bedrock. In glaciers and ice sheets on silicate bedrock, substantial long-term drawdown of atmospheric CO2 occurs.

Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage† †Electronic supplementary information (ESI) available: Experimental and computational details, free energy plots for the NH3 evolution and N2 reduction with Co3N/Co, Fe4N/Fe, Mn5N2/Mn4N, Mo2N/Mo, CrN/Cr2N, TaN/Ta2N, NbN/Nb2N, Li3N/LiH, Ba3N2/BaH2, Sr3N2/SrH2, and Ca3N2/CaH2, surface oxidation energetics, ΔGvac[NH*x, yH*] based on gas phase H2 as hydrogen source, NH3 evolution with Fe-doped Mn4N, NH3 evolution with Mn6N2.58, Ca3N2 and Sr2N after correcting for partial nitride hydrolysis, NH3 yield from Ca3N2vs. time and H2 gas flow rate. See DOI: 10.1039/c5sc00789e

PubMed Central

Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A.

2015-01-01

The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH3), a fertilizer and chemical fuel, from N2 and H2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn6N2.58 to Mn4N and hydrogenation of Ca3N2 and Sr2N to Ca2NH and SrH2, respectively. PMID:29218166

Drivers of multi-century trends in the atmospheric CO2 mean annual cycle in a prognostic ESM

NASA Astrophysics Data System (ADS)

Liptak, Jessica; Keppel-Aleks, Gretchen; Lindsay, Keith

2017-03-01

The amplitude of the mean annual cycle of atmospheric CO2 is a diagnostic of seasonal surface-atmosphere carbon exchange. Atmospheric observations show that this quantity has increased over most of the Northern Hemisphere (NH) extratropics during the last 3 decades, likely from a combination of enhanced atmospheric CO2, climate change, and anthropogenic land use change. Accurate climate prediction requires accounting for long-term interactions between the environment and carbon cycling; thus, analysis of the evolution of the mean annual cycle in a fully prognostic Earth system model may provide insight into the multi-decadal influence of environmental change on the carbon cycle. We analyzed the evolution of the mean annual cycle in atmospheric CO2 simulated by the Community Earth System Model (CESM) from 1950 to 2300 under three scenarios designed to separate the effects of climate change, atmospheric CO2 fertilization, and land use change. The NH CO2 seasonal amplitude increase in the CESM mainly reflected enhanced primary productivity during the growing season due to climate change and the combined effects of CO2 fertilization and nitrogen deposition over the mid- and high latitudes. However, the simulations revealed shifts in key climate drivers of the atmospheric CO2 seasonality that were not apparent before 2100. CO2 fertilization and nitrogen deposition in boreal and temperate ecosystems were the largest contributors to mean annual cycle amplification over the midlatitudes for the duration of the simulation (1950-2300). Climate change from boreal ecosystems was the main driver of Arctic CO2 annual cycle amplification between 1950 and 2100, but CO2 fertilization had a stronger effect on the Arctic CO2 annual cycle amplitude during 2100-2300. Prior to 2100, the NH CO2 annual cycle amplitude increased in conjunction with an increase in the NH land carbon sink. However, these trends decoupled after 2100, underscoring that an increasing atmospheric CO2 annual cycle amplitude does not necessarily imply a strengthened terrestrial carbon sink.

Thermal induced BCN nanosheets evolution and its usage as metal-free catalyst in ethylbenzene dehydrogenation

NASA Astrophysics Data System (ADS)

Wang, Liancheng; Wang, Conghui; Zhang, Zhenwei; Wu, Jianghong; Ding, Ruimin; Lv, Baoliang

2017-11-01

Compared with mushroomed progress in metal-free C-rich BCN catalysts, little is known about the BN-rich BCN or even BN ones. Its related study has drawn great interest recently but still in its infancy stage. In this study, three kinds of BCN nanosheets (NSs) with tuned surface carbon contents (5.5-14.3%), specific surface area (SSA, 82-290 m2/g) and morphologies (ultrathin nanosheets, triangular plates) were fabricated through a solid state reaction by simply adjusting the reaction temperature, and those effects on the ethylbenzene dehydrogenation performances were studied in CO2 atmosphere. The morphology evolution of BCN NSs from ultrathin nanosheets to the triangular plates was observed and control experiments were carried out. The BCN nanosheets show relatively strong interaction with CO2 and distinct CO2 absorption properties. The CO2 temperature programmed desorption also indicates that the desorption peaks of CO2 are above 400 °C, enabling them potential CO2 utilization catalysts. A weak association was found between the surface C contents and the catalytic performance as it normalized with SSA, and the B-O species could be taken as an active site in CO2 atmosphere. Though much progress still needed, it is convincing that the BCN catalyst could be a promising metal-free catalyst in dehydrogenation beyond carbocatalyst.

ALMA Observations of the Molecular Gas in the Debris Disk of the 30 Myr Old Star HD 21997

NASA Technical Reports Server (NTRS)

Kospal, A.; Moor, A.; Juhasz, A.; Abraham, P.; Apai, D.; Csengeri, T.; Grady, C. A.; Henning, Th.; Hughes, A. M.; Kiss, Cs.;

Land plants, weathering, and Paleozoic climatic evolution

NASA Astrophysics Data System (ADS)

Goddéris, Yves; Maffre, Pierre; Donnadieu, Yannick; Carretier, Sébastien

2017-04-01

At the end of the Paleozoic, the Earth plunged into the longest and most severe glaciation of the Phanerozoic eon (Montanez et al., 2013). The triggers for this event (called the Late Paleozoic Ice Age, LPIA) are still debated. Based on field observations and laboratory experiments showing that CO2 consumption by rock weathering is enhanced by the presence of plants, the onset of the LPIA has been related to the colonization of the continents by vascular plants in the latest Devonian. By releasing organic acids, concentrating respired CO2 in the soil, and by mechanically breaking rocks with their roots, land plants may have increased the weatherability of the continental surfaces. The "greening" of the continents may also have contributed to an enhanced burial of organic carbon in continental sedimentary basins, assuming that lignin decomposers have not yet evolved (Berner, 2004). As a consequence, CO2 went down, setting the conditions for the onset of the LPIA. This scenario is now widely accepted in the scientific community, and reinforces the feeling that biotic evolutionary steps are main drivers of the long-term climatic evolution. Although appealing, this scenario suffers from some weaknesses. The timing of the continent colonization by vascular plants was achieved in the late Devonian, several tens of million years before the onset of the LPIA (Davies and Gibling, 2013). Second, lignin decomposer fungi were present at the beginning of the Carboniferous, 360 million years ago while the LPIA started around 340-330 Ma (Nelsen et al., 2016). Land plants have also decreased the continental albedo, warming the Earth surface and promoting runoff. Weathering was thus facilitated and CO2 went down. Yet, temperature may have stayed constant, the albedo change compensating for the CO2 fall (Le Hir et al., 2010). From a modelling point of view, the effect of land plants on CO2 consumption by rock weathering is accounted for by forcing the weatherability of the continents to rise by a factor of 6 (Berner, 2004). This factor has been inferred from studies of the weathering rate of rocks in young environments, such as recent lava flows colonized by the vegetation (e.g. Moulton et al., 2001). Nevertheless, present-day continental areas displaying a dense vegetal cover (equatorial forests) are characterized by low weathering rates (West, 2012). Indeed, the development of thick and depleted weathering profiles has shifted those systems into a supply-limited regime. The arising questions are thus: is the land plant effect on CO2 consumption by weathering only transient, and if yes, how long does it last? Thousand, million, or tens of million years? Is a world fully vegetated weathering faster than a naked world? Those questions will be investigated through a modelling study simulating the colonization of the continents by land plants in the late Paleozoic using a simple cellular automata algorithm, coupled to a weathering model accounting for the role of the regolith thickness on the weathering regime.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances.

PubMed

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-25

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co 9 S 8 aerogel with a high surface area (274.2 m 2 g -1 ) and large pore volume (0.87 cm 3 g -1 ) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co 9 S 8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g -1 at 1 A g -1 ), good rate capability (74.3% capacitance retention from 1 to 20 A g -1 ) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

NASA Astrophysics Data System (ADS)

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-01

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

A model for the evolution of CO2 on Mars

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Tyler, D.; Mckay, C. P.; Davis, W. L.

1993-01-01

There are several lines of evidence that suggest early Mars was warmer and wetter than it is at present. Perhaps the most convincing of these are the valley networks and degraded craters that characterize much of the ancient terrains. In both cases, fluvial activity associated with liquid water is believed to be involved. Thus, Mars appears to have had a warmer climate early in its history than it does today. How much warmer is not clear, but a common perception has been that global mean surface temperatures must have been near freezing - almost 55 K warmer than at present. The most plausible way to increase surface temperatures is through the greenhouse effect, and the most plausible greenhouse gas is CO2. Pollack et al. estimate that in the presence of the faint young Sun, the early Martian atmosphere would have to contain almost 5 bar of CO2 to raise the mean surface temperature up to the freezing level; only 1 bar would be required if the fluvial features were formed near the calculations now appear to be wrong since Kasting showed that CO2 will condense in the atmosphere at these pressures and that this greatly reduces the greenhouse effect of a pure CO2 atmosphere. He suggested that alternative greenhouse gases such as CH4 or NH3, are required. The early Mars dilemma is approached from a slightly different point of view. In particular, a model for the evolution of CO2 on Mars that draws upon published processes that affect such evolution was constructed. Thus, the model accounts for the variation of solar luminosity with time, the greenhouse effect, regolith uptake, polar cap formation, escape, and weathering.

Porosity and Permeability Evolution in Cemented Rock Cores under Reactive Flowing Conditions: Comparative Analysis between Limestone and Sandstone Host Rocks

NASA Astrophysics Data System (ADS)

Cao, P.; Karpyn, Z.; Li, L.

2013-12-01

CO2-brine has the potential to alter wellbore cement in depleted oil and gas reservoirs under geological CO2 sequestration conditions. A better understanding of CO2-brine-cement-rock interaction is needed to evaluate the seal integrity of candidate sequestration formation in the long run. This work investigates possible alteration of wellbore cement when bonded by different host formation rock upon exposure to CO2-saturated brine. Composite cement-sandstone and cement-limestone core samples were created to perform reactive coreflood experiments. After an eight-day dynamic flow-through period, both cores had a similar extent of porosity increase, while the cement-limestone core experienced a ten-fold higher increase in permeability. With the aid of X-ray Micro-CT imaging and Scanning Electron Microscopy, it is observed that cement underwent greater degradation at the cement-sandstone interface. Degradation of cement-limestone core mainly took place on the host rock matrix. Worm holes were developed and a solution channel was formed in the limestone, creating a dominant flow path that altered both flow and reaction behavior. Limestone buffered the injected acidic brine preventing further deterioration of cement near the core outlet. Changes in fluid chemistry of limestone and sandstone coreflood effluents are compared. Results from this work are aimed at assisting the development and validation of robust reactive transport models through direct measurement of cemented rock core porosity and permeability evolution as well as the effluent aqueous chemistry change. This will subsequently improve predictive capabilities of reactive transport models associated with CO2 sequestration in geologic environments. Permeability Evolution of Cement-Rock Core Sample during Dynamic Flow of CO2-Brine