Mechanical instability of monocrystalline and polycrystalline methane hydrates

PubMed Central

Wu, Jianyang; Ning, Fulong; Trinh, Thuat T.; Kjelstrup, Signe; Vlugt, Thijs J. H.; He, Jianying; Skallerud, Bjørn H.; Zhang, Zhiliang

2015-01-01

Despite observations of massive methane release and geohazards associated with gas hydrate instability in nature, as well as ductile flow accompanying hydrate dissociation in artificial polycrystalline methane hydrates in the laboratory, the destabilising mechanisms of gas hydrates under deformation and their grain-boundary structures have not yet been elucidated at the molecular level. Here we report direct molecular dynamics simulations of the material instability of monocrystalline and polycrystalline methane hydrates under mechanical loading. The results show dislocation-free brittle failure in monocrystalline hydrates and an unexpected crossover from strengthening to weakening in polycrystals. Upon uniaxial depressurisation, strain-induced hydrate dissociation accompanied by grain-boundary decohesion and sliding destabilises the polycrystals. In contrast, upon compression, appreciable solid-state structural transformation dominates the response. These findings provide molecular insight not only into the metastable structures of grain boundaries, but also into unusual ductile flow with hydrate dissociation as observed during macroscopic compression experiments. PMID:26522051

Evaluation of simulated corn yields and associated uncertainty in different climate zones of China using Daycent Model

NASA Astrophysics Data System (ADS)

Fu, A.; Xue, Y.

2017-12-01

Corn is one of most important agricultural production in China. Research on the simulation of corn yields and the impacts of climate change and agricultural management practices on corn yields is important in maintaining the stable corn production. After climatic data including daily temperature, precipitation, solar radiation, relative humidity, and wind speed from 1948 to 2010, soil properties, observed corn yields, and farmland management information were collected, corn yields grown in humidity and hot environment (Sichuang province) and cold and dry environment (Hebei province) in China in the past 63 years were simulated by Daycent, and the results was evaluated based on published yield record. The relationship between regional climate change, global warming and corn yield were analyzed, the uncertainties of simulation derived from agricultural management practices by changing fertilization levels, land fertilizer maintenance and tillage methods were reported. The results showed that: (1) Daycent model is capable to simulate corn yields under the different climatic background in China. (2) When studying the relationship between regional climate change and corn yields, it has been found that observed and simulated corn yields increased along with total regional climate change. (3) When studying the relationship between the global warming and corn yields, It was discovered that newly-simulated corn yields after removing the global warming trend of original temperature data were lower than before.

New observations and insights into the morphology and growth kinetics of hydrate films.

PubMed

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K

2014-02-19

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6.

New Observations and Insights into the Morphology and Growth Kinetics of Hydrate Films

PubMed Central

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K.

2014-01-01

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6. PMID:24549241

Visual observation of gas hydrates nucleation and growth at a water - organic liquid interface

NASA Astrophysics Data System (ADS)

Stoporev, Andrey S.; Semenov, Anton P.; Medvedev, Vladimir I.; Sizikov, Artem A.; Gushchin, Pavel A.; Vinokurov, Vladimir A.; Manakov, Andrey Yu.

2018-03-01

Visual observation of nucleation sites of methane and methane-ethane-propane hydrates and their further growth in water - organic liquid - gas systems with/without surfactants was carried out. Sapphire Rocking Cell RCS6 with transparent sapphire cells was used. The experiments were conducted at the supercooling ΔTsub = 20.2 °C. Decane, toluene and crude oils were used as organics. Gas hydrate nucleation occurred on water - metal - gas and water - sapphire - organic liquid three-phase contact lines. At the initial stage of growth hydrate crystals rapidly covered the water - gas or water - organics interfaces (depending on the nucleation site). Further hydrate phase accrete on cell walls (sapphire surface) and into the organics volume. At this stage, growth was accompanied by water «drawing out» from under initial hydrate film formed at water - organic interface. Apparently, it takes place due to water capillary inflow in the reaction zone. It was shown that the hydrate crystal morphology depends on the organic phase composition. In the case of water-in-decane emulsion relay hydrate crystallization was observed in the whole sample, originating most likely due to the hydrate crystal intergrowth through decane. Contacts of such crystals with adjacent water droplets result in rapid hydrate crystallization on this droplet.

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

USGS Publications Warehouse

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

2003-01-01

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

Magnetic Tracking of Gas Hydrate Deposits.

NASA Astrophysics Data System (ADS)

Lowe, C.; Enkin, R. J.; Judith, B.; Dallimore, S. R.

2005-12-01

Analysis of recovered core from the Mallik gas hydrate field in the Mackenzie Delta, Northwest Territories, Canada demonstrates that the magnetic properties of hydrate-bearing strata differ significantly from those strata lacking gas hydrate. The recovered core, which extends from just above (885 m) to just below (1152 m) observed gas hydrate occurrences (891-1107 m), comprises a series of six stratigraphic units that are either sand or silt dominated. Gas hydrate is preferentially concentrated in the higher porosity, sand-dominated units. Although the sediment source region for the Mackenzie Delta is sufficiently large that silts and sands have similar primary mineralogy, their magnetic properties are distinct. Magnetite, apparent in silt units with porosities too low to accommodate significant gas hydrate deposits, is reduced to iron sulphide in the gas hydrate-bearing sand horizons. The degree of the observed magnetic reduction increases with increasing gas hydrate concentration. Furthermore, silts retain their primary magnetism, whereas sands are remagnetized. Two independent investigations of marine gas hydrate occurrences (Blake Ridge, offshore eastern USA and Cascadia, offshore western Canada) demonstrate similar magnetic reduction within known gas hydrate fields, and an even larger depletion of magnetic minerals in vent zones where methane is actively fluxing to surface. Collectively, the findings from these three regions indicate that porosity and structure are fundamental controls on methane pathways. Investigations are presently underway to determine the precise triggers and chemical pathways of the observed magnetic reductions. However, findings to date indicate that magnetic studies of host sediments in gas hydrate systems provide a powerful lithologic correlation tool, a window into the processes associated with gas hydrate formation, and form the basis of quantitative analysis of magnetic surveys over gas hydrate deposits.

Phase transitions in mixed gas hydrates: experimental observations versus calculated data.

PubMed

Schicks, Judith M; Naumann, Rudolf; Erzinger, Jörg; Hester, Keith C; Koh, Carolyn A; Sloan, E Dendy

2006-06-15

This paper presents the phase behavior of multicomponent gas hydrate systems formed from primarily methane with small amounts of ethane and propane. Experimental conditions were typically in a pressure range between 1 and 6 MPa, and the temperature range was between 260 and 290 K. These multicomponent systems have been investigated using a variety of techniques including microscopic observations, Raman spectroscopy, and X-ray diffraction. These techniques, used in combination, allowed for measurement of the hydrate structure and composition, while observing the morphology of the hydrate crystals measured. The hydrate formed immediately below the three-phase line (V-L --> V-L-H) and contained crystals that were both light and dark in appearance. The light crystals, which visually were a single solid phase, showed a spectroscopic indication for the presence of occluded free gas in the hydrate. In contrast, the dark crystals were measured to be structure II (sII) without the presence of these occluded phases. Along with hydrate measurements near the decomposition line, an unexpected transformation process was visually observed at P-T-conditions in the stability field of the hydrates. Larger crystallites transformed into a foamy solid upon cooling over this transition line (between 5 and 10 K below the decomposition temperature). Below the transition line, a mixture of sI and sII was detected. This is the first time that these multicomponent systems have been investigated at these pressure and temperature conditions using both visual and spectroscopic techniques. These techniques enabled us to observe and measure the unexpected transformation process showing coexistence of different gas hydrate phases.

Mineralogical Study of Hydrated IDPs: X-Ray Diffraction and Transmission Electron Microscopy

NASA Technical Reports Server (NTRS)

Nakamura, K.; Keller, L. P.; Nakamura, T.; Noguchi, T.; Zolensky, M. E.

2004-01-01

Chondritic hydrated interplanetary dust particles (IDPs) comprise up to 50% of all IDPs collected in the stratosphere [1]. Hydrated IDPs are generally believed to be derived from asteroidal sources that have undergone aqueous alteration. However, the high C contents of hydrated IDPs (by 2 to 6X CI levels [2,3]) indicate that they are probably not derived from the same parent bodies sampled by the known chondritic meteorites. Some hydrated IDPs exhibit large deuterium enrichments [4] similar to those observed in anhydrous IDPs. Both anhydrous and hydrated IDPs contain a variety of anhydrous minerals such as silicates, sulfides, oxides, and carbonates. Controversies on hydrated IDPs still exist regarding their formation, history, and relationship to other primitive solar system materials, because of the lack of a systematic series of analysis on individual hydrated IDPs. In this study, we combine our observations of the bulk mineralogy, mineral/ organic chemistry in order to derive a more complete picture of hydrated IDPs.

Characterization of Gas-Hydrate Sediment: In Situ Evaluation of Hydrate Saturation in Pores of Pressured Sedimental Samples

NASA Astrophysics Data System (ADS)

Jin, Y.; Konno, Y.; Kida, M.; Nagao, J.

2014-12-01

Hydrate saturation of gas-hydrate bearing sediment is a key of gas production from natural gas-hydrate reservoir. Developable natural gas-hydrates by conventional gas/oil production apparatus almost exist in unconsolidated sedimental layer. Generally, hydrate saturations of sedimental samples are directly estimated by volume of gas generated from dissociation of gas hydrates in pore spaces, porosity data and volume of the sediments. Furthermore, hydrate saturation can be also assessed using velocity of P-wave through sedimental samples. Nevertheless, hydrate saturation would be changed by morphological variations (grain-coating, cementing and pore-filling model) of gas hydrates in pore spaces. Jin et al.[1,2] recently observed the O-H stretching bands of H2O molecules of methane hydrate in porous media using an attenuated total reflection IR (ATR-IR) spectra. They observed in situ hydrate formation/dissociation process in sandy samples (Tohoku Keisya number 8, grain size of ca. 110 μm). In this presentation, we present IR spectroscopy approach to in situ evaluation of hydrate saturation of pressured gas-hydrate sediments. This work was supported by funding from the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by the Ministry of Economy, Trade and Industry (METI), Japan. [1] Jin, Y.; Konno, Y.; Nagao, J. Energy Fules, 2012, 26, 2242-2247. [2] Jin, Y.; Oyama, H.; Nagao, J. Jpn. J. Appl. Phys. 2009, 48, No. 108001.

Spatial and temporal dependencies of structure II to structure I methane hydrate transformation in porous media under moderate pressure and temperature conditions

NASA Astrophysics Data System (ADS)

Dong, T.; Lin, J. F.; Gu, J. T.; Polito, P. J.; O'Connell, J.; Flemings, P. B.

2017-12-01

We used Raman spectroscopy to monitor methane hydrates transforming from structure II to structure I at the pore scale as a function of space and time. It is well documented that structure I hydrate is the thermodynamically stable phase for pure methane hydrate (<100 MPa, < 20 °C), but due to kinetic limitation, initial methane hydrate formation produces a mixture of structure I and structure II hydrates. We observed that the structure transformation originated around the porous medium grains and over time slowly migrated into the pore space. We synthesized methane hydrates in spherical glass beads (210-297 µm in diameter) in a pressure cell with a sapphire window to integrate optical observations with Raman measurements. We injected CH4 vapor into the cell and supplied only deionized water thereafter to maintain a constant pressure of 14.6 MPa at 3.5 °C, with 14.5 °C subcooling. We used Raman spectroscopy to map the methane hydrates in pore spaces at 5-25 µm resolution, in order to monitor the occupancy ratio of CH4 in large cages to CH4 in small cages, by their Raman peak intensity ratio, i.e., I( 2905 cm-1)/I( 2915 cm-1). We identified 3 stages of hydrate formation at the pore scale: (1) after the initial hydrate formation, Raman mapping revealed that the occupancy ratio ranged from 0.5 to 3, indicating a mixture of structure I and II hydrates; (2) within 1 week, we observed that all structure I hydrates occurred on the glass bead surfaces and structure II hydrates occupied the pore spaces; (3) over the following 2 weeks, structure II hydrates gradually recrystallized into structure I hydrates from glass bead surfaces towards the pore space. These results imply that (1) due to kinetics, the formation of methane hydrate in porous media is more complex than previously thought, and (2) the bulk physical and chemical properties of laboratory-synthesized methane hydrates in porous media may drift over time, as methane hydrates recrystallize from a metastable phase (structure II) to the thermodynamically stable phase (structure I).

Simulation of corn yields and parameters uncertainties analysis in Hebei and Sichuang, China

NASA Astrophysics Data System (ADS)

Fu, A.; Xue, Y.; Hartman, M. D.; Chandran, A.; Qiu, B.; Liu, Y.

2016-12-01

Corn is one of most important agricultural production in China. Research on the impacts of climate change and human activities on corn yields is important in understanding and mitigating the negative effects of environmental factors on corn yields and maintaining the stable corn production. Using climatic data, including daily temperature, precipitation, and solar radiation from 1948 to 2010, soil properties, observed corn yields, and farmland management information, corn yields in Sichuang and Hebei Provinces of China in the past 63 years were simulated using the Daycent model, and the results was evaluated using Root mean square errors, bias, simulation efficiency, and standard deviation. The primary climatic factors influencing corn yields were examined, the uncertainties of climatic factors was analyzed, and the uncertainties of human activity parameters were also studied by changing fertilization levels and cultivated ways. The results showed that: (1) Daycent model is capable to simulate corn yields in Sichuang and Hebei provinces of China. Observed and simulated corn yields have the similar increasing trend with time. (2) The minimum daily temperature is the primary factor influencing corn yields in Sichuang. In Hebei Province, daily temperature, precipitation and wind speed significantly affect corn yields.(3) When the global warming trend of original data was removed, simulated corn yields were lower than before, decreased by about 687 kg/hm2 from 1992 to 2010; When the fertilization levels, cultivated ways were increased and decreased by 50% and 75%, respectively in the Schedule file in Daycent model, the simulated corn yields increased by 1206 kg/hm2 and 776 kg/hm2, respectively, with the enhancement of fertilization level and the improvement of cultivated way. This study provides a scientific base for selecting a suitable fertilization level and cultivated way in corn fields in China.

Investigation on the effect of THF on Nitrogen Hydrate formation under isobaric condition

NASA Astrophysics Data System (ADS)

Jamil, N.; Husin, H.; Aman, Z.; Hassan, Z.

2018-03-01

In this paper, we studied nitrogen (N2) hydrate formation in the presence of tetrahydrofuran (THF) under 3 different conditions; different concentration of THF (0, 3 and 30 %(v/v), different temperature setting (room temperature and induced temperature) and different water content (15, 35 and 55 mL) in an isobaric condition. We found that in the presence of THF which acting as an enhancer, hydrate formation kinetic is highly influenced by these parameters. We observed a striking contrast in hydrate formation behaviour observed at room temperature (RT) and induced temperature (IT) with and without the presence of THF under similar operating conditions. At the presence of 30 %(v/v) of THF in 15 mL water, it can be seen that, hydrate tend to form faster than other samples. Visual observation of N2hydrates are also conducted at 30 %(v/v) of THF in 15 mL water.

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. II. Two-dimensional infrared and peak shift observables within different theoretical approximations.

PubMed

Gruenbaum, Scott M; Pieniazek, Piotr A; Skinner, J L

2011-10-28

In a previous report, we calculated the infrared absorption spectrum and both the isotropic and anisotropic pump-probe signals for the OD stretch of isotopically dilute water in dilauroylphosphatidylcholine (DLPC) multi-bilayers as a function of the lipid hydration level. These results were then compared to recent experimental measurements and are in generally good agreement. In this paper, we will further investigate the structure and dynamics of hydration water using molecular dynamics simulations and calculations of the two-dimensional infrared and vibrational echo peak shift observables for hydration water in DLPC membranes. These observables have not yet been measured experimentally, but future comparisons may provide insight into spectral diffusion processes and hydration water heterogeneity. We find that at low hydration levels the motion of water molecules inside the lipid membrane is significantly arrested, resulting in very slow spectral diffusion. At higher hydration levels, spectral diffusion is more rapid, but still slower than in bulk water. We also investigate the effects of several common approximations on the calculation of spectroscopic observables by computing these observables within multiple levels of theory. The impact of these approximations on the resulting spectra affects our interpretation of these measurements and reveals that, for example, the cumulant approximation, which may be valid for certain systems, is not a good approximation for a highly heterogeneous environment such as hydration water in lipid multi-bilayers.

Mimicking gluten functionality with β-conglycinin concentrate: Evaluation in gluten free yeast-leavened breads.

PubMed

Espinosa-Ramírez, Johanan; Garzon, Raquel; Serna-Saldivar, Sergio O; Rosell, Cristina M

2018-04-01

Fractionation of soy proteins has proved to produce protein concentrates with viscoelastic properties. In the present study, a β-conglycinin concentrate (βCC) obtained by a pH fractionation of soy flour was tested as structuring agent in gluten-free yeast-leavened bread model. A lean formulation with βCC and corn starch was used to produce gluten-free breads with two hydration conditions and three levels of protein (5%, 10% and 15%). Vital gluten was used to compare the functionality of βCC protein and its performance for breadmaking. Breads were characterized in moisture, color, textural parameters and image analysis. βCC presented lower hydration properties and higher emulsifying activity compared to vital gluten. Blends βCC:starch had higher water binding capacity compared to vital gluten blends. The hydration conditions tested affected the moisture, color and cell density of breads. Breads produced with βCC presented higher 2D area and height and presented higher crumb softness and cohesiveness, and did not present significant differences in springiness and resilience compared to vital gluten breads. The image analysis of crumbs showed higher cell density but lower porosity and mean cell areas in βCC breads. Thus, βCC proved to have potential as a structuring agent in gluten-free breads. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-01

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.

PubMed

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-06

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system.

PubMed

Kim, Jakyung; Shin, Kyuchul; Seo, Yutaek; Cho, Seong Jun; Lee, Ju Dong

2014-07-31

This study investigates the hydrate inhibition performance of monoethylene glycol (MEG) with poly(vinylcaprolactam) (PVCap) for retarding the hydrate onset as well as preventing the agglomeration of hydrate particles. A high-pressure autoclave was used to determine the hydrate onset time, subcooling temperature, hydrate fraction in the liquid phase, and torque changes during hydrate formation in pure water, 0.2 wt % PVCap solution, and 20 and 30 wt % MEG solutions. In comparison to water with no inhibitors, the addition of PVCap delays the hydrate onset time but cannot reduce the hydrate fraction, leading to a sharp increase in torque. The 20 and 30 wt % MEG solutions also delay the hydrate onset time slightly and reduce the hydrate fraction to 0.15. The addition of 0.2 wt % PVCap to the 20 wt % MEG solution, however, delays the hydrate onset time substantially, and the hydrate fraction was less than 0.19. The torque changes were negligible during the hydrate formation, suggesting the homogeneous dispersion of hydrate particles in the liquid phase. The well-dispersed hydrate particles do not agglomerate or deposit under stirring. Moreover, when 0.2 wt % PVCap was added to the 30 wt % MEG solution, no hydrate formation was observed for at least 24 h. These results suggest that mixing of MEG with a small amount of PVCap in underinhibited conditions will induce the synergistic inhibition of hydrate by delaying the hydrate onset time as well as preventing the agglomeration and deposition of hydrate particles. Decreasing the hydrate fraction in the liquid phase might be the reason for negligible torque changes during the hydrate formation in the 0.2 wt % PVCap and 20 wt % MEG solution. Simple structure II was confirmed by in situ Raman spectroscopy for the synergistic inhibition system, while coexisting structures I and II are observed in 0.2 wt % PVCap solution.

Entrapment of Hydrate-coated Gas Bubbles into Oil and Separation of Gas and Hydrate-film; Seafloor Experiments with ROV

NASA Astrophysics Data System (ADS)

Hiruta, A.; Matsumoto, R.

2015-12-01

We trapped gas bubbles emitted from the seafloor into oil-containing collector and observed an unique phenomena. Gas hydrate formation needs water for the crystal lattice; however, gas hydrates in some areas are associated with hydrophobic crude oil or asphalt. In order to understand gas hydrate growth in oil-bearing sediments, an experiment with cooking oil was made at gas hydrate stability condition. We collected venting gas bubbles into a collector with canola oil during ROV survey at a gas hydrate area in the eastern margin of the Sea of Japan. When the gas bubbles were trapped into collector with oil, gas phase appeared above the oil and gas hydrates, between oil and gas phase. At this study area within gas hydrate stability condition, control experiment with oil-free collector suggested that gas bubbles emitted from the seafloor were quickly covered with gas hydrate film. Therefore it is improbable that gas bubbles entered into the oil phase before hydrate skin formation. After the gas phase formation in oil-containing collector, the ROV floated outside of hydrate stability condition for gas hydrate dissociation and re-dived to the venting site. During the re-dive within hydrate stability condition, gas hydrate was not formed. The result suggests that moisture in the oil is not enough for hydrate formation. Therefore gas hydrates that appeared at the oil/gas phase boundary were already formed before bubbles enter into the oil. Hydrate film is the only possible origin. This observation suggests that hydrate film coating gas hydrate was broken at the sea water/oil boundary or inside oil. Further experiments may contribute for revealing kinetics of hydrate film and formation. This work was a part of METI (Ministry of Economy, Trade and Industry)'s project entitled "FY2014 Promoting research and development of methane hydrate". We also appreciate support of AIST (National Institute of Advanced Industrial Science and Technology).

Intraguild competition and enhanced survival of western bean cutworm (Lepidoptera: Noctuidae) on transgenic Cry1Ab (MON810) Bacillus thuringiensis corn.

PubMed

Dorhout, David L; Rice, Marlin E

2010-02-01

The effect of genetically modified corn (event MON810, YieldGard Corn Borer) expressing the Bacillus thuringiensis sp. kurstaki (Berliner) (Bt) endotoxin, Cry1Ab, on the survival of western bean cutworm, Striacosta albicosta (Smith), larvae was examined during intraguild competition studies with either European corn borer, Ostrinia nubilalis (Hübner), or corn earworm, Helicoverpa zea (Boddie), larvae. Competition scenarios were constructed by using either a laboratory or field competition arena containing one of five different diets and one of 13 different larval size-by-species scenarios. The survival of western bean cutworms competing with corn earworms in the laboratory arenas on either a meridic diet or isoline corn silk diet was significantly lower (P < or = 0.01) than the controls in 13 out of 14 competition scenarios and larval survival was frequently zero. In contrast, the survival of western bean cutworm competing with corn earworm on a Cry1Ab-MON810 corn silk diet was significant higher (P < or = 0.01) than the controls in four out of six competition scenarios. The results observed in the three way competitions involving the addition of European corn borers generally did not alter the outcomes observed in the western bean cutworm and corn earworm only two-way competitions. These data suggest that Cry1Ab-MON810 corn may confer a competitive advantage to western bean cutworm larvae during intraguild competition, particularly from corn earworms, and that western bean cutworms become equal competitors only when they are of equal or larger size and the diet is Cry1Ab-MON810 corn.

First report of damping-off of dent corn seedlings caused by Pythium graminicola in Georgia

USDA-ARS?s Scientific Manuscript database

An unknown disease was observed on corn seedlings in commercial corn fields in Tift County, Georgia, in April 2015. Stems of corn seedlings were brown, water-soaked, soft, decayed, and broke off easily. Disease incidence ranged from 2 to 3%. A fungus-like organism was isolated from all infected stem...

Effects of cyclic structure inhibitors on the morphology and growth of tetrahydrofuran hydrate crystals

NASA Astrophysics Data System (ADS)

Li, Sijia; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2013-08-01

Morphology and growth of hydrate crystals with cyclic structure inhibitors at a hydrate-liquid interface were directly observed through a microscopic manipulating apparatus. Tetrahydrofuran (THF) hydrate was employed as an objective. The effects of four kind of cyclic structure inhibitors, polyvinylpyrrolidone (PVP), poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine) (PVPP), poly(2-vinyl pyridine-co-N-vinylcaprolactam) (PVPC) and poly(N-vinylcaprolactam) (PVCap), were investigated. Morphological patterns between each hydrate crystal growth from hydrate-liquid interface into droplet were found differ significantly. Lamellar structure growth of hydrate crystal was observed without inhibitor, while with PVP was featheriness-like, PVPP was like long dendritic crystal, PVPC was Mimosa pudica leaf-like and PVCap was like weeds. The growth rate of hydrate crystal without inhibitor was 0.00498 mm3/s, while with PVPP, PVPC and PVCap, were 0.00339 mm3/s, 0.00350 mm3/s, 0.00386 mm3/s and 0.00426 mm3/s, respectively. Cyclic structure inhibitors can decrease the growth rate, degree of reduction in growth rate of hydrate crystals decrease with the increase of cylinder number.

Evaluation of corn grain with the genetically modified input trait DAS-59122-7 fed to growing-finishing pigs.

PubMed

Stein, H H; Rice, D W; Smith, B L; Hinds, M A; Sauber, T E; Pedersen, C; Wulf, D M; Peters, D N

2009-04-01

A growth performance experiment was conducted to assess the feeding value of a double-stacked transgenic corn grain for growing-finishing pigs. The genetically modified corn grain contained event DAS-59122-7, which expresses the Cry34/35Ab1 binary insecticidal protein for the control of corn rootworm. This modified transgenic grain is resistant to western corn rootworm and is also tolerant to herbicides containing the active ingredient glufosinate-ammonium. The modified grain (59122), a nontransgenic near-isoline grain (control corn), and a commercial corn (Pioneer brand hybrid 35P12) were grown in a 2005 production trial in individually isolated plots that were located 201 m apart. A total of 108 pigs were allotted to corn-soybean meal diets containing 1 of the 3 grains as the sole source of corn. There were 3 pigs per pen and 12 replicate pens per treatment. Pigs were fed grower diets from 37 to 60 kg, early finisher diets from 60 to 90 kg, and late finisher diets from 90 to 127 kg. Within each phase, data for ADG, ADFI, and G:F were calculated. At the conclusion of the experiment, pigs were slaughtered and data for carcass quality were collected. Differences between 59122 and the control corn were evaluated, with statistical significance at P<0.05. No differences in ADG, ADFI, or G:F between pigs fed the control corn and pigs fed the modified corn were observed during the grower, early finisher, or late finisher phases. For the entire experimental period, no difference between pigs fed the control and the 59122 corn were observed for final BW (128.9 vs. 127.1 kg), ADG (1.02 vs. 1.00 kg), ADFI (2.88 vs. 2.80 kg), or G:F (0.356 vs. 0.345 kg/kg). Likewise, no differences in dressing percentage (76.48 vs. 76.30%), LM area (49.8 vs. 50.4 cm(2)), 10th-rib back fat (2.20 vs. 2.12 cm), and carcass lean content (52.9 vs. 53.4%) were observed between pigs fed the control and the 59122 corn grain. It was concluded that the nutritional value of the modified transgenic corn grain containing event DAS-59122-7 was similar to that of the nontransgenic near-isoline control.

A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

2011-02-01

Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

The Role of Natural Hydrate on the Strength of Sands: Load-bearing or Cementing?

NASA Astrophysics Data System (ADS)

Priest, J. A.; Hayley, J. L.

2017-12-01

The strength of hydrate bearing sands is a key parameter for simulating the long-term performance of hydrate reservoirs during gas production and assessing reservoir and wellbore stability. Historically this parameter has been determined from testing synthesized hydrate sand samples, which has led to significant differences in measured strength that appears to reflect different formation methods adopted. At present, formation methods can be grouped into either those that form hydrate at grain contacts leading to a high strength `cemented' sand, or those where the hydrate forms a `load-bearing' structure in which the hydrate grains reside in the pore space resulting in more subtle changes in strength. Recovered natural hydrate-bearing cores typically exhibit this `load-bearing' behavior, although these cores have generally undergone significant changes in temperature and pressure during recovery, which may have altered the structure of the hydrate and sediment. Recent drilling expeditions using pressure coring, such as NGHP2 offshore India, have enabled intact hydrate bearing sediments to be recovered that have maintained hydrostatic stresses minimizing any changes in the hydrate structure within the core. Triaxial testing on these samples highlight enhanced strength even at zero effective stresses. This suggests that the hydrate forms a connected framework within the pore space apparently `cementing' the sand grains in place: we differentiate here between true cementation where hydrate is sintered onto the sand grains and typical observed behavior for cemented sands (cohesion, peak strength, post-peak strain softening). This inter-connected hydrate, and its ability to increase strength of the sands, appears to occur even at hydrate saturations as low as 30%, where typical `load-bearing' hydrates just start to increase strength. The results from pressure cores suggest that hydrate formation techniques that lead to `load-bearing' behavior may not capture the true interaction between the hydrate and sand and thus further research is needed to form synthesized hydrate bearing samples that more realistically mimic the observed strength behavior of natural hydrate bearing cores.

Experiments with Corn To Demonstrate Plant Growth and Development.

ERIC Educational Resources Information Center

Haldeman, Janice H.; Gray, Margarit S.

2000-01-01

Explores using corn seeds to demonstrate plant growth and development. This experiment allows students to formulate hypotheses, observe and record information, and practice mathematics. Presents background information, materials, procedures, and observations. (SAH)

Pore Effect on the Occurrence and Formation of Gas Hydrate in Permafrost of Qilian Mountain, Qinghai-Tibet Plateau, China

NASA Astrophysics Data System (ADS)

Gao, H.; Lu, H.; Lu, Z.

2014-12-01

Gas hydrates were found in the permafrost of Qilian Mountain, Qinghai- Tibet Plateau, China in 2008. It has been found that gas hydrates occur in Jurassic sedimentary rocks, and the hydrated gases are mainly thermogenic. Different from the gas hydrates existing in loose sands in Mallik, Mackenzie Delta, Canada and North Slope, Alaska, USA, the gas hydrates in Qilian Mountain occurred in hard rocks. For understanding the occurrence and formation mechanism of gas hydrate in hard rcok, extensive experimental investigations have been conducted to study the pore features and hydrate formation in the rocks recovered from the hydrate layers in Qilian Mountain. The structures of sedimentary rock were observed by high-resolution X-ray CT, and pore size distribution of a rock specimen was measured with the mercury-injection method. Methane hydrate was synthesized in water-saturated rocks, and the saturations of hydrate in sedimentary rocks of various types were estimated from the amount of gas released from certain volume of rock. X-ray CT observation revealed that fractures were developed in the rocks associated with faults, while those away from faults were generally with massive structure. The mercury-injection analysis of pore features found that the porosities of the hydrate-existing rocks were generally less than 3%, and the pore sizes were generally smaller than 100 nm. The synthesizing experiments found that the saturation of methane hydrate were generally lower than 6% of pore space in rocks, but up to 16% when fractures developed. The low hydrate saturation in Qilian sedimentary rocks has been found mainly due to the small pore size of rock. The low hydrate saturation in the rocks might be the reason for the failure of regional seismic and logging detections of gas hydrates in Qilian Mountain.

Cytological study of radiation induced alterations in cytoplasmic factors controlling male sterility in corn. Progress report, February 28, 1973--December 1, 1973

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

Edwardson, J.R.

1973-01-01

Cytoplasmic male sterile accessions, other than T-type, are being backcrossed to adapted maintainer and restorer inbred corn lines. Fertile selections from gamma -irradiated T-type corn continue to exhibit resistance to infection by race-T of Helminthosporium maydis in field and greenhouse tests. Cytological comparisons of these fertile selections and T-sterile, maintainer, and restorer lines are continuing. Dominant male sterility and its suppression in S-cytoplasm corn is being investigated. lnduction of cytoplasmic male sterility in normal cytoplasm corn and suppression of susceptibility to Helminthosporium maydis infection in T cytoplasm corn is being attempted with chemical mutagens. Consistent differences in cytoplasmic inclusions inmore » sterile and maintainer Vicia faba were observed. Consistent differences in mitochondria were observed in cytological comparisons of normal and sterile corn. These abnormal mitochondria and non-Mendelian plastid abnormalities in corn, sorghum, tobacco, and petunia will be used in studying the fertilization process. Investigations of the properties of Datura Q-virus are near completion. Cytological and serological studies indicate the Q-virus is a strain of tobacco streak virus. Graft-transmission of cytoplasmic male sterility is being attempted in sunflower. (auth)« less

Effects of fracture and crack healing in sI methane and sII methane-ethane gas hydrate

NASA Astrophysics Data System (ADS)

Helgerud, M. B.; Waite, W. F.; Stern, L. A.; Kirby, S. H.

2005-12-01

Cracking within gas hydrate-bearing sediment can occur in the field at core-scales, due to unloading as material is brought to the surface during conventional coring, and at reservoir scales if the formation is fractured prior to production. Cracking can weaken hydrate-bearing sediment, but can also provide additional surface area for dissociation and permeability pathways for enhanced gas and fluid flow. In pulse-transmission wave speed measurements, we observe cracking in laboratory-formed pure sI methane and sII methane-ethane hydrates when samples are axially unloaded while being held under gas pressure to maintain hydrate stability. Cracking events are inferred from repeated, sharp decreases in shear wave speed occurring concurrently with abrupt increases in sample length. We also visually observe cracks in the solid samples after their recovery from the apparatus following each experiment. Following a cracking event, we observe evidence of rapid crack healing, or annealing expressed as nearly complete recovery of the shear wave speed within approximately 20 minutes. Gas hydrate recrystallization, grain growth, and annealing have also been observed in optical cell experiments and SEM imagery over a similar time frame. In a recovered hydrate-bearing core that is repressurized for storage or experimentation, rapid crack healing and recrystallization can partly restore lost mechanical strength and raise wave speeds. In a fractured portion of a hydrate-bearing reservoir, the rapid healing process can close permeable cracks and reduce the surface area available for dissociation.

Modeling the formation of methane hydrate-bearing intervals in fine-grained sediments

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

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Sediment grain size exerts a fundamental control on how methane hydrates are distributed within the pore space. Fine-grained muds are the predominant sediments in continental margins, and hydrates in these sediments have often been observed in semi-vertical veins and fractures. In several instances, these hydrate veins/fractures are found in discrete depth intervals a few tens meters thick within the gas hydrate stability zone (GHSZ) surrounded by hydrate-free sediments above and below. As they are not obviously connected with free gas occurring beneath the base of the GHSZ, these isolated hydrate-bearing intervals have been interpreted as formed by microbial methane generatedmore » in situ. To investigate further the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, solute diffusion, and microbial methane generation. The microbial methane generation term depends on the amount of metabolizable organic carbon deposited at the seafloor, which is degraded at a prescribed rate resulting in methane formation beneath the sulfate reduction zone. In the model, methane hydrate precipitates once the dissolved methane concentration is greater than solubility, or hydrate dissolves if concentration goes below solubility. If the deposition of organic carbon at the seafloor is kept constant in time, we found that the predicted amounts of hydrate formed in discrete intervals within the GHSZ are much less than those estimated from observations. We then investigated the effect of temporal variations in the deposition of organic carbon. If greater amounts of organic carbon are deposited during some time interval, methane generation is enhanced during burial in the corresponding sediment interval. With variations in organic carbon deposition that are consistent with observations in continental margin sediments, we were able to reproduce the methane hydrate contents estimated in discrete depth intervals. Our results support the suggestion that in situ microbial methane generation is the source for hydrates within fine-grained sediments.« less

Corn blight watch experiment results

NASA Technical Reports Server (NTRS)

Johannsen, C. J.; Bauer, M. E.

1972-01-01

Results pertaining to the detection and assessment of the severity and extent of southern corn leaf blight in the Corn Belt area are discussed. Ground observations, interpretation of color infrared photography, and machine analysis of multispectral scanner data were used to identify the blight.

A 90-day oral (dietary) toxicity and mass balance study of corn starch fiber in Sprague Dawley rats.

PubMed

Crincoli, Christine M; Nikiforov, Andrey I; Rihner, Marisa O; Lambert, Elizabeth A; Greeley, Melanie A; Godsey, Justin; Eapen, Alex K; van de Ligt, Jennifer L G

2016-11-01

The potential toxicity of corn starch fiber was assessed and compared to polydextrose, a commonly used bulking agent with a long history of safe use in the food supply. Groups of male and female Crl:CD(SD) rats were fed 0 (control), 1,000, 3,000, or 10,000 mg/kg-bw/day corn starch fiber in the diet for 90 days. The polydextrose reference article was offered on a comparable regimen at 10,000 mg/kg-bw/day. Following a single gavage dose of [ 14 C]-corn starch fiber on study day 13 or 90, the mass balance of the test article was assessed by analysis of excreta samples collected from 0 to 168 h post-dose. There were no toxicologically or biologically relevant findings in any of the test article-treated groups. The few minor differences observed between the corn starch fiber and polydextrose exposed groups were considered to be due to normal biological variation. Following [ 14 C]-corn starch fiber dosing, nearly complete excretion of the administered dose occurred over 168 h post-dosing, with the majority excreted in the feces. The dietary no-observed-adverse-effect level of corn starch fiber after 90 days was 10,000 mg/kg-bw/day. Similar toxicity profiles for corn starch fiber and polydextrose were observed due to the structural and compositional similarities of these materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determining the mechanism and parameters of hydrate formation and loss in glucose.

PubMed

Scholl, Sarah K; Schmidt, Shelly J

2014-11-01

Water-solid interactions are known to play a major role in the chemical and physical stability of food materials. Despite its extensive use throughout the food industry, the mechanism and parameters of hydrate formation and loss in glucose are not well characterized. Hydrate formation in alpha-anhydrous glucose (α-AG) and hydrate loss in glucose monohydrate (GM) were studied under equilibrium conditions at various relative humidity (RH) values using saturated salt slurries for 1 y. The mechanism of hydrate formation and hydrate loss were determined through mathematical modeling of Dynamic Vapor Sorption data and Raman spectroscopy was used to confirm the mechanisms. The critical temperature for hydrate loss in GM was determined using thermogravimetric analysis (TGA). The moisture sorption profiles of α-AG and GM were also studied under dynamic conditions using an AquaSorp Isotherm Generator. Hydrate formation was observed at and above 68% RH at 25 °C and the conversion of α-AG to GM can best be described as following a nucleation mechanism, however, diffusion and/or geometric contraction mechanisms were also observed by Raman spectroscopy subsequent to the coalescence of initial nucleation sites. Hydrate loss was observed to occur at and below 11% RH at 25 °C during RH storage and at 70 °C during TGA. The conversion of GM to α-AG follows nucleation and diffusion mechanisms. Hydrate formation was evident under dynamic conditions in α-AG and GM prior to deliquescence. This research is the first to report hydrate formation and loss parameters for crystalline α-AG and GM during extended storage at 25 ˚C. © 2014 Institute of Food Technologists®

The interaction of climate change and methane hydrates

USGS Publications Warehouse

Ruppel, Carolyn D.; Kessler, John D.

2017-01-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

NASA Astrophysics Data System (ADS)

Ruppel, Carolyn D.; Kessler, John D.

2017-03-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

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

Ruppel, Carolyn D.; Kessler, John D.

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

The interaction of climate change and methane hydrates

DOE PAGES

Ruppel, Carolyn D.; Kessler, John D.

2016-12-14

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ

PubMed Central

Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

2015-01-01

Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles. PMID:25996055

Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ.

PubMed

Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

2015-05-21

Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.

Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

DOE PAGES

Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; ...

2015-05-21

Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions.more » We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.« less

Experimental and Numerical Observations of Hydrate Reformation during Depressurization in a Core-Scale Reactor

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

Seol, Yongkoo; Myshakin, Evgeniy

2011-01-01

Gas hydrate has been predicted to reform around a wellbore during depressurization-based gas production from gas hydrate-bearing reservoirs. This process has an adverse effect on gas production rates and it requires time and sometimes special measures to resume gas flow to producing wells. Due to lack of applicable field data, laboratory scale experiments remain a valuable source of information to study hydrate reformation. In this work, we report laboratory experiments and complementary numerical simulations executed to investigate the hydrate reformation phenomenon. Gas production from a pressure vessel filled with hydrate-bearing sand was induced by depressurization with and without heat fluxmore » through the boundaries. Hydrate decomposition was monitored with a medical X-ray CT scanner and pressure and temperature measurements. CT images of the hydrate-bearing sample were processed to provide 3-dimensional data of heterogeneous porosity and phase saturations suitable for numerical simulations. In the experiments, gas hydrate reformation was observed only in the case of no-heat supply from surroundings, a finding consistent with numerical simulation. By allowing gas production on either side of the core, numerical simulations showed that initial hydrate distribution patterns affect gas distribution and flow inside the sample. This is a direct consequence of the heterogeneous pore network resulting in varying hydraulic properties of the hydrate-bearing sediment.« less

A multi-year field study to evaluate the environmental fate and agronomic effects of insecticide mixtures.

PubMed

Whiting, Sara A; Strain, Katherine E; Campbell, Laura A; Young, Bryan G; Lydy, Michael J

2014-11-01

A mixture of insecticides used in corn production was monitored over a three-year period in a field study to determine how long each persists in the environment, where each insecticide travels within the corn field, and the efficacy of using soil-applied insecticides with genetically modified corn. The genetically modified corn contained the insecticidal Cry1Ab and Cry3Bb1 proteins (Bt corn) and the Cry1Ab protein was found to persist only during the corn growing season in soil, runoff water, and runoff sediment with highest concentrations measured during pollination. Very low concentrations of Cry1Ab proteins were measured in soil collected in the non-Bt corn field, and no Cry1Ab proteins were detected in shallow groundwater or soil pore water. Clothianidin, a neonicotinoid insecticide used as a seed coating, was detected in all matrices and remained persistent throughout the year in soil pore water. Tefluthrin, a pyrethroid insecticide applied at planting to control corn rootworm larvae (Diabrotica spp., Coleoptera: Chrysomelidae) populations, was consistently detected in soil, runoff water, and runoff sediment during the corn growing season, but was not detected in groundwater or soil pore water. Tefluthrin did not have an effect on root damage from corn rootworm larvae feeding to Bt corn, but did prevent damage to non-Bt corn. A slight reduction in grain yield was observed in the non-Bt, no tefluthrin treatment when compared to all other treatments, but no significant difference in grain yield was observed among Bt corn treatments regardless of soil insecticide application. In the current study, the use of tefluthrin on Bt corn did not significantly affect crop damage or yield, and tefluthrin may travel off-site in runoff water and sediment. Copyright © 2014 Elsevier B.V. All rights reserved.

Mapping Hydrated Materials with MER Pancam and MSL Mastcam: Results from Gusev Crater and Meridiani Planum, and Plans for Gale Crater

NASA Astrophysics Data System (ADS)

Rice, M. S.; Bell, J. F.

2011-12-01

We have developed a "hydration signature" for mapping H2O- and/or OH-bearing materials at Mars landing sites using multispectral visible to near-infrared (Vis-NIR) observations from the Mars Exploration Rover (MER) Panoramic Camera (Pancam). Pancam's 13 narrowband geology filters cover 11 unique wavelengths in the visible and near infrared (434 to 1009 nm). The hydration signature is based on a strongly negative slope from 934 to 1009 nm that characterizes the spectra of hydrated silica-rich rocks and soils observed by MER Spirit; this feature is likely due to the 2ν1 + ν3 H2O combination band and/or the 3vOH overtone centered near ~1000 nm, whose positions vary slightly depending on bonding to nearest-neighbor atoms. Here we present the ways we have used this hydration signature, in combination with observations of morphology and texture, to remotely identify candidate hydrated materials in Pancam observations. At Gusev Crater, we find that the hydration signature is widespread along Spirit's traverse in the Columbia Hills, which adds to the growing body of evidence that aqueous alteration has played a significant role in the complex geologic history of this site. At Meridiani Planum, the hydration signature is associated with a specific stratigraphic layer ("Smith") exposed within the walls of Victoria Crater. We also discuss limitations to the use of the hydration signature, which can give false detections under specific viewing geometries. This hydration signature can similarly be used to map hydrated materials at the Mars Science Laboratory (MSL) landing site, Gale Crater. The MSL Mast Camera (Mastcam) is a two-instrument suite of fixed-focal length (FFL) cameras, one with a 15-degree field of view (FOV) and the other with a 5.1-degree FOV. Mastcam's narrowband filters cover 9 unique wavelengths in the visible and near-infrared (band centers near 440, 525, 675, 750, 800, 865, 905, 935, and 1035 nm), and are distributed between the two FFL cameras. Full-filter multispectral observations of the region of overlap between the two cameras can be used for our hydration signature mapping. Mastcam's longest-wavelength filter should be able to detect hydrated and/or hydroxylated minerals with strong absorptions between ~990 and ~1080 nm; because of the width of this IR filter, Mastcam will be sensitive to more H2O and/or OH-bearing species than Pancam. Here we summarize the minerals Mastcam should be able to detect if present at Gale Crater, and our plans for hydration signature mapping with MSL.

Nutritive value of corn silage as affected by maturity and mechanical processing: a contemporary review.

PubMed

Johnson, L; Harrison, J H; Hunt, C; Shinners, K; Doggett, C G; Sapienza, D

1999-12-01

Stage of maturity at harvest and mechanical processing affect the nutritive value of corn silage. The change in nutritive value of corn silage as maturity advances can be measured by animal digestion and macro in situ degradation studies among other methods. Predictive equations using climatic data, vitreousness of corn grain in corn silage, starch reactivity, gelatinization enthalpy, dry matter (DM) of corn grain in corn silage, and DM of corn silage can be used to estimate starch digestibility of corn silage. Whole plant corn silage can be mechanically processed either pre- or postensiling with a kernel processor mounted on a forage harvester, a recutter screen on a forage harvester, or a stationary roller mill. Mechanical processing of corn silage can improve ensiling characteristics, reduce DM losses during ensiling, and improve starch and fiber digestion as a result of fracturing the corn kernels and crushing and shearing the stover and cobs. Improvements in milk production have ranged from 0.2 to 2.0 kg/d when cows were fed mechanically processed corn silage. A consistent improvement in milk protein yield has also been observed when mechanically processed corn silage has been fed. With the advent of mechanical processors, alternative strategies are evident for corn silage management, such as a longer harvest window.

Observed correlation between the depth to base and top of gas hydrate occurrence from review of global drilling data

NASA Astrophysics Data System (ADS)

Riedel, M.; Collett, T. S.

2017-07-01

A global inventory of data from gas hydrate drilling expeditions is used to develop relationships between the base of structure I gas hydrate stability, top of gas hydrate occurrence, sulfate-methane transition depth, pressure (water depth), and geothermal gradients. The motivation of this study is to provide first-order estimates of the top of gas hydrate occurrence and associated thickness of the gas hydrate occurrence zone for climate-change scenarios, global carbon budget analyses, or gas hydrate resource assessments. Results from publically available drilling campaigns (21 expeditions and 52 drill sites) off Cascadia, Blake Ridge, India, Korea, South China Sea, Japan, Chile, Peru, Costa Rica, Gulf of Mexico, and Borneo reveal a first-order linear relationship between the depth to the top and base of gas hydrate occurrence. The reason for these nearly linear relationships is believed to be the strong pressure and temperature dependence of methane solubility in the absence of large difference in thermal gradients between the various sites assessed. In addition, a statistically robust relationship was defined between the thickness of the gas hydrate occurrence zone and the base of gas hydrate stability (in meters below seafloor). The relationship developed is able to predict the depth of the top of gas hydrate occurrence zone using observed depths of the base of gas hydrate stability within less than 50 m at most locations examined in this study. No clear correlation of the depth to the top and base of gas hydrate occurrences with geothermal gradient and sulfate-methane transition depth was identified.

Observed correlation between the depth to base and top of gas hydrate occurrence from review of global drilling data

USGS Publications Warehouse

Riedel, Michael; Collett, Timothy S.

2017-01-01

A global inventory of data from gas hydrate drilling expeditions is used to develop relationships between the base of structure I gas hydrate stability, top of gas hydrate occurrence, sulfate-methane transition depth, pressure (water depth), and geothermal gradients. The motivation of this study is to provide first-order estimates of the top of gas hydrate occurrence and associated thickness of the gas hydrate occurrence zone for climate-change scenarios, global carbon budget analyses, or gas hydrate resource assessments. Results from publically available drilling campaigns (21 expeditions and 52 drill sites) off Cascadia, Blake Ridge, India, Korea, South China Sea, Japan, Chile, Peru, Costa Rica, Gulf of Mexico, and Borneo reveal a first-order linear relationship between the depth to the top and base of gas hydrate occurrence. The reason for these nearly linear relationships is believed to be the strong pressure and temperature dependence of methane solubility in the absence of large difference in thermal gradients between the various sites assessed. In addition, a statistically robust relationship was defined between the thickness of the gas hydrate occurrence zone and the base of gas hydrate stability (in meters below seafloor). The relationship developed is able to predict the depth of the top of gas hydrate occurrence zone using observed depths of the base of gas hydrate stability within less than 50 m at most locations examined in this study. No clear correlation of the depth to the top and base of gas hydrate occurrences with geothermal gradient and sulfate-methane transition depth was identified.

Influence of variety and harvest maturity on phytochemical content in corn silk.

PubMed

Sarepoua, Eakrin; Tangwongchai, Ratchada; Suriharn, Bhalang; Lertrat, Kamol

2015-02-15

Corn silk has been used as a traditional herb in Asia. The objective of this study was to evaluate variability in phytochemicals in corn varieties at three maturity stages of corn silk. Ten vegetable corn varieties were evaluated in a completely randomized design with three replications. Data were recorded for total phenolic (TPC), total flavonoids (TFC), total anthocyanin (TAC) and antioxidant activity (AA) by DPPH free-radical-scavenging assays. Differences among corn varieties were observed for all parameters at all maturity stages, and the interactions between maturity stage and corn variety were significant. TPC and TAC were highest at the milky stage, whereas TFC and AA were highest at the silking stage. TPC, TFC and AA were highest in super sweet corn and white corn at the silking stage. PWC5 variety of purple waxy corn at the milky stage had the highest values for all parameters, and it is useful for further development of functional food products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of polymeric excipient properties on crystal hydrate formation kinetics of caffeine in aqueous slurries.

PubMed

Gift, Alan D; Southard, Leslie A; Riesberg, Amanda L

2012-05-01

The influence of polymeric excipients on the hydrate transformation of caffeine (CAF) was studied. Anhydrous CAF was added to aqueous solutions containing different additives and the transformation to the hydrate form was monitored using in-line Raman spectroscopy. Various properties of two known inhibitors of CAF hydrate formation, polyacrylic acid (PAA) and polyvinyl alcohol (PVA), were investigated. For inhibition by PAA, a pH dependence was observed: at low pH, the inhibition was greatest, whereas no inhibitory effects were observed at pH above 6.5. For PVA, grades with high percent hydrolysis were the most effective at inhibiting the transformation. In addition, PVA with higher molecular weight showed slightly more inhibition than the shorter chain PVA polymers. A variety of other hydroxyl containing compounds were examined but none inhibited the CAF anhydrate-to-hydrate transformation. The observed inhibitory effects of PAA and PVA are attributed to the large number of closely spaced hydrogen bond donating groups of the polymer molecule, which can interact with the CAF hydrate crystal. Copyright © 2012 Wiley Periodicals, Inc.

Detecting gas hydrate behavior in crude oil using NMR.

PubMed

Gao, Shuqiang; House, Waylon; Chapman, Walter G

2006-04-06

Because of the associated experimental difficulties, natural gas hydrate behavior in black oil is poorly understood despite its grave importance in deep-water flow assurance. Since the hydrate cannot be visually observed in black oil, traditional methods often rely on gas pressure changes to monitor hydrate formation and dissociation. Because gases have to diffuse through the liquid phase for hydrate behavior to create pressure responses, the complication of gas mass transfer is involved and hydrate behavior is only indirectly observed. This pressure monitoring technique encounters difficulties when the oil phase is too viscous, the amount of water is too small, or the gas phase is absent. In this work we employ proton nuclear magnetic resonance (NMR) spectroscopy to observe directly the liquid-to-solid conversion of the water component in black oil emulsions. The technique relies on two facts. The first, well-known, is that water becomes essentially invisible to liquid state NMR as it becomes immobile, as in hydrate or ice formation. The second, our recent finding, is that in high magnetic fields of sufficient homogeneity, it is possible to distinguish water from black oil spectrally by their chemical shifts. By following changes in the area of the water peak, the process of hydrate conversion can be measured, and, at lower temperatures, the formation of ice. Taking only seconds to accomplish, this measurement is nearly direct in contrast to conventional techniques that measure the pressure changes of the whole system and assume these changes represent formation or dissociation of hydrates - rather than simply changes in solubility. This new technique clearly can provide accurate hydrate thermodynamic data in black oils. Because the technique measures the total mobile water with rapidity, extensions should prove valuable in studying the dynamics of phase transitions in emulsions.

The history and future trends of ocean warming-induced gas hydrate dissociation in the SW Barents Sea

NASA Astrophysics Data System (ADS)

Vadakkepuliyambatta, Sunil; Chand, Shyam; Bünz, Stefan

2017-01-01

The Barents Sea is a major part of the Arctic where the Gulf Stream mixes with the cold Arctic waters. Late Cenozoic uplift and glacial erosion have resulted in hydrocarbon leakage from reservoirs, evolution of fluid flow systems, shallow gas accumulations, and hydrate formation throughout the Barents Sea. Here we integrate seismic data observations of gas hydrate accumulations along with gas hydrate stability modeling to analyze the impact of warming ocean waters in the recent past and future (1960-2060). Seismic observations of bottom-simulating reflectors (BSRs) indicate significant thermogenic gas input into the hydrate stability zone throughout the SW Barents Sea. The distribution of BSR is controlled primarily by fluid flow focusing features, such as gas chimneys and faults. Warming ocean bottom temperatures over the recent past and in future (1960-2060) can result in hydrate dissociation over an area covering 0.03-38% of the SW Barents Sea.

Observations of gas hydrates in marine sediments, offshore northern California

USGS Publications Warehouse

Brooks, J.M.; Field, M.E.; Kennicutt, M.C.

1991-01-01

Biogenic gas hydrates were recovered in shallow cores (< 6 m deep) from the Eel River basin in offshore northern California between 40??38??? and 40??56???N. The gas hydrates contained primarily methane (??13C = -57.6 to -69.1???) and occurred as dispersed crystals, small (2-20 mm) nodules, and layered bands within the sediment. These hydrates, recovered in sediment at water depths between 510 and 642 m, coincide nearly, but not exactly, with areas showing bottom-simulating reflectors (BSRs) on seismic-reflection records. This study confirms indirect geophysical and geologic observations that gas hydrates are present north of the Mendocino Fracture Zone in sediment of the Eel River basin but probably are absent to the south in the Point Arena basin. This discovery extends the confirmed sites of gas hydrates in the eastern Pacific region beyond the Peruvian and Central American margins to the northern California margin. ?? 1991.

Estimating pore-space gas hydrate saturations from well log acoustic data

NASA Astrophysics Data System (ADS)

Lee, Myung W.; Waite, William F.

2008-07-01

Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate-bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

Determination of pore-scale hydrate phase equilibria in sediments using lab-on-a-chip technology.

PubMed

Almenningen, Stian; Flatlandsmo, Josef; Kovscek, Anthony R; Ersland, Geir; Fernø, Martin A

2017-11-21

We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.

Biological and genetic characterization of new and known necroviruses causing an emerging systemic necrosis disease of corn salad (Valerianella locusta L.) in France.

PubMed

Verdin, Eric; Marais, Armelle; Wipf-Scheibel, Catherine; Faure, Chantal; Pelletier, Brigitte; David, Perrine; Svanella-Dumas, Laurence; Poisblaud, Clement; Lecoq, Herve'; Candresse, Thierry

2018-02-28

An emerging systemic necrosis disease of corn salad was first observed in the Nantes region of France in the late 2000's. Classical virology and high-throughput sequencing approaches demonstrated that the disease is associated with four different necroviruses, tobacco necrosis virus A (TNVA), tobacco necrosis virus D (TNVD), olive mild mosaic virus (OMMV) and a novel recombinant Alphanecrovirus for which the name corn salad necrosis virus (CSNV) is proposed. Satellite tobacco necrosis virus (STNV) was also frequently observed. Koch's postulates were completed for all four agents, each one alone being able to cause systemic necrosis of varying severity in corn salad. OMMV was the most frequently observed virus and causes the most severe symptoms. TNVA was the second, both in terms of prevalence and symptom severity while TNVD and CSNV were only rarely observed and cause the less severe symptoms. The emergence of this systemic disease may have been favoured by the short and repeated cropping cycles used for corn salad, possibly allowing the selection of necrovirus isolates with an improved ability to systemically invade this specialty crop.

Skin hydration and lifestyle-related factors in community-dwelling older people.

PubMed

Iizaka, Shinji

2017-09-01

This study aimed to investigate skin hydration status of the lower legs by comparing several methods and examining lifestyle-related factors in community-dwelling older people. A cross-sectional study was conducted in three community settings in Japan from autumn to winter. Participants were older people aged ≥65 years (n=118). Skin hydration status of the lower legs was evaluated by stratum corneum hydration using an electrical device, clinical symptoms by an expert's observation and the visual analogue scale. Lifestyle factors of skin care were evaluated by a self-administered questionnaire. The mean age of participants was 74.4 years and 83.9% were women. Stratum corneum hydration was significantly correlated with clinical scores by an expert's observation (rho=-0.46, P<0.001), but it was not correlated with the visual analogue scale (rho=-0.08, P=0.435). Among participants who did not perceive dry skin, 57.5% showed low stratum corneum hydration. Hospitalization in the past year (b=-9.4, P=0.008), excessive bathing habits (b=-4.6, P=0.014), and having an outdoor hobby (b=-5.7, P=0.007) were negatively associated, and diuretics (b=11.5, P=0.002) and lotion-type moisturizer use (b=4.6, P=0.022) were positively associated with stratum corneum hydration. Stratum corneum hydration measurements show an adequate association with observation-based evaluation by an expert, but poor agreement with subjective evaluation in community-dwelling older people. Hospitalization experience and lifestyle factors are associated with skin hydration. Copyright © 2017 Elsevier B.V. All rights reserved.

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X-ray computed tomographic microscopy

NASA Astrophysics Data System (ADS)

Chaouachi, Marwen; Falenty, Andrzej; Sell, Kathleen; Enzmann, Frieder; Kersten, Michael; Haberthür, David; Kuhs, Werner F.

2015-06-01

The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in situ at submicron resolution. Here we report on synchrotron-based microtomographic studies by which the nucleation and growth processes of gas hydrate were observed at 276 K in various sedimentary matrices such as natural quartz (with and without admixtures of montmorillonite type clay) or glass beads with different surface properties, at varying water saturation. Both juvenile water and metastably gas-enriched water obtained from gas hydrate decomposition was used. Xenon gas was employed to enhance the density contrast between gas hydrate and the fluid phases involved. The nucleation sites can be easily identified and the various growth patterns are clearly established. In sediments under-saturated with juvenile water, nucleation starts at the water-gas interface resulting in an initially several micrometer thick gas hydrate film; further growth proceeds to form isometric single crystals of 10-20 µm size. The growth of gas hydrate from gas-enriched water follows a different pattern, via the nucleation in the bulk of liquid producing polyhedral single crystals. A striking feature in both cases is the systematic appearance of a fluid phase film of up to several micron thickness between gas hydrates and the surface of the quartz grains. These microstructural findings are relevant for future efforts of quantitative rock physics modeling of gas hydrates in sedimentary matrices and explain the anomalous attenuation of seismic/sonic waves.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

NASA Astrophysics Data System (ADS)

Braun, Doris E.; Griesser, Ulrich J.

2018-02-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4'-diaminodiphenyl sulfone, DDS) 0.33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and a stable anhydrate at room temperature (form III) differ only by approximately 1 kJ mol–1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study addresses the critical class of non-stoichiometric hydrates, highlighting that only a multidisciplinary investigation can unravel hydrate formation at a molecular level, knowledge which is a requirement in modern drug development.

Gas hydrate volume estimations on the South Shetland continental margin, Antarctic Peninsula

USGS Publications Warehouse

Jin, Y.K.; Lee, M.W.; Kim, Y.; Nam, S.H.; Kim, K.J.

2003-01-01

Multi-channel seismic data acquired on the South Shetland margin, northern Antarctic Peninsula, show that Bottom Simulating Reflectors (BSRs) are widespread in the area, implying large volumes of gas hydrates. In order to estimate the volume of gas hydrate in the area, interval velocities were determined using a 1-D velocity inversion method and porosities were deduced from their relationship with sub-bottom depth for terrigenous sediments. Because data such as well logs are not available, we made two baseline models for the velocities and porosities of non-gas hydrate-bearing sediments in the area, considering the velocity jump observed at the shallow sub-bottom depth due to joint contributions of gas hydrate and a shallow unconformity. The difference between the results of the two models is not significant. The parameters used to estimate the total volume of gas hydrate in the study area were 145 km of total length of BSRs identified on seismic profiles, 350 m thickness and 15 km width of gas hydrate-bearing sediments, and 6.3% of the average volume gas hydrate concentration (based on the second baseline model). Assuming that gas hydrates exist only where BSRs are observed, the total volume of gas hydrates along the seismic profiles in the area is about 4.8 ?? 1010 m3 (7.7 ?? 1012 m3 volume of methane at standard temperature and pressure).

High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer.

PubMed

Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S

2017-02-01

Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer

NASA Astrophysics Data System (ADS)

Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S.

2017-02-01

Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

Gas hydrates (clathrates) causing pore-water freshening and oxygen isotope fractionation in deep-water sedimentary sections of terrigenous continental margins

USGS Publications Warehouse

Hesse, R.; Harrison, W.E.

1981-01-01

The occurrence of gas hydrates in deep-water sections of the continental margins predicted from anomalous acoustic reflectors on seismic profiles has been confirmed by recent deep-sea drilling results. On the Pacific continental slope off Guatemala gas hydrates were brought up for the first time from two holes (497, 498A) drilled during Leg 67 of the DSDP in water depths of 2360 and 5500 m, respectively. The hydrates occur in organic matter-rich Pleistocene to Miocene terrigenous sediments. In the hydrate-bearing zone a marked decrease in interstitial water chlorinities was observed starting at about 10-20 m subbottom depth. Pore waters at the bottom of the holes (near 400 m subbottom) have as little as half the chlorinity of seawater (i.e. 9???). Similar, but less pronounced, trends were observed during previous legs of the DSDP in other hydrate-prone segments of the continental margins where recharge of fresh water from the continent can be excluded (e.g. Leg 11). The crystallization of hydrates, like ice, excludes salt ions from the crystal structure. During burial the dissolved salts are separated from the solids. Subsidence results in a downward motion of the solids (including hydrates) relative to the pore fluids. Thawing of hydrates during recovery releases fresh water which is remixed with the pore fluid not involved in hydrate formation. The volume of the latter decreases downhole thus causing downward decreasing salinity (chlorinity). Hydrate formation is responsible for oxygen isotope fractionation with 18O-enrichment in the hydrate explaining increasingly more positive ??18O values in the pore fluids recovered (after hydrate dissociation) with depth. ?? 1981.

Evaluation of Gas Hydrate at Alaminos Canyon 810, Northern Gulf of Mexico Slope

NASA Astrophysics Data System (ADS)

Yang, C.; Cook, A.; Sawyer, D.; Hillman, J. I. T.

2016-12-01

We characterize the gas hydrate reservoir in Alaminos Canyon Block 810 (AC810) on the northern Gulf of Mexico slope, approximately 400 km southeast of Houston, Texas, USA. Three-dimensional seismic data shows a bottom-simulating-reflection (BSR), over 30 km2, which suggests that a significant gas hydrate accumulation may occur at AC810. Furthermore, logging while drilling (LWD) data acquired from a Statoil well located that penetrated the BSR near the crest of the regional anticline indicates two possible gas hydrate units (Hydrate Unit A and Hydrate Unit B). LWD data in this interval are limited to gamma ray and resistivity only. Resistivity curve separations are observed in Hydrate Unit A (131 to 253 mbsf) suggesting hydrate-filled fractures in marine mud. A spiky high resistivity response in Hydrate Unit B (308 to 354 mbsf) could either be a marine mud or a sand-prone interval. The abrupt decrease (from 7 to 1 Ωm) in resistivity logs at 357 mbsf generally corresponds with the interpreted base of hydrate stability, as the BSR is observed near 350 mbsf on the seismic data. To further investigate the formation characteristics, we generate synthetic traces using general velocity and density trends for marine sediments to match the seismic trace extracted at the Statoil well. We consider models with 1) free gas and 2) water only below the base of hydrate stability. In our free gas-below models, we find the velocity of Hydrate Unit A and Hydrate Unit B is generally low and does not deviate significantly from the general velocity trends, suggesting that gas hydrate is present in a marine mud. In the water-below model, the compressional velocity of Hydrate Unit B ranges from 2450 m/s to 3150 m/s. This velocity is similar to the velocity of high hydrate saturation in sand; typically greater than 2500 m/s. This may indicate that Hydrate Unit B is sand with high hydrate saturation; however, to achieve a suitable match between the water-below synthetic seismogram and the trace, a high velocity layer was required below the base of hydrate stability, which is not indicated by the well logs. Our models indicate that at AC810, Hydrate Unit A probably contains hydrate filled fractures in a marine mud. For Hydrate Unit B, our models suggest hydrate may occur in a sand-prone interval, but is more likely to be gas hydrate filled fractures in marine mud.

Composition of grain and forage from insect-protected and herbicide-tolerant corn, MON 89034 × TC1507 × MON 88017 × DAS-59122-7 (SmartStax), is equivalent to that of conventional corn (Zea mays L.).

PubMed

Lundry, Denise R; Burns, J Austin; Nemeth, Margaret A; Riordan, Susan G

2013-02-27

Monsanto Company and Dow AgroSciences LLC have developed the combined-trait corn product MON 89034 × TC1507 × MON 88017 × DAS-59122-7 (SmartStax, a registered trademark of Monsanto Technology LLC). The combination of four biotechnology-derived events into a single corn product (stacking) through conventional breeding provides broad protection against lepidopteran and corn rootworm insect pests as well as tolerance to the glyphosate and glufosinate-ammonium herbicide families. The purpose of the work described here was to assess whether the nutrient, antinutrient, and secondary metabolite levels in grain and forage tissues of the combined-trait product are comparable to those in conventional corn. Compositional analyses were conducted on grain and forage from SmartStax, a near-isogenic conventional corn hybrid (XE6001), and 14 conventional reference hybrids, grown at multiple locations across the United States. No statistically significant differences between SmartStax and conventional corn were observed for the 8 components analyzed in forage and for 46 of the 52 components analyzed in grain. The six significant differences observed in grain components (p < 0.05) were assessed in context of the natural variability for that component. These results demonstrate that the stacked product, SmartStax, produced through conventional breeding of four single-event products containing eight proteins, is compositionally equivalent to conventional corn, as previously demonstrated for the single-event products.

The effect of elevated methane pressure on methane hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

Grain-scale imaging and compositional characterization of cryo-preserved India NGHP 01 gas-hydrate-bearing cores

USGS Publications Warehouse

Stern, Laura A.; Lorenson, T.D.

2014-01-01

We report on grain-scale characteristics and gas analyses of gas-hydrate-bearing samples retrieved by NGHP Expedition 01 as part of a large-scale effort to study gas hydrate occurrences off the eastern-Indian Peninsula and along the Andaman convergent margin. Using cryogenic scanning electron microscopy, X-ray spectroscopy, and gas chromatography, we investigated gas hydrate grain morphology and distribution within sediments, gas hydrate composition, and methane isotopic composition of samples from Krishna–Godavari (KG) basin and Andaman back-arc basin borehole sites from depths ranging 26 to 525 mbsf. Gas hydrate in KG-basin samples commonly occurs as nodules or coarse veins with typical hydrate grain size of 30–80 μm, as small pods or thin veins 50 to several hundred microns in width, or disseminated in sediment. Nodules contain abundant and commonly isolated macropores, in some places suggesting the original presence of a free gas phase. Gas hydrate also occurs as faceted crystals lining the interiors of cavities. While these vug-like structures constitute a relatively minor mode of gas hydrate occurrence, they were observed in near-seafloor KG-basin samples as well as in those of deeper origin (>100 mbsf) and may be original formation features. Other samples exhibit gas hydrate grains rimmed by NaCl-bearing material, presumably produced by salt exclusion during original hydrate formation. Well-preserved microfossil and other biogenic detritus are also found within several samples, most abundantly in Andaman core material where gas hydrate fills microfossil crevices. The range of gas hydrate modes of occurrence observed in the full suite of samples suggests a range of formation processes were involved, as influenced by local in situconditions. The hydrate-forming gas is predominantly methane with trace quantities of higher molecular weight hydrocarbons of primarily microbial origin. The composition indicates the gas hydrate is Structure I.

Combustion of Methane Hydrate

NASA Astrophysics Data System (ADS)

Roshandell, Melika

A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and methane release, some of the water from the dissociated zone needs to be drained. The results are consistent with the experimental observations. The understanding derived from the experiments and the numerical model permitted a brief exploration into the potential effects of pressure on the combustion of methane hydrates. The prediction is that combustion should improve under high pressure conditions because the evaporation of water is suppressed allowing more energy into the dissociation. Future experiments are needed to validate these initial findings.

Spatial variation of corn canopy temperature as dependent upon soil texture and crop rooting characteristics

NASA Technical Reports Server (NTRS)

Choudhury, B. J.

1983-01-01

A soil plant atmosphere model for corn (Zea mays L.) together with the scaling theory for soil hydraulic heterogeneity are used to study the sensitivity of spatial variation of canopy temperature to field averaged soil texture and crop rooting characteristics. The soil plant atmosphere model explicitly solves a continuity equation for water flux resulting from root water uptake, changes in plant water storage and transpirational flux. Dynamical equations for root zone soil water potential and the plant water storage models the progressive drying of soil, and day time dehydration and night time hydration of the crop. The statistic of scaling parameter which describes the spatial variation of soil hydraulic conductivity and matric potential is assumed to be independent of soil texture class. The field averaged soil hydraulic characteristics are chosen to be representative of loamy sand and clay loam soils. Two rooting characteristics are chosen, one shallow and the other deep rooted. The simulation shows that the range of canopy temperatures in the clayey soil is less than 1K, but for the sandy soil the range is about 2.5 and 5.0 K, respectively, for the shallow and deep rooted crops.

Study on small-strain behaviours of methane hydrate sandy sediments using discrete element method

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

Yu Yanxin; Cheng Yipik; Xu Xiaomin

Methane hydrate bearing soil has attracted increasing interest as a potential energy resource where methane gas can be extracted from dissociating hydrate-bearing sediments. Seismic testing techniques have been applied extensively and in various ways, to detect the presence of hydrates, due to the fact that hydrates increase the stiffness of hydrate-bearing sediments. With the recognition of the limitations of laboratory and field tests, wave propagation modelling using Discrete Element Method (DEM) was conducted in this study in order to provide some particle-scale insights on the hydrate-bearing sandy sediment models with pore-filling and cementation hydrate distributions. The relationship between shear wavemore » velocity and hydrate saturation was established by both DEM simulations and analytical solutions. Obvious differences were observed in the dependence of wave velocity on hydrate saturation for these two cases. From the shear wave velocity measurement and particle-scale analysis, it was found that the small-strain mechanical properties of hydrate-bearing sandy sediments are governed by both the hydrate distribution patterns and hydrate saturation.« less

Metabolism of the hydrochlorofluorocarbon 1,2-dichloro-1,1-difluoroethane.

PubMed

Harris, J W; Anders, M W

1991-01-01

1,2-Dichloro-1,1-difluoroethane (HCFC-132b) is a potential substitute for some ozone-depleting chlorofluorocarbons and a model for other 1,1,1,2-tetrahaloethanes under consideration as chlorofluorocarbon substitutes. Male Fischer 344 rats were given 10 mmol/kg HCFC-132b dissolved in corn oil by intraperitoneal injection. An NMR assay for covalent binding of HCFC-132b metabolites to liver proteins was negative, whereas binding was observed in halothane-treated rats. Total urinary metabolites excreted by rats given HCFC-132b during the first 24 h amounted to 1.8 +/- 0.1% of the injected dose, as determined by 19F NMR. During the first 6 h, metabolites of HCFC-132b corresponding to 2-chloro-2,2-difluoroethyl glucuronide, unknown metabolite A, chlorodifluoroacetic acid, and chlorodifluoroacetaldehyde hydrate [both free and conjugated (unknown metabolite B)] were excreted in urine in the approximate ratio 100:9:3:7, respectively. Metabolite A is apparently an O-conjugate of 2-chloro-2,2-difluoroethanol; unconjugated 2-chloro-2,2-difluoroethanol was not detected in urine. The 19F NMR spectrum of metabolite B indicates the formation of a hemiacetal of chlorodifluoroacetaldehyde. Repeated exposure of rats to HCFC-132b significantly increased both the rate of chlorodifluoroacetic acid excretion and the relative fraction of the HCFC-132b dose excreted as chlorodifluoroacetic acid in urine. Incubation of HCFC-132b with rat hepatic microsomes yielded chlorodifluoroacetaldehyde hydrate as the only fluorinated product. The in vitro metabolism of HCFC-132b was increased in microsomes from pyridine-treated rats as compared with control rats, and HCFC-132b metabolism was inhibited by p-nitrophenol, indicating that the cytochrome P-450 isoform IIE1 is largely responsible for the initial hydroxylation of HCFC-132b.

I-Hydrate training intervention for staff working in a care home setting: An observational study.

PubMed

Greene, Carolynn; Canning, Deebs; Wilson, Jennie; Bak, Aggie; Tingle, Alison; Tsiami, Amalia; Loveday, Heather

2018-05-23

Dehydration is a complex and well-recognised problem for older people residing in care homes. Within the social care sector support staff provide the majority of direct care for residents, and yet receive minimal training. To design, deliver and evaluate a hydration specific training session for care home staff to develop their knowledge and skills in supporting the hydration of care home residents. An observational study comprising a pre-test post-test survey of staff knowledge following a training intervention. Training of care home staff took place in two care homes in North West London. An interactive training session was developed and delivered, with content informed by observations of hydration care within the two homes and evaluated using CIRO model. Participant self-evaluation forms were used to collect data after the session regarding satisfaction and usefulness of the session, and pre and post levels of self-reported knowledge across six facets of hydration care. Training facilitators captured qualitative data in the form of field notes. Observations of hydration care explored the impact of training on practice. Eighteen training sessions were delivered. A total of 161 participant evaluation forms were returned. There was a significant increase in self-reported knowledge across all six facets of hydration care (p = 0.000). The majority of participants found the training enjoyable and useful, and expressed an expected change in their practice. Participants enjoyed the interactive components of the training. A lack of reflective practice skills meant participants were unable to reflect realistically about the hydration care provided in the home. Focused training on hydration in the care home environment benefits from being interactive and experiential. Although such training can be effective in increasing staff knowledge, inclusion of skills in reflective practice is required if this knowledge is to be translated into practice. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dynamic morphology of gas hydrate on a methane bubble in water: Observations and new insights for hydrate film models

NASA Astrophysics Data System (ADS)

Warzinski, Robert P.; Lynn, Ronald; Haljasmaa, Igor; Leifer, Ira; Shaffer, Frank; Anderson, Brian J.; Levine, Jonathan S.

2014-10-01

Predicting the fate of subsea hydrocarbon gases escaping into seawater is complicated by potential formation of hydrate on rising bubbles that can enhance their survival in the water column, allowing gas to reach shallower depths and the atmosphere. The precise nature and influence of hydrate coatings on bubble hydrodynamics and dissolution is largely unknown. Here we present high-definition, experimental observations of complex surficial mechanisms governing methane bubble hydrate formation and dissociation during transit of a simulated oceanic water column that reveal a temporal progression of deep-sea controlling mechanisms. Synergistic feedbacks between bubble hydrodynamics, hydrate morphology, and coverage characteristics were discovered. Morphological changes on the bubble surface appear analogous to macroscale, sea ice processes, presenting new mechanistic insights. An inverse linear relationship between hydrate coverage and bubble dissolution rate is indicated. Understanding and incorporating these phenomena into bubble and bubble plume models will be necessary to accurately predict global greenhouse gas budgets for warming ocean scenarios and hydrocarbon transport from anthropogenic or natural deep-sea eruptions.

Micro-Tomographic Investigation of Ice and Clathrate Formation and Decomposition under Thermodynamic Monitoring.

PubMed

Arzbacher, Stefan; Petrasch, Jörg; Ostermann, Alexander; Loerting, Thomas

2016-08-08

Clathrate hydrates are inclusion compounds in which guest molecules are trapped in a host lattice formed by water molecules. They are considered an interesting option for future energy supply and storage technologies. In the current paper, time lapse 3D micro computed tomographic (µCT) imaging with ice and tetrahydrofuran (THF) clathrate hydrate particles is carried out in conjunction with an accurate temperature control and pressure monitoring. µCT imaging reveals similar behavior of the ice and the THF clathrate hydrate at low temperatures while at higher temperatures (3 K below the melting point), significant differences can be observed. Strong indications for micropores are found in the ice as well as the THF clathrate hydrate. They are stable in the ice while unstable in the clathrate hydrate at temperatures slightly below the melting point. Significant transformations in surface and bulk structure can be observed within the full temperature range investigated in both the ice and the THF clathrate hydrate. Additionally, our results point towards an uptake of molecular nitrogen in the THF clathrate hydrate at ambient pressures and temperatures from 230 K to 271 K.

[In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation].

PubMed

Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei

2011-06-01

Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

Microwave-assisted co-pyrolysis of brown coal and corn stover for oil production.

PubMed

Zhang, Yaning; Fan, Liangliang; Liu, Shiyu; Zhou, Nan; Ding, Kuan; Peng, Peng; Anderson, Erik; Addy, Min; Cheng, Yanling; Liu, Yuhuan; Li, Bingxi; Snyder, John; Chen, Paul; Ruan, Roger

2018-07-01

The controversial synergistic effect between brown coal and biomass during co-pyrolysis deserves further investigation. This study detailed the oil production from microwave-assisted co-pyrolysis of brown coal (BC) and corn stover (CS) at different CS/BC ratios (0, 0.33, 0.50, 0.67, and 1) and pyrolysis temperatures (500, 550, and 600 °C). The results showed that a higher CS/BC ratio resulted in higher oil yield, and a higher pyrolysis temperature increased oil yield for brown coal and coal/corn mixtures. Corn stover and brown coal showed different pyrolysis characteristics, and positive synergistic effect on oil yield was observed only at CS/BC ratio of 0.33 and pyrolysis temperature of 600 °C. Oils from brown coal mainly included hydrocarbons and phenols whereas oils from corn stover and coal/corn mixtures were dominated by ketones, phenols, and aldehydes. Positive synergistic effects were observed for ketones, aldehydes, acids, and esters whereas negative synergistic effects for hydrocarbons, phenols and alcohols. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydration water dynamics in biopolymers from NMR relaxation in the rotating frame.

PubMed

Blicharska, Barbara; Peemoeller, Hartwig; Witek, Magdalena

2010-12-01

Assuming dipole-dipole interaction as the dominant relaxation mechanism of protons of water molecules adsorbed onto macromolecule (biopolymer) surfaces we have been able to model the dependences of relaxation rates on temperature and frequency. For adsorbed water molecules the correlation times are of the order of 10(-5)s, for which the dispersion region of spin-lattice relaxation rates in the rotating frame R(1)(ρ)=1/T(1)(ρ) appears over a range of easily accessible B(1) values. Measurements of T(1)(ρ) at constant temperature and different B(1) values then give the "dispersion profiles" for biopolymers. Fitting a theoretical relaxation model to these profiles allows for the estimation of correlation times. This way of obtaining the correlation time is easier and faster than approaches involving measurements of the temperature dependence of R(1)=1/T(1). The T(1)(ρ) dispersion approach, as a tool for molecular dynamics study, has been demonstrated for several hydrated biopolymer systems including crystalline cellulose, starch of different origins (potato, corn, oat, wheat), paper (modern, old) and lyophilized proteins (albumin, lysozyme). Copyright © 2010 Elsevier Inc. All rights reserved.

Degradation of Aflatoxin B1 during the Fermentation of Alcoholic Beverages

PubMed Central

Inoue, Tomonori; Nagatomi, Yasushi; Uyama, Atsuo; Mochizuki, Naoki

2013-01-01

Aflatoxin B1 (AFB1) is a contaminant of grain and fruit and has one of the highest levels of carcinogenicity of any natural toxin. AFB1 and the fungi that produce it can also contaminate the raw materials used for beer and wine manufacture, such as corn and grapes. Therefore, brewers must ensure strict monitoring to reduce the risk of contamination. In this study, the fate of AFB1 during the fermentation process was investigated using laboratory-scale bottom and top beer fermentation and wine fermentation. During fermentation, cool wort beer samples and wine must samples were artificially spiked with AFB1 and the levels of AFB1 remaining after fermentation were analyzed. AFB1 levels were unchanged during both types of fermentation used for beer but were reduced to 30% of their initial concentration in wine. Differential analysis of the spiked and unspiked wine samples showed that the degradation compound was AFB2a, a hydrated derivative of AFB1. Thus, the results showed that the risk of AFB1 carryover was still present for both types of beer fermentation but was reduced in the case of wine fermentation because of hydration. PMID:23812408

Estimating pore-space gas hydrate saturations from well log acoustic data

USGS Publications Warehouse

Lee, Myung W.; Waite, William F.

2008-01-01

Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate–bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

The assessment of different production methods for hydrate bearing sediments - results from small and large scale experiments

NASA Astrophysics Data System (ADS)

Schicks, Judith; Heeschen, Katja; Spangenberg, Erik; Luzi-Helbing, Manja; Beeskow-Strauch, Bettina; Priegnitz, Mike; Giese, Ronny; Abendroth, Sven; Thaler, Jan

2017-04-01

Natural gas hydrates occur at all active and passive continental margins, in permafrost regions, and deep lakes. Since they are supposed to contain enormous amounts of methane, gas hydrates are discussed as an energy resource. For the production of gas from hydrate bearing sediments, three different production methods were tested during the last decade: depressurization, thermal and chemical stimulation as well as combinations of these methods. In the framework of the SUGAR project we developed a Large Scale Reservoir Simulator (LARS) with a total volume of 425L to test these three methods in a pilot plant scale. For this purpose we formed hydrate from methane saturated brine in sediments under conditions close to natural gas hydrate deposits. The obtained hydrate saturations varied between 40-90%. Hydrate saturation and distribution were determined using electrical resistivity tomography (ERT). The volumes of the produced gas and water were determined and the gas phase was analyzed via gas chromatography. Multi-step depressurization, thermal stimulation applying in-situ combustion as well as chemical stimulation via the injection of CO2 and a CO2-N2-mixture were tested. Depressurization and thermal stimulation appear to be less complicated compared to the chemical stimulation. For the understanding of the macroscopically observed processes on a molecular level, we also performed experiments on a smaller scale using microscopic observation, Raman spectroscopy and X-ray diffraction. The results of these experiments are of particular importance for the understanding of the processes occurring during the CO2-CH4 swapping. Under the chosen experimental conditions the observations indicate a (partial) decomposition and reformation of the hydrate structure rather than a diffusion-controlled exchange of the molecules.

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

USGS Publications Warehouse

Stern, L.A.; Hogenboom, D.L.; Durham, W.B.; Kirby, S.H.; Chou, I.-Ming

1998-01-01

We previously reported indirect but compelling evidence that fine-grained H2O ice under elevated CH4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H2O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6-8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H2O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice-hydrate interface. Results from similar tests using CO2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH4-H2O system.

Widespread gas hydrate instability on the upper U.S. Beaufort margin

NASA Astrophysics Data System (ADS)

Phrampus, Benjamin J.; Hornbach, Matthew J.; Ruppel, Carolyn D.; Hart, Patrick E.

2014-12-01

The most climate-sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three-dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5-7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.

Along - Strike Analysis of Contemporary Ocean Temperature Change on the Cascadia Margin and Implications to Upper Slope Hydrate Instability

NASA Astrophysics Data System (ADS)

Phrampus, B.; Harris, R. N.; Trehu, A. M.; Embley, R. W.; Merle, S. G.

2017-12-01

Gas hydrates are found globally on continental margins and due to the large amount of sequestered carbon in hydrate reservoirs, whether these deposits are dynamic or stable has significant implications for slope stability, ocean/atmosphere carbon budget, and deep-water energy exploration. Recent studies indicate that upper slope hydrate degradation may be relatively widespread on passive margins due to recent ocean temperature warming between 0.012 and 0.033 °C/yr (e.g. Svalbard, North Alaska, and US Atlantic margin). However, the potential and breadth of warming induced hydrate instability remains contentious based on multiple observations including: 1) seep locations not consistent with locations of hydrate dissociation, 2) a lack of hydrate in regions of warming, and 3) evidence for long-lived seepage in regions associated with contemporary warming-induced hydrate dissociation. At the Cascadia margin, a recent study suggests that contemporary warming of intermediate water intersects the hydrate stability zone leading to hydrate dissociation that feeds upper slope seeps. Here, we provide a systematic analysis of along-strike variations in hydrate distribution along the Cascadia margin combined with a multivariable regression of ocean temperatures to characterize the potential of upper slope hydrate instability. Preliminary seep locations reveal upper slope seeps and observed regions of hydrate are correlated spatially between 42.5 and 48.0 °N, outside this region there is a dearth of identified upper slope hydrate and seeps. Between 44.5 and 48.0 °N a contemporary warming trend is as large as 0.006 °C/yr and is collocated with upper slope hydrate and gas seepage. This warming rate is relatively small, 2-5x smaller than warming trends identified in the Arctic where temperature induced hydrate instability remains uncertain. Additionally, we identify a region between 42.5 and 44.5 °N with collocated upper slope seepage and hydrate but no evidence of ocean warming, suggesting upper slope seepage is not driven by temperature induced hydrate instability, but maybe driven by tectonic uplift. These results highlight the absence of temperature driven seepage and slope instability on the Cascadia margin and deemphasize the impact of lower latitude warming on global hydrate dynamics and carbon budget.

Kinetic studies of methane-ethane mixed gas hydrates by neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Kuhs, Werner F

2009-04-16

In situ formations of CH(4)-C(2)H(6) mixed gas hydrates were made using high flux neutron diffraction at 270 K and 5 MPa. For this purpose, a feed gas composition of CH(4) and C(2)H(6) (95 mol% CH(4)) was employed. The rates of transformation of spherical grains of deuterated ice Ih into hydrates were measured by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. Phase fractions of the crystalline constituents were obtained from Rietveld refinements. A concomitant formation of structure type I (sI) and structure type II (sII) hydrates were observed soon after the gas pressure was applied. The initial fast formation of sII hydrate reached its maximum volume and started declining very slowly. The formation of sI hydrate followed a sigmoid growth kinetics that slowed down due to diffusion limitation. This observation has been interpreted in terms of a kinetically favored nucleation of the sII hydrate along with a slow transformation into sI. Both powder diffraction and Raman spectroscopic results suggest that a C(2)H(6)-rich sII hydrate was formed at the early part of the clathration, which slowly decreased to approximately 3% after a reaction of 158 days as confirmed by synchrotron XRD. The final persistence of a small portion of sII hydrate points to a miscibility gap between CH(4)-rich sI and C(2)H(6)-rich sII hydrates.

Prestack Waveform Inversion and Well Log Examination at GC955 and WR313 in the Gulf of Mexico for Estimation of Methane Hydrate Concentrations

NASA Astrophysics Data System (ADS)

Fortin, W.; Goldberg, D.; Kucuk, H. M.

2017-12-01

Gas hydrates are naturally occurring compounds, which, at a molecular scale, are lattice structures of ice embedded with various gas molecules in the lattice voids. Volumetric estimates of associated hydrocarbons vary greatly due to the difficulty in remotely estimating hydrate concentrations in marine sediments but embedded hydrocarbon stores are thought to represent a significant portion of global deposits. Inherent hydrate instabilities obscure our understanding of and complicates processes related to resource extraction and hydrate response to disturbances in the local environment. Understanding the spatial extent and variability of hydrate deposits have important implications for potential economic production, climate change, and assessing natural hazards risks. Seismic reflection techniques are capable of determining the extent of gas hydrate deposits, often through the observation of bottom simulating reflectors (BSRs). However, BSRs are not present everywhere gas hydrates exist. Using high resolution prestack time migrated seismic data and prestack waveform inversion (PWI) we produce highly resolved velocity models and compare them to co-located well logs. Coupling our PWI results with velocity-porosity relationships and nearby well control, we map hydrate properties at GC955 and WR313. Integrating small scale heterogeneities and variations along the velocity model with in-situ measurements, we develop a workflow aimed to quantify hydrate concentrations observed in seismic data over large areas in great detail regardless of the existence of a BSR.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone.

PubMed

Braun, Doris E; Griesser, Ulrich J

2018-01-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4'-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III ) differ only by ~1 kJ mol -1 . The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

Determination of Protein Surface Hydration by Systematic Charge Mutations

NASA Astrophysics Data System (ADS)

Yang, Jin; Jia, Menghui; Qin, Yangzhong; Wang, Dihao; Pan, Haifeng; Wang, Lijuan; Xu, Jianhua; Zhong, Dongping; Dongping Zhong Collaboration; Jianhua Xu Collaboration

Protein surface hydration is critical to its structural stability, flexibility, dynamics and function. Recent observations of surface solvation on picosecond time scales have evoked debate on the origin of such relatively slow motions, from hydration water or protein charged sidechains, especially with molecular dynamics simulations. Here, we used a unique nuclease with a single tryptophan as a local probe and systematically mutated neighboring three charged residues to differentiate the contributions from hydration water and charged sidechains. By mutations of alternative one and two and all three charged residues, we observed slight increases in the total tryptophan Stokes shifts with less neighboring charged residue(s) and found insensitivity of charged sidechains to the relaxation patterns. The dynamics is correlated with hydration water relaxation with the slowest time in a dense charged environment and the fastest time at a hydrophobic site. On such picosecond time scales, the protein surface motion is restricted. The total Stokes shifts are dominantly from hydration water relaxation and the slow dynamics is from water-driven relaxation, coupled with local protein fluctuations.

Soil diversity and hydration as observed by ChemCam at Gale crater, Mars

USGS Publications Warehouse

Meslin, P.-Y.; Gasnault, O.; Forni, O.; Schroder, S.; Cousin, A.; Berger, G.; Clegg, S.M.; Lasue, J.; Maurice, S.; Sautter, V.; Le Mouélic, S.; Wiens, R.C.; Fabre, C.; Goetz, W.; Bish, D.L.; Mangold, N.; Ehlmann, B.; Lanza, N.; Harri, A.-M.; Anderson, Ryan Bradley; Rampe, E.; McConnochie, T.H.; Pinet, P.; Blaney, D.; ,; Archer, D.; Barraclough, B.; Bender, S.; Blake, D.; Blank, J.G.; Bridges, N.; Clark, B. C.; DeFlores, L.; Delapp, D.; Dromart, G.; Dyar, M.D.; Fisk, M. R.; Gondet, B.; Grotzinger, J.; Herkenhoff, K.; Johnson, J.; Lacour, J.-L.; Langevin, Y.; Leshin, L.; Lewin, E.; Madsen, M.B.; Melikechi, N.; Mezzacappa, Alissa; Mischna, M.A.; Moores, J.E.; Newsom, H.; Ollila, A.; ,; Renno, N.; Sirven, J.B.; Tokar, R.; de la Torre, M.; d'Uston, L.; Vaniman, D.; Yingst, A.

2013-01-01

The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.

Soil diversity and hydration as observed by ChemCam at Gale crater, Mars.

PubMed

Meslin, P-Y; Gasnault, O; Forni, O; Schröder, S; Cousin, A; Berger, G; Clegg, S M; Lasue, J; Maurice, S; Sautter, V; Le Mouélic, S; Wiens, R C; Fabre, C; Goetz, W; Bish, D; Mangold, N; Ehlmann, B; Lanza, N; Harri, A-M; Anderson, R; Rampe, E; McConnochie, T H; Pinet, P; Blaney, D; Léveillé, R; Archer, D; Barraclough, B; Bender, S; Blake, D; Blank, J G; Bridges, N; Clark, B C; DeFlores, L; Delapp, D; Dromart, G; Dyar, M D; Fisk, M; Gondet, B; Grotzinger, J; Herkenhoff, K; Johnson, J; Lacour, J-L; Langevin, Y; Leshin, L; Lewin, E; Madsen, M B; Melikechi, N; Mezzacappa, A; Mischna, M A; Moores, J E; Newsom, H; Ollila, A; Perez, R; Renno, N; Sirven, J-B; Tokar, R; de la Torre, M; d'Uston, L; Vaniman, D; Yingst, A

2013-09-27

The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.

SOFIA + FORCAST Observations of 10 Aqueously Altered Asteroids

NASA Astrophysics Data System (ADS)

McAdam, Margaret; Sunshine, Jessica M.; Kelley, Michael S.; Bus, Schelte J.

2016-10-01

Aqueous alteration, or the reaction of water and minerals to produce hydrated minerals, has affected certain groups of carbonaceous meteorites (e.g., the CM and CI meteorites) and asteroids. In the visible/near-infrared (VNIR), CM/CI meteorites and some dark C-complex asteroids are known to have 0.7-µm absorptions that indicate the presence of hydrated minerals [1, 2, 3]. However, this feature does not provide any information about the amount of hydrated minerals in asteroids or meteorites [1]. In contrast, at mid-infrared (MIR) wavelengths, strong spectral features change continuously with amount of hydrated minerals in a suite of well-characterized CM/CI meteorites [1].Using these results, we analyze the spectra of 10 C-complex asteroids observed by SOFIA + FORCAST. These targets are large objects (>95 km diameter) situated in the mid to outer Main Asteroid Belt (2.4 - 3.4 AU). We present spectra of the following asteroids, spectral types in parentheses: 36 Atalante (C), 38 Leda (Cgh), 62 Erato (Ch), 121 Hermione (Ch), 165 Loreley (Cb), 194 Prokne (C), 203 Pompeja (C), 266 Aline (Ch), 52 Europa (Ch), and 19 Fortuna (Ch). Spectra were obtained in two wavelength regions: 8.5-13.6-μm and 17.6-27.7-μm. In these spectral regions, mineralogical features that are known to change continuously with amount of hydrated minerals appear. Most of these targets are known to have hydrated minerals on their surfaces by the presence of the 0.7-μm feature [e.g. 3, 4] or from observations in the 3-μm region [5]. We interpret the spectral features observed using SOFIA and estimate the abundances of hydrated minerals for each asteroid. Additionally, we compare these observations to Spitzer observations of similar objects. A subset of these asteroids have also been measured in VNIR, which allows us to directly compare the signatures of hydration in both the VNIR and the MIR.[1] McAdam et al., (2015), Icarus, 245, 320-332. [2] Cloutis, et al., (2011), Icarus, 216, 309-346. [3] Vilas and Gaffey (1989), Science, 246, 790-792. [4] Bus and Binzel (2002), Icarus, 158, 146-177. Takir and Emery (2012), Icarus, 219, 641-654.

Crystal structure of zwitterionic bisimidazolium sulfonates

NASA Astrophysics Data System (ADS)

Kohmoto, Shigeo; Okuyama, Shinpei; Yokota, Nobuyuki; Takahashi, Masahiro; Kishikawa, Keiki; Masu, Hyuma; Azumaya, Isao

2012-05-01

Crystal structures of three zwitterionic bisimidazolium salts 1-3 in which imidazolium sulfonate moieties were connected with aromatic linkers, p-xylylene, 4,4'-dimethylenebiphenyl, and phenylene, respectively, were examined. The latter two were obtained as hydrates. An S-shaped molecular structure in which the sulfonate moiety was placed on the imidazolium ring was observed for 1. A helical array of hydrated water molecules was obtained for 2 while a linear array of hydrated water molecules was observed for 3.

Geomechanical Modeling of Gas Hydrate Bearing Sediments

NASA Astrophysics Data System (ADS)

Sanchez, M. J.; Gai, X., Sr.

2015-12-01

This contribution focuses on an advance geomechanical model for methane hydrate-bearing soils based on concepts of elasto-plasticity for strain hardening/softening soils and incorporates bonding and damage effects. The core of the proposed model includes: a hierarchical single surface critical state framework, sub-loading concepts for modeling the plastic strains generally observed inside the yield surface and a hydrate enhancement factor to account for the cementing effects provided by the presence of hydrates in sediments. The proposed framework has been validated against recently published experiments involving both, synthetic and natural hydrate soils, as well as different sediments types (i.e., different hydrate saturations, and different hydrates morphologies) and confinement conditions. The performance of the model in these different case studies was very satisfactory.

Hydration Effects on Skin Microstructure as Probed by High-Resolution Cryo-Scanning Electron Microscopy and Mechanistic Implications to Enhanced Transcutaneous Delivery of Biomacromolecules

PubMed Central

Tan, Grace; Xu, Peng; Lawson, Louise B.; He, Jibao; Freytag, Lucia C.; Clements, John D.; John, Vijay T.

2010-01-01

Although hydration is long known to improve the permeability of skin, penetration of macromolecules such as proteins is limited and the understanding of enhanced transport is based on empirical observations. This study uses high-resolution cryo-scanning electron microscopy to visualize microstructural changes in the stratum corneum (SC) and enable a mechanistic interpretation of biomacromolecule penetration through highly hydrated porcine skin. Swollen corneocytes, separation of lipid bilayers in the SC intercellular space to form cisternae, and networks of spherical particulates are observed in porcine skin tissue hydrated for a period of 4–10 h. This is explained through compaction of skin lipids when hydrated, a reversal in the conformational transition from unilamellar liposomes in lamellar granules to lamellae between keratinocytes when the SC skin barrier is initially established. Confocal microscopy studies show distinct enhancement in penetration of fluorescein isothiocyanate-bovine serum albumin (FITC-BSA) through skin hydrated for 4–10 h, and limited penetration of FITC-BSA once skin is restored to its natively hydrated structure when exposed to the environment for 2–3 h. These results demonstrate the effectiveness of a 4–10 h hydration period to enhance transcutaneous penetration of large biomacromolecules without permanently damaging the skin. PMID:19582754

Resveratrol-Loaded Lipid Nanocarriers: Correlation between In Vitro Occlusion Factor and In Vivo Skin Hydrating Effect

PubMed Central

Parenti, Carmela; Turnaturi, Rita

2017-01-01

Lipid nanocarriers show occlusive properties that may be related to their ability to improve skin hydration. The aim of this work was to evaluate the relationship between in vitro occlusion factor and in vivo skin hydration for three types of lipid nanocarriers: nanoemulsions (NEs), solid lipid nanoparticles (SLNs) and nanostructured lipid carriers (NLCs). These lipid nanocarriers were loaded with trans-resveratrol (RSV) and incorporated in gel vehicles. In vitro occlusion factor was in the order SLNs > NLCs > NEs. Gels containing unloaded or RSV loaded lipid nanocarriers were applied on the back of a hand of 12 healthy volunteers twice a day for one week, recording skin hydration changes using the instrument Soft Plus. An increase of skin hydration was observed for all lipid nanocarriers (SLNs > NLCs > NEs). RSV loading into these nanocarriers did not affect in vitro and in vivo lipid nanocarriers effects. A linear relationship (r2 = 0.969) was observed between occlusion factor and in vivo increase of skin hydration. Therefore, the results of this study showed the feasibility of using the occlusion factor to predict in vivo skin hydration resulting from topical application of different lipid nanocarriers loading an active ingredient with no inherent hydrating activity. PMID:29232856

Elastic properties of gas hydrate-bearing sediments

USGS Publications Warehouse

Lee, M.W.; Collett, T.S.

2001-01-01

Downhole-measured compressional- and shear-wave velocities acquired in the Mallik 2L-38 gas hydrate research well, northwestern Canada, reveal that the dominant effect of gas hydrate on the elastic properties of gas hydrate-bearing sediments is as a pore-filling constituent. As opposed to high elastic velocities predicted from a cementation theory, whereby a small amount of gas hydrate in the pore space significantly increases the elastic velocities, the velocity increase from gas hydrate saturation in the sediment pore space is small. Both the effective medium theory and a weighted equation predict a slight increase of velocities from gas hydrate concentration, similar to the field-observed velocities; however, the weighted equation more accurately describes the compressional- and shear-wave velocities of gas hydrate-bearing sediments. A decrease of Poisson's ratio with an increase in the gas hydrate concentration is similar to a decrease of Poisson's ratio with a decrease in the sediment porosity. Poisson's ratios greater than 0.33 for gas hydrate-bearing sediments imply the unconsolidated nature of gas hydrate-bearing sediments at this well site. The seismic characteristics of gas hydrate-bearing sediments at this site can be used to compare and evaluate other gas hydrate-bearing sediments in the Arctic.

Failure Mechanism of Cemented Hydrate-bearing Sand at Microscales

NASA Astrophysics Data System (ADS)

Yoneda, J.; Jin, Y.; Katagiri, J.; Tenma, N.

2016-12-01

On the basis of hypothetical particle-level mechanisms, several constitutive models of hydrate-bearing sediments have been proposed previously for gas production. However, to the best of our knowledge, the microstructural large-strain behaviors of hydrate-bearing sediments has not been reported to date because of the experimental challenges posed by the high-pressure and low-temperature testing conditions. Herein, as a part of a Japanese National hydrate research program (MH21, funded by METI), a novel microtriaxial testing apparatus was developed, and the mechanical large strain behavior of hydrate-bearing sediments with various hydrate saturation values (Sh = 0%, 39%, and 62%) were analyzed using microfocus X-ray computed tomography. Patchy hydrates were observed in the sediments at Sh = 39%. The obtained stress-strain relationships indicated strengthening with increasing hydrate saturation and a brittle failure mode of the hydrate-bearing sand. Localized deformations were quantified via image processing at the submillimeter and micrometer scale. Shear planes and particle deformation and/or rotation were detected, and the shear band thickness decreased with increasing hydrate saturation.

Primary radical yields in pulse irradiated alkaline aqueous solution

NASA Technical Reports Server (NTRS)

Fielden, E. M.; Hart, E. J.

1969-01-01

Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

Modulation of the Fecal Microbiota in Sprague-Dawley Rats Using Genetically Modified and Isogenic Corn Lines.

PubMed

Li, Penggao; Yang, Chun; Yue, Rong; Zhen, Yaping; Zhuo, Qin; Piao, Jianhua; Yang, Xiaoguang; Xiao, Rong

2018-01-17

This study investigated the composition and proportions of fecal microbiota in Sprague-Dawley rats after consuming two genetically modified (GM) corn lines in comparison with the isogenic corn and the AIN93G standard feed for 10 weeks using bar-coded 16S rRNA gene sequencing. As a result, GM corn did not significantly alter the overall health and alpha-diversity of fecal microbiota. Fecal microbiota structures could be separated into noncorn and corn but not non-GM and GM corn subgroups. Both non-GM and GM corn caused the increase in bacterial populations related to carbohydrates utilization, such as Lactobacillus, Barnesiella, and Bifidobacterium, and the reduction in potentially pathogenic populations, such as Tannerella and Moraxellaceae. In conclusion, similar effects on the fecal microbiota were observed after consuming a GM- and non-GM-corn-based diet for long periods. Further studies are warranted to elucidate the functional relevance of the changes in the proportions of bacterial populations in these diets.

Testing short-range migration of microbial methane as a hydrate formation mechanism: Results from Andaman Sea and Kumano Basin drill sites and global implications

NASA Astrophysics Data System (ADS)

Malinverno, Alberto; Goldberg, David S.

2015-07-01

Methane gas hydrates in marine sediments often concentrate in coarse-grained layers surrounded by fine-grained marine muds that are hydrate-free. Methane in these hydrate deposits is typically microbial, and must have migrated from its source as the coarse-grained sediments contain little or no organic matter. In "long-range" migration, fluid flow through permeable layers transports methane from deeper sources into the gas hydrate stability zone (GHSZ). In "short-range" migration, microbial methane is generated within the GHSZ in fine-grained sediments, where small pore sizes inhibit hydrate formation. Dissolved methane can then diffuse into adjacent sand layers, where pore size does not restrict hydrate formation and hydrates can accumulate. Short-range migration has been used to explain hydrate accumulations in sand layers observed in drill sites on the northern Cascadia margin and in the Gulf of Mexico. Here we test the feasibility of short-range migration in two additional locations, where gas hydrates have been found in coarse-grained volcanic ash layers (Site NGHP-01-17, Andaman Sea, Indian Ocean) and turbidite sand beds (Site IODP-C0002, Kumano forearc basin, Nankai Trough, western Pacific). We apply reaction-transport modeling to calculate dissolved methane concentration and gas hydrate amounts resulting from microbial methane generated within the GHSZ. Model results show that short-range migration of microbial methane can explain the overall amounts of methane hydrate observed at the two sites. Short-range migration has been shown to be feasible in diverse margin environments and is likely to be a widespread methane transport mechanism in gas hydrate systems. It only requires a small amount of organic carbon and sediment sequences consisting of thin coarse-grained layers that can concentrate microbial methane generated within thick fine-grained sediment beds; these conditions are common along continental margins around the globe.

Far-infrared investigations of a methanol clathrate hydrate - Implications for astronomical observations

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Moore, Marla H.

1993-01-01

Observations of nonterrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over 40 years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. We have prepared a methanol (CH3OH) clathrate hydrate, using a recently published procedure, and have investigated its far-infrared spectrum. The spectrum is quite different from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Lu, H.; Lorenson, T.D.; Moudrakovski, I.L.; Ripmeester, J.A.; Collett, T.S.; Hunter, R.B.; Ratcliffe, C.I.

2011-01-01

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH4 gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state 13C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean ??13C=-48.6??? and ??D=-248??? for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage. ?? 2010 Elsevier Ltd.

Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

USGS Publications Warehouse

Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

2007-01-01

The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

NASA Astrophysics Data System (ADS)

Malinverno, A.; Cook, A.; Daigle, H.

2016-12-01

Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction, solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.

Widespread gas hydrate instability on the upper U.S. Beaufort margin

USGS Publications Warehouse

Phrampus, Benjamin J.; Hornbach, Matthew J.; Ruppel, Carolyn D.; Hart, Patrick E.

2014-01-01

The most climate-sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three-dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5–7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.

Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

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

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction,more » solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.« less

High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Sun, Y.; Goldberg, D.; Collett, T.; Hunter, R.

2011-01-01

A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis. ?? 2010 Elsevier Ltd.

Hydrogen-Bonding System in Barium Nitroprusside 6.5-Hydrate

NASA Astrophysics Data System (ADS)

Navaza, A.; Chevrier, G.; Guida, J. A.

1995-01-01

The hydrogen-bond system in barium nitroprusside 6.5-hydrate, [Ba 2(H 2O) 10][Fe(CN) 5NOl 23H 2O], has been determined by neutron diffraction on monocrystals. Results show the compound to be orthorhombic, space group Cmc2 1 (36), a = 16.008(43), b = 11.550(3), c = 16.648(5) Å, V = 3078(3) Å 3, Z = 4. Refinement of the structure, using 973 observed structure factors, converged to the final RW factor of 0.058. The 2 independent barium atoms, separated 4.60 Å, share a plane of three water molecules forming dimeric tetravalent units. The nitroprusside anions deviate from the C4r ideal symmetry, but this deviation is less than that observed in other nitroprussides. The 10 crystallographically independent water molecules have been classified according to their coordination. Analysis of the H-bond strength, together with a comparison of the packing of the two known barium nitroprusside hydrates (3-hydrate and 6.5-hydrate), suggests that the water molecules labeled as W(1), W(7), W(8), and W(9) could be lost during the partial dehydration of 6.5-hydrate into 3-hydrate.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ripmeester, J. A.

2010-04-01

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

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

PubMed

Alavi, Saman; Ripmeester, J A

2010-04-14

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

Low-frequency Raman scattering in a Xe hydrate.

PubMed

Adichtchev, S V; Belosludov, V R; Ildyakov, A V; Malinovsky, V K; Manakov, A Yu; Subbotin, O S; Surovtsev, N V

2013-09-12

The physics of gas hydrates are rich in interesting phenomena such as anomalies for thermal conductivity, self-preservation effects for decomposition, and others. Some of these phenomena are presumably attributed to the resonance interaction of the rattling motions of guest molecules or atoms with the lattice modes. This can be expected to induce some specific features in the low-frequency (THz) vibrational response. Here we present results for low-frequency Raman scattering in a Xe hydrate, supported by numerical calculations of vibrational density of states. A number of narrow lines, located in the range from 18 to 90 cm(-1), were found in the Raman spectrum. Numerical calculations confirm that these lines correspond to resonance modes of the Xe hydrate. Also, low-frequency Raman scattering was studied during gas hydrate decomposition, and two scenarios were observed. The first one is the direct decomposition of the Xe hydrate to water and gas. The second one is the hydrate decomposition to ice and gas with subsequent melting of ice. In the latter case, a transient low-frequency Raman band is observed, which is associated with low-frequency bands (e.g., boson peak) of disordered solids.

Micro-Tomographic Investigation of Ice and Clathrate Formation and Decomposition under Thermodynamic Monitoring

PubMed Central

Arzbacher, Stefan; Petrasch, Jörg; Ostermann, Alexander; Loerting, Thomas

2016-01-01

Clathrate hydrates are inclusion compounds in which guest molecules are trapped in a host lattice formed by water molecules. They are considered an interesting option for future energy supply and storage technologies. In the current paper, time lapse 3D micro computed tomographic (µCT) imaging with ice and tetrahydrofuran (THF) clathrate hydrate particles is carried out in conjunction with an accurate temperature control and pressure monitoring. µCT imaging reveals similar behavior of the ice and the THF clathrate hydrate at low temperatures while at higher temperatures (3 K below the melting point), significant differences can be observed. Strong indications for micropores are found in the ice as well as the THF clathrate hydrate. They are stable in the ice while unstable in the clathrate hydrate at temperatures slightly below the melting point. Significant transformations in surface and bulk structure can be observed within the full temperature range investigated in both the ice and the THF clathrate hydrate. Additionally, our results point towards an uptake of molecular nitrogen in the THF clathrate hydrate at ambient pressures and temperatures from 230 K to 271 K. PMID:28773789

Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

PubMed

Yamamoto, Yo-ichi; Suzuki, Yoshi-Ichi; Tomasello, Gaia; Horio, Takuya; Karashima, Shutaro; Mitríc, Roland; Suzuki, Toshinori

2014-05-09

We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and I- in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed.

Shortwave infrared detection of vegetation

NASA Technical Reports Server (NTRS)

Goward, S. N. (Principal Investigator)

1985-01-01

The potential of short wave infrared (SWIR) measurements in vegetation discrimination is further substantiated through a discussion of field studies and an examination of the physical bases which cause SWIR measurements to vary with the vegetation type observed. The research reported herein supported the AGRISTARS program objective to incorporate TM measurements in the analysis of agricultural activity. Field measurements on corn and soybeans in Iowa were conducted, and the mean and variance of canopy reflectance were computed for each observation date. The Suits canopy reflectance model was used to evaluate possible explanations of the observed corn/soybeans reflectance patterns /39/. The SWIR measurements were shown to effectively discriminate corn and soybeans on the basis of leaf absorption properties.

Examination of core samples from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Effects of retrieval and preservation

USGS Publications Warehouse

Kneafsey, T.J.; Lu, H.; Winters, W.; Boswell, R.; Hunter, R.; Collett, T.S.

2011-01-01

Collecting and preserving undamaged core samples containing gas hydrates from depth is difficult because of the pressure and temperature changes encountered upon retrieval. Hydrate-bearing core samples were collected at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well in February 2007. Coring was performed while using a custom oil-based drilling mud, and the cores were retrieved by a wireline. The samples were characterized and subsampled at the surface under ambient winter arctic conditions. Samples thought to be hydrate bearing were preserved either by immersion in liquid nitrogen (LN), or by storage under methane pressure at ambient arctic conditions, and later depressurized and immersed in LN. Eleven core samples from hydrate-bearing zones were scanned using x-ray computed tomography to examine core structure and homogeneity. Features observed include radial fractures, spalling-type fractures, and reduced density near the periphery. These features were induced during sample collection, handling, and preservation. Isotopic analysis of the methane from hydrate in an initially LN-preserved core and a pressure-preserved core indicate that secondary hydrate formation occurred throughout the pressurized core, whereas none occurred in the LN-preserved core, however no hydrate was found near the periphery of the LN-preserved core. To replicate some aspects of the preservation methods, natural and laboratory-made saturated porous media samples were frozen in a variety of ways, with radial fractures observed in some LN-frozen sands, and needle-like ice crystals forming in slowly frozen clay-rich sediments. Suggestions for hydrate-bearing core preservation are presented.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

PubMed Central

Braun, Doris E.; Griesser, Ulrich J.

2018-01-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

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

2009-03-12

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

Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

NASA Astrophysics Data System (ADS)

Burchwell, A.; Cook, A.

2015-12-01

Characterizing gas hydrate in a reservoir typically involves a full suite of geophysical well logs. The most common method involves using resistivity measurements to quantify the decrease in electrically conductive water when replaced with gas hydrate. Compressional velocity measurements are also used because the gas hydrate significantly strengthens the moduli of the sediment. At many gas hydrate sites, nuclear well logs, which include the photoelectric effect, formation sigma, carbon/oxygen ratio and neutron porosity, are also collected but often not used. In fact, the nuclear response of a gas hydrate reservoir is not known. In this research we will focus on the nuclear log response in gas hydrate reservoirs at the Mallik Field at the Mackenzie Delta, Northwest Territories, Canada, and the Gas Hydrate Joint Industry Project Leg 2 sites in the northern Gulf of Mexico. Nuclear logs may add increased robustness to the investigation into the properties of gas hydrates and some types of logs may offer an opportunity to distinguish between gas hydrate and permafrost. For example, a true formation sigma log measures the thermal neutron capture cross section of a formation and pore constituents; it is especially sensitive to hydrogen and chlorine in the pore space. Chlorine has a high absorption potential, and is used to determine the amount of saline water within pore spaces. Gas hydrate offers a difference in elemental composition compared to water-saturated intervals. Thus, in permafrost areas, the carbon/oxygen ratio may vary between gas hydrate and permafrost, due to the increase of carbon in gas hydrate accumulations. At the Mallik site, we observe a hydrate-bearing sand (1085-1107 m) above a water-bearing sand (1107-1140 m), which was confirmed through core samples and mud gas analysis. We observe a decrease in the photoelectric absorption of ~0.5 barnes/e-, as well as an increase in the formation sigma readings of ~5 capture units in the water-bearing sand as compared to the hydrate sand interval. This is further correlated with the carbon/oxygen ratio showing a decrease of 20% in the water sand compared to the hydrate sand above. In future research, we will quantify the effect of gas hydrate on the nuclear logs at the Mallik well and compare it to wells in the Gulf of Mexico.

The influence of diets containing either conventional corn, conventional corn with choice white grease, high oil corn, or high oil high oleic corn on belly/bacon quality.

PubMed

Rentfrow, G; Sauber, T E; Allee, G L; Berg, E P

2003-08-01

The objectives of this study were to evaluate diets possessing different fatty acid profiles (as influenced by corn type) with regard to fatty acid profile and firmness of pork bellies. Crossbred barrows (n=196) were fed one of four corn-based diets consisting of conventional corn (CONV), CONV with choice white grease (CWG), high oil corn (HOC), or high oleic, high oil corn (HOHOC). Following 98 days on test, two animals representing the average pen weight (118 kg) were selected for harvest (n=56). A 50-g fat sample was removed from each belly for fatty acid profile analysis. Lateral and vertical flex tests were performed to determine belly firmness. Bellies were pumped and cooked according to a commercial protocol. Total saturated fatty acids increased (P<0.001) and total unsaturated fatty acids decreased (P<0.05) when CWG was added to the CONV diet or when HOC or HOHOC were substituted for CONV corn. Pigs fed CONV corn had firmer bellies, while those fed HOC were softer. No differences were observed across treatment for percentage pump retention, smokehouse yield, or slicing yield (P>0.05). Based on the results of this study, corn type influences fatty acid profile, and belly firmness, but does not affect pump retention, or slicing yields.

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2001-01-01

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Microstructural characteristics of natural gas hydrates hosted in various sand sediments.

PubMed

Zhao, Jiafei; Yang, Lei; Liu, Yu; Song, Yongchen

2015-09-21

Natural gas hydrates have aroused worldwide interest due to their energy potential and possible impact on climate. The occurrence of natural gas hydrates hosted in the pores of sediments governs the seismic exploration, resource assessment, stability of deposits, and gas production from natural gas hydrate reserves. In order to investigate the microstructure of natural gas hydrates occurring in pores, natural gas hydrate-bearing sediments were visualized using microfocus X-ray computed tomography (CT). Various types of sands with different grain sizes and wettability were used to study the effect of porous materials on the occurrence of natural gas hydrates. Spatial distributions of methane gas, natural gas hydrates, water, and sands were directly identified. This work indicates that natural gas hydrates tend to reside mainly within pore spaces and do not come in contact with adjacent sands. Such an occurring model of natural gas hydrates is termed the floating model. Furthermore, natural gas hydrates were observed to nucleate at gas-water interfaces as lens-shaped clusters. Smaller sand grain sizes contribute to higher hydrate saturation. The wetting behavior of various sands had little effect on the occurrence of natural gas hydrates within pores. Additionally, geometric properties of the sediments were collected through CT image reconstructions. These findings will be instructive for understanding the microstructure of natural gas hydrates within major global reserves and for future resource utilization of natural gas hydrates.

Magnetic Diagenesis in the Gas Hydrate System

NASA Astrophysics Data System (ADS)

Enkin, R. J.; Hamilton, T. S.; Esteban, L.

2009-05-01

Natural gas hydrate is a methane-bearing form of ice which occurs in permafrost and continental slope settings. Geochemical processes associated with gas hydrate formation lead to the growth of iron sulphides which have a geophysically measurable magnetic signature. Detailed magnetic investigation and complementary petrological observations were undertaken on unconsolidated sediments from three gas hydrate (GH) settings: permafrost in fluvial-deltaic silts and sands in the Western Canadian Arctic (Japex et al. Mallik 5L-38 in 2002); diamictons and hemipelagics in the Cascadia accretionary wedge west of Vancouver Island (IODP Exp.311 in 2006); and marine sands and hemipelagics from the Bay of Bengal (NGHP Exp.01 in 2007). These magnetic measurements provide stratigraphic profiles which reveal fine scale variations in lithology, magnetic grain size, and paleo-pore fluid geochemistry. The highest magnetic susceptibility values are observed in strata which preserve high initial concentrations of detrital magnetite, such as glacial deposits. The lowest values of magnetic susceptibility are observed where iron has been reduced to paramagnetic pyrite, formed in settings with high methane and sulphate flux such as at methane vents. Enhanced values of magnetic susceptibility characterize the introduction of the ferrimagnetic iron sulphide minerals greigite and smythite. These magnetic minerals are mostly found immediately adjacent to the sedimentary horizons which host the gas hydrate and their textures and compositions indicate rapid disequilibrium crystallization. The observed diagenesis result from the unique physical and geochemical properties of the environment where gas hydrates form: methane is available to fuel microbiological activity and the freezing which accompanied GH crystallization quickly removed pure water, froze the sediments into an impermeable solid and expelled more concentrated brines into the adjacent less permeable strata to the point of inducing fracture formation. Magnetic surveying techniques can help delineate anomalies related to gas hydrate deposits, and magnetic logging of wells and core samples provide information on the original lithology and diagenesis caused by gas hydrate formation.

Strengthening mechanism of cemented hydrate-bearing sand at microscales

NASA Astrophysics Data System (ADS)

Yoneda, Jun; Jin, Yusuke; Katagiri, Jun; Tenma, Norio

2016-07-01

On the basis of hypothetical particle-level mechanisms, several constitutive models of hydrate-bearing sediments have been proposed previously for gas production. However, to the best of our knowledge, the microstructural large-strain behaviors of hydrate-bearing sediments have not been reported to date because of the experimental challenges posed by the high-pressure and low-temperature testing conditions. Herein, a novel microtriaxial testing apparatus was developed, and the mechanical large-strain behavior of hydrate-bearing sediments with various hydrate saturation values (Sh = 0%, 39%, and 62%) was analyzed using microfocus X-ray computed tomography. Patchy hydrates were observed in the sediments at Sh = 39%. The obtained stress-strain relationships indicated strengthening with increasing hydrate saturation and a brittle failure mode of the hydrate-bearing sand. Localized deformations were quantified via image processing at the submillimeter and micrometer scale. Shear planes and particle deformation and/or rotation were detected, and the shear band thickness decreased with increasing hydrate saturation.

Development and characterization of morin hydrate loaded microemulsion for the management of Alzheimer's disease.

PubMed

Sharma, Dheeraj; Singh, Manpreet; Kumar, Punnet; Vikram, Vir; Mishra, Neeraj

2017-12-01

The aim of this study is to prepare and characterize intranasal delivery of morin hydrate loaded microemulsion for the management of Alzheimer's diseases. After intranasal delivery, brain and blood drug concentrations were found to be higher for optimized morin hydrate loaded microemulsion as compared to plain morin hydrate. Significant (P < 0.05) reduction in assessed pharmacodynamic parameters was observed after intranasal administration of morin hydrate loaded microemulsion as compared to sham control group. Daily chronic treatment with morin loaded microemulsion till the 21st day significantly increased the memory in wistar rats with STZ-induced dementia.

Direct three-dimensional observation of the microstructure and chemistry of C{sub 3}S hydration

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

Hu, Qinang; Aboustait, Mohammed; Kim, Taehwan

Disagreements about the mechanisms of cement hydration remain despite the fact that portland cement has been studied extensively for over 100 years. One reason for this is that direct observation of the change in microstructure and chemistry are challenging for many experimental techniques. This paper presents results from synchrotron nano X-ray tomography and fluorescence imaging. The data show unprecedented direct observations of small collections of C{sub 3}S particles before and after different periods of hydration in 15 mmol/L lime solution. X-ray absorption contrast is used to make three dimensional maps of the changes of these materials with time. The chemicalmore » compositions of hydration products are then identified with X-ray fluorescence mapping and scanning electron microscopy. These experiments are used to provide insight into the rate and morphology of the microstructure formation.« less

Shallow methane hydrate system controls ongoing, downslope sediment transport in a low-velocity active submarine landslide complex, Hikurangi Margin, New Zealand

NASA Astrophysics Data System (ADS)

Mountjoy, Joshu J.; Pecher, Ingo; Henrys, Stuart; Crutchley, Gareth; Barnes, Philip M.; Plaza-Faverola, Andreia

2014-11-01

Morphological and seismic data from a submarine landslide complex east of New Zealand indicate flow-like deformation within gas hydrate-bearing sediment. This "creeping" deformation occurs immediately downslope of where the base of gas hydrate stability reaches the seafloor, suggesting involvement of gas hydrates. We present evidence that, contrary to conventional views, gas hydrates can directly destabilize the seafloor. Three mechanisms could explain how the shallow gas hydrate system could control these landslides. (1) Gas hydrate dissociation could result in excess pore pressure within the upper reaches of the landslide. (2) Overpressure below low-permeability gas hydrate-bearing sediments could cause hydrofracturing in the gas hydrate zone valving excess pore pressure into the landslide body. (3) Gas hydrate-bearing sediment could exhibit time-dependent plastic deformation enabling glacial-style deformation. We favor the final hypothesis that the landslides are actually creeping seafloor glaciers. The viability of rheologically controlled deformation of a hydrate sediment mix is supported by recent laboratory observations of time-dependent deformation behavior of gas hydrate-bearing sands. The controlling hydrate is likely to be strongly dependent on formation controls and intersediment hydrate morphology. Our results constitute a paradigm shift for evaluating the effect of gas hydrates on seafloor strength which, given the widespread occurrence of gas hydrates in the submarine environment, may require a reevaluation of slope stability following future climate-forced variation in bottom-water temperature.

[Progress in Raman spectroscopic measurement of methane hydrate].

PubMed

Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun

2009-09-01

Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

Molecular dynamics study of methane hydrate formation at a water/methane interface.

PubMed

Zhang, Junfang; Hawtin, R W; Yang, Ye; Nakagava, Edson; Rivero, M; Choi, S K; Rodger, P M

2008-08-28

We present molecular dynamics simulation results of a liquid water/methane interface, with and without an oligomer of poly(methylaminoethylmethacrylate), PMAEMA. PMAEMA is an active component of a commercial low dosage hydrate inhibitor (LDHI). Simulations were performed in the constant NPT ensemble at temperatures of 220, 235, 240, 245, and 250 K and a pressure of 300 bar. The simulations show the onset of methane hydrate growth within 30 ns for temperatures below 245 K in the methane/water systems; at 240 K there is an induction period of ca. 20 ns, but at lower temperatures growth commences immediately. The simulations were analyzed to calculate hydrate content, the propensity for hydrogen bond formation, and how these were affected by both temperature and the presence of the LDHI. As expected, both the hydrogen bond number and hydrate content decreased with increasing temperature, though little difference was observed between the lowest two temperatures considered. In the presence of PMAEMA, the temperature below which sustained hydrate growth occurred was observed to decrease. Some of the implications for the role of PMAEMA in LDHIs are discussed.

Ammonium, Nitrate, and Phosphate Sorption to and Solute Leaching from Biochars Prepared from Corn Stover ( L.) and Oak Wood ( spp.).

PubMed

Hollister, C Colin; Bisogni, James J; Lehmann, Johannes

2013-01-01

Biochar (BC) was evaluated for nitrogen (N) and phosphorus (P) removal from aqueous solution to quantify its nutrient pollution mitigation potential in agroecosystems. Sorption isotherms were prepared for solutions of ammonium (NH), nitrate (NO), and phosphate (PO-P) using BC of corn ( L.) and oak ( spp.) feedstock, each pyrolyzed at 350 and 550°C highest treatment temperature (HTT). Sorption experiments were performed on original BC as well as on BC that went through a water extraction pretreatment (denoted WX-BC). Ammonium sorption was observed for WX-Oak-BC and WX-Corn-BC, and Freundlich model linearization showed that a 200°C increase in HTT resulted in a 55% decrease in * values for WX-Oak-BC and a 69% decrease in * for WX-Corn-BC. Nitrate sorption was not observed for any BC. Removing metals by water extraction from WX-Oak-350 and WX-Oak-550 resulted in a 25 to 100% decrease in phosphate removal efficiency relative to original Oak-350 and Oak-550, respectively. No PO-P sorption was observed using any Corn-BC. Calcium (Ca) leached from BC produced at 550°C was 63 and 104% higher than from BC produced at 350°C for corn and oak, respectively. Leaching of P was two orders of magnitude lower in WX-Oak-BC than in WX-Corn-BC, concurrent with similar difference in magnesium (Mg). Nitrate and NH leaching from consecutive water extractions of all tested BCs was mostly below detection limits. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations.

PubMed

Schicks, J M; Luzi, M; Beeskow-Strauch, B

2011-11-24

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Does the "sleeping Dragon" Really Sleep?: the Case for Continuous Long-Term Monitoring at a Gulf of Mexico Cold Seep Site

NASA Astrophysics Data System (ADS)

Wilson, R. M.; Lapham, L.; Farr, N.; Lutken, C.; MacDonald, I. R.; Macelloni, L.; Riedel, M.; Sleeper, K.; Chanton, J.

2011-12-01

Continuous porewater monitoring indicates that the methane flux away from exposed hydrate mounds can vary considerably over time. Recently, we retrieved a Pore Fluid Array instrument pack from a hydrate outcrop adjacent to a NEPTUNE Canada observatory node. The sampler was designed to continuously collect and store sediment pore fluids over the course of 9 months. On analysis, we observed a 35mM variation in methane concentrations corresponding with an abrupt shift in current direction at the site. Video and resistivity data have led to previous speculation that hydrate growth and dissolution/dissociation may be seasonally variable. Cumulatively, these findings suggest that the persistence of hydrate outcrops may be extremely dynamic, driven by fluctuations in physical conditions on short time scales. Short-term monitoring in the Gulf of Mexico within Mississippi Canyon lease block 118 (MC118), a known hydrate-bearing site, indicates that physical conditions even at these depths (~540-890m) may be highly variable. Pressure can vary within hours, and recorded temperature changes of ~1.5°C have been associated with passing storms. Moreover, increased particle abundance was observed at the site in 2007 suggesting that organic matter flux to the sediments may vary on the scale of months to years. These inputs have the potential to alter the chemical environment surrounding the hydrate, thereby affecting dissolution rates. Continuous, long-term observations of physical conditions at MC118 could provide information about the potential for natural perturbations to impact hydrate dynamics on the scale of weeks or even days necessary for assessing the long-term persistence of hydrate outcrops. Sleeping Dragon is a massive hydrate outcrop at MC118 that has been monitored since 2006. Three years ago, researchers returning to the site found it visibly diminished relative to previous observations. This apparent shift toward net dissolution of the mound may have been precipitated by changes in physical and chemical conditions at the site. We propose that the dynamics of hydrate stability may be compared to an oscillating "see-saw" where fluctuations in physical conditions tip the balance alternately in favor of dissociation/dissolution or hydrate growth. The chemical environment at MC118 results from the interaction among physical parameters, fluid/particle flux, and biological processes occurring near the hydrate surface. Given that these parameters may be varying on the scale of days, weeks, months, and possibly even years, long-term continuous monitoring will play a key role in understanding the stability conditions at MC118 and the potential for gas release from this methane reservoir should the dragon be awakened.

Raman studies of methane-ethane hydrate metastability.

PubMed

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Pro-apoptotic and anti-proliferative effects of corn silk extract on human colon cancer cell lines.

PubMed

Guo, Hao; Guan, Hong; Yang, Wenqin; Liu, Han; Hou, Huiling; Chen, Xue; Liu, Zhenyan; Zang, Chuangang; Liu, Yuchao; Liu, Jicheng

2017-02-01

Corn silk is an economically and nutritionally significant natural product as it represents a staple food for a large proportion of the world population. This study investigated the anticancer activity of corn silk extract in human colon cancer cells and human gastric cancer cells. Following treatment with corn silk extract, certain apoptosis-related events were observed, including inhibition of cell proliferation, loss of mitochondrial membrane potential (ΔΨm), release of Ca2+ and release of cytochrome c from the mitochondria into the cytosol. Our results revealed that corn silk extract inhibited the proliferation of cancer cells and increased the level of apoptosis in a concentration-dependent manner. Western blot analysis revealed that corn silk extract upregulated the levels of Bax, cytochrome c , caspase-3 and caspase-9, but downregulated the levels of B-cell lymphoma 2. These results suggest that corn silk extract may induce apoptosis through the mitochondria-mediated pathway.

Aspergillus flavus Infection and Aflatoxin Production in Corn: Influence of Trace Elements

PubMed Central

Lillehoj, E. B.; Garcia, W. J.; Lambrow, M.

1974-01-01

Distribution of trace element levels in corn germ fractions from kernels naturally infected with Aspergillus flavus and from kernels free of the fungus demonstrated an association between the presence of A. flavus and higher levels of metals. A. flavus production of aflatoxin on various autoclaved corn media showed that ground, whole corn was an excellent substrate; similar high levels of toxin were observed on full-fat corn germ but endosperm and defatted corn germ supported reduced yields. The influence of trace elements and their availability in defatted corn germ to A. flavus-mediated aflatoxin biosynthesis were measured. Enrichment of the substrate with 5 to 10 μg of manganese, copper, cadmium, or chromium per g of germ increased toxin yields. Addition of lead or zinc (50 to 250 μg/g) also enhanced toxin accumulation. Aflatoxin elaboration was reduced by the addition of 25 μg of cadmium per g or 500 μg of copper per g of germ. PMID:4216287

Surfactant Effect on Hydrate Crystallization at the Oil-Water Interface.

PubMed

Dann, Kevin; Rosenfeld, Liat

2018-05-29

Gas hydrates pose economic and environmental risks to the oil and gas industry when plug formation occurs in pipelines. A novel approach was applied to understand cyclopentane clathrate hydrate formation in the presence of nonionic surfactant to achieve hydrate inhibition at low percent weight compared to thermodynamic inhibitors. The hydrate-inhibiting performance of low (CMC) concentrations of Span 20, Span 80, Pluronic L31, and Tween 65 at 2 °C on a manually nucleated 2 μL droplet showed a morphological shift in crystallization from planar shell growth to conical growth. Monitoring the internal pressure of the water droplet undergoing hydrate crystallization provides information on the change in interfacial tension during the crystallization process. The results of this study will provide information on the surfactant effect on hydrate crystallization and inhibition. At low surfactant concentrations (below CMC), a planar hydrate crystal was formed. Decreasing interfacial tension was observed, which can be related to the shrinking area of the water-cyclopentane interface. At high surfactant concentration, the crystal morphology was shifted to conical. Interfacial tension measurements reveal oscillations of the interfacial tension during the crystallization process. The oscillations of the interfacial tension result from the fact that once the crystal has reached a critical size a portion of the cone breaks free from the droplet surface, which results in a sudden increase in the available surface for the surfactant molecules. Hence, a temporary increase in the interfacial tension can be observed. The oscillatory behavior of the interfacial tension is a result of the growth and release of the hydrate cones from the surface of the droplet. We have found that the most efficient surfactant in hydrate inhibition would be the one with HLB closest to 10 (equal hydrophilic-hydrophobic parts). In this way, the surfactant molecules will stay at the interface as they observe equal affinities for both the oil and water phases. Surfactant molecules that have the strongest affinity to the interface will be able to inhibit the growth of the crystal as they will force the cones to break and will not allow them to grow.

Crystal structure, stability and spectroscopic properties of methane and CO2 hydrates.

PubMed

Martos-Villa, Ruben; Francisco-Márquez, Misaela; Mata, M Pilar; Sainz-Díaz, C Ignacio

2013-07-01

Methane hydrates are highly present in sea-floors and in other planets and their moons. Hence, these compounds are of great interest for environment, global climate change, energy resources, and Cosmochemistry. The knowledge of stability and physical-chemical properties of methane hydrate crystal structure is important for evaluating some new green becoming technologies such as, strategies to produce natural gas from marine methane hydrates and simultaneously store CO2 as hydrates. However, some aspects related with their stability, spectroscopic and other chemical-physical properties of both hydrates are not well understood yet. The structure and stability of crystal structure of methane and CO2 hydrates have been investigated by means of calculations with empirical interatomic potentials and quantum-mechanical methods based on Hartree-Fock and Density Functional Theory (DFT) approximations. Molecular Dynamic simulations have been also performed exploring different configurations reproducing the experimental crystallographic properties. Spectroscopic properties have also been studied. Frequency shifts of the main vibration modes were observed upon the formation of these hydrates, confirming that vibration stretching peaks of C-H at 2915cm(-1) and 2905cm(-1) are due to methane in small and large cages, respectively. Similar effect is observed in the CO2 clathrates. The guest-host binding energy in these clathrates calculated with different methods are compared and discussed in terms of adequacy of empirical potentials and DFT methods for describing the interactions between gas guest and the host water cage, proving an exothermic nature of methane and CO2 hydrates formation process. Copyright © 2013 Elsevier Inc. All rights reserved.

Pore fluid geochemistry from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Torres, M.E.; Collett, T.S.; Rose, K.K.; Sample, J.C.; Agena, W.F.; Rosenbaum, E.J.

2011-01-01

The BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well was drilled and cored from 606.5 to 760.1. m on the North Slope of Alaska, to evaluate the occurrence, distribution and formation of gas hydrate in sediments below the base of the ice-bearing permafrost. Both the dissolved chloride and the isotopic composition of the water co-vary in the gas hydrate-bearing zones, consistent with gas hydrate dissociation during core recovery, and they provide independent indicators to constrain the zone of gas hydrate occurrence. Analyses of chloride and water isotope data indicate that an observed increase in salinity towards the top of the cored section reflects the presence of residual fluids from ion exclusion during ice formation at the base of the permafrost layer. These salinity changes are the main factor controlling major and minor ion distributions in the Mount Elbert Well. The resulting background chloride can be simulated with a one-dimensional diffusion model, and the results suggest that the ion exclusion at the top of the cored section reflects deepening of the permafrost layer following the last glaciation (???100 kyr), consistent with published thermal models. Gas hydrate saturation values estimated from dissolved chloride agree with estimates based on logging data when the gas hydrate occupies more than 20% of the pore space; the correlation is less robust at lower saturation values. The highest gas hydrate concentrations at the Mount Elbert Well are clearly associated with coarse-grained sedimentary sections, as expected from theoretical calculations and field observations in marine and other arctic sediment cores. ?? 2009 Elsevier Ltd.

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

USGS Publications Warehouse

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-01-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°–225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests ~2 orders of magnitude higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60–150 °C, suggest that if sufficient hot water or steam is available, any rhyolite flow greater than ~5 m thick can develop the observed ~250-µm hydration rinds within the expected timescale of cooling (weeks–years). As the process of hydration involves shattering of 30- to 100-µm-thick slivers to expose unhydrated rhyolite glass, the time required for hydration may be even shorter. Rapid hydration and formation of relatively thick-walled glass shards allow perlites to provide a snapshot view of the meteoric water (and thus climate) at the time of initial alteration. Perlites retain their initial hydration D/H signal better than thin-walled ash, which in contrast hydrates over many thousands of years with time-averaged precipitation.

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

NASA Astrophysics Data System (ADS)

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-11-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant "onion-skin" fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2-3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched "hydration fronts" where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between 110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°-225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests 2 orders of magnitude higher rates of diffusion at 60-110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are -150 to -191 or 20-40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60-150 °C, suggest that if sufficient hot water or steam is available, any rhyolite flow greater than 5 m thick can develop the observed 250-µm hydration rinds within the expected timescale of cooling (weeks-years). As the process of hydration involves shattering of 30- to 100-µm-thick slivers to expose unhydrated rhyolite glass, the time required for hydration may be even shorter. Rapid hydration and formation of relatively thick-walled glass shards allow perlites to provide a snapshot view of the meteoric water (and thus climate) at the time of initial alteration. Perlites retain their initial hydration D/H signal better than thin-walled ash, which in contrast hydrates over many thousands of years with time-averaged precipitation.

Effects of various vehicles on skin hydration in vivo.

PubMed

Wiedersberg, S; Leopold, C S; Guy, R H

2009-01-01

The stratum corneum, the outermost layer of the skin, regulates the passive loss of water to the environment. Furthermore, it is well accepted that drug penetration is influenced by skin hydration, which may be manipulated by the application of moisturizing or oleaginous vehicles. Measurements of transepidermal water loss (TEWL), and of skin hydration using a corneometer, were used to assess the effect of different vehicles on stratum corneum barrier function in vivo in human volunteers. A microemulsion significantly increased skin hydration relative to a reference vehicle based on medium chain triglycerides; in contrast, Transcutol(R) lowered skin hydration. TEWL measurements confirmed these observations. Copyright 2009 S. Karger AG, Basel.

Production of ethanol and xylitol from corn cobs by yeasts.

PubMed

Latif, F; Rajoka, M I

2001-03-01

Saccharomyces cerevisiae and Candida tropicalis were used separately and as co-culture for simultaneous saccharification and fermentation (SSF) of 5-20% (w/v) dry corn cobs. A maximal ethanol concentration of 27, 23, 21 g/l (w/v) from 200 g/l (w/v) dry corn cobs was obtained by S. cerevisiae, C. tropicalis and the co-culture, respectively, after 96 h of fermentation. However, theoretical yields of 82%, 71% and 63% were observed from 50 g/l dry corn cobs for the above cultures, respectively. Maximal xylitol concentration of 21, 20 and 15 g/l from 200 g/l (w/v) dry corn cobs was obtained by C. tropicalis, co-culture, and S. cerevisiae, respectively. Maximum theoretical yields of 79.0%, 77.0% and 58% were observed from 50 g/l of corn cobs, respectively. The volumetric productivities for ethanol and xylitol increased with the increase in substrate concentration, whereas, yield decreased. Glycerol and acetic acid were formed as minor by-products. S. cerevisiae and C. tropicalis resulted in better product yields (0.42 and 0.36 g/g) for ethanol and (0.52 and 0.71 g/g) for xylitol, respectively, whereas, the co-culture showed moderate level of ethanol (0.32 g/g) and almost maximal levels of xylitol (0.69 g/g).

Contribution of Methane Accumulation and Pore Water Flow to Forming High Concentration of Gas Hydrate in Sandy Sediments

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Fujii, T.

2006-12-01

The geological and geophysical evaluations have suggested worldwide methane contents in gas hydrate beneath deep sea floors as well as permafrost-related zones to about twice the total reserves of conventional and unconventional hydrocarbon. In 1998 and 2002 Mallik wells were drilled in the Canadian Arctic that clarified the characteristics of gas hydrate-concentrated sandy layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data, anomalies of chloride contents in pore waters, core temperature depression as well as visible gas hydrates have confirmed the highly saturated pore-space hydrate as intergranular pore filling, whose saturations are evaluated higher than 80 percent in pore volume. In the Nankai Trough forearc basins and accretionary prisms developed and BSRs (bottom simulating reflectors) have been recognized widely, where the multiple wells were drilled in 2000 and 2004, and revealed the presence of pore-space hydrate in sandy layers. It is remarked that there are many similar features in appearance and characteristics between the Mallik and Nankai Trough areas with observations of well- interconnected and highly saturated pore-space hydrate. High concentration of gas hydrate may need original pore space large enough to occur within a host sandy sediment, and this appears to be a similar mode for conventional petroleum accumulations. The distribution of a porous and coarser-grained sandy sediments should be one of the most important factors controlling occurrences and distributions of gas hydrate, as well as physicochemical conditions. Supplying methane for forming deep marine gas hydrate is commonly attributed to microbial conversion of organic material within the zone of stability or to migration of methane-containing fluids from a deeper source area. Pore water flows are considered to a macroscopic migration through faults/fractures and a microscopic flow in intergranular pore systems of sediment. We should assess the influence of methane supply on observable features of hydrate occurrences.

In-situ Micro-structural Studies of Gas Hydrate Formation in Sedimentary Matrices

NASA Astrophysics Data System (ADS)

Kuhs, Werner F.; Chaouachi, Marwen; Falenty, Andrzej; Sell, Kathleen; Schwarz, Jens-Oliver; Wolf, Martin; Enzmann, Frieder; Kersten, Michael; Haberthür, David

2015-04-01

The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in-situ with sub-micron resolution. Here, we report on synchrotron-based micro-tomographic studies by which the nucleation and growth processes of gas hydrate were observed in different sedimentary matrices (natural quartz, glass beds with different surface properties, with and without admixtures of kaolinite and montmorillonite) at varying water saturation. The nucleation sites can be easily identified and the growth pattern is clearly established. In under-saturated sediments the nucleation starts at the water-gas interface and proceeds from there to form predominantly isometric single crystals of 10-20μm size. Using a newly developed synchrotron-based method we have determined the crystallite size distributions (CSD) of the gas hydrate in the sedimentary matrix confirming in a quantitative and statistically relevant manner the impressions from the tomographic reconstructions. It is noteworthy that the CSDs from synthetic hydrates are distinctly smaller than those of natural gas hydrates [1], which suggest that coarsening processes take place in the sedimentary matrix after the initial hydrate formation. Understanding the processes of formation and coarsening may eventually permit the determination of the age of gas hydrates in sedimentary matrices [2], which are largely unknown at present. Furthermore, the full micro-structural picture and its evolution will enable quantitative digital rock physics modeling to reveal poroelastic properties and in this way to support the exploration and exploitation of gas hydrate resources in the future. [1] Klapp S.A., Hemes S., Klein H., Bohrmann G., McDonald I., Kuhs W.F. Grain size measurements of natural gas hydrates. Marine Geology 2010; 274(1-4):85-94. [2] Klapp S.A., Klein H, Kuhs W.F. First determination of gas hydrate crystallite size distribution using high-energy synchrotron radiation. Geophys.Res.Letters, 2007 ; 34 : L13608, DOI:10.1029/2006GL029134

Methane hydrate induced permeability modification for multiphase flow in unsaturated porous media

NASA Astrophysics Data System (ADS)

Seol, Yongkoo; Kneafsey, Timothy J.

2011-08-01

An experimental study was performed using X-ray computed tomography (CT) scanning to capture three-dimensional (3-D) methane hydrate distributions and potential discrete flow pathways in a sand pack sample. A numerical study was also performed to develop and analyze empirical relations that describe the impacts of hydrate accumulation habits within pore space (e.g., pore filling or grain cementing) on multiphase fluid migration. In the experimental study, water was injected into a hydrate-bearing sand sample that was monitored using an X-ray CT scanner. The CT images were converted into numerical grid elements, providing intrinsic sample data including porosity and phase saturations. The impacts of hydrate accumulation were examined by adapting empirical relations into the flow simulations as additional relations governing the evolution of absolute permeability of hydrate bearing sediment with hydrate deposition. The impacts of pore space hydrate accumulation habits on fluid migration were examined by comparing numerical predictions with experimentally measured water saturation distributions and breakthrough curves. A model case with 3-D heterogeneous initial conditions (hydrate saturation, porosity, and water saturation) and pore body-preferred hydrate accumulations best captured water migration behavior through the hydrate-bearing sample observed in the experiment. In the best matching model, absolute permeability in the hydrate bearing sample does not decrease significantly with increasing hydrate saturation until hydrate saturation reaches about 40%, after which it drops rapidly, and complete blockage of flow through the sample can occur as hydrate accumulations approach 70%. The result highlights the importance of permeability modification due to hydrate accumulation habits when predicting multiphase flow through high-saturation, reservoir quality hydrate-bearing sediments.

Gas hydrate inhibition by perturbation of liquid water structure

NASA Astrophysics Data System (ADS)

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

2015-06-01

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

Gas hydrate inhibition by perturbation of liquid water structure.

PubMed

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

2015-06-17

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

Gas hydrate dissociation off Svalbard induced by isostatic rebound rather than global warming.

PubMed

Wallmann, Klaus; Riedel, M; Hong, W L; Patton, H; Hubbard, A; Pape, T; Hsu, C W; Schmidt, C; Johnson, J E; Torres, M E; Andreassen, K; Berndt, C; Bohrmann, G

2018-01-08

Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

Hydrated Minerals on Asteroids: The Astronomical Record

NASA Technical Reports Server (NTRS)

Rivkin, A. S.; Howell, E. S.; Vilas, F.; Lebofsky, L. A.

2002-01-01

Knowledge of the hydrated mineral inventory on the asteroids is important for deducing the origin of Earth's water, interpreting the meteorite record, and unraveling the processes occurring during the earliest times in solar system history. Reflectance spectroscopy shows absorption features in both the 0.6-0.8 and 2.5-3.5 micrometers regions, which are diagnostic of or associated with hydrated minerals. Observations in those regions show that hydrated minerals are common in the mid-asteroid belt, and can be found in unexpected spectral groupings, as well. Asteroid groups formerly associated with mineralogies assumed to have high temperature formation, such as M- and E-class asteroids, have been observed to have hydration features in their reflectance spectra. Some asteroids have apparently been heated to several hundred degrees Celsius, enough to destroy some fraction of their phyllosilicates. Others have rotational variation suggesting that heating was uneven. We summarize this work, and present the astronomical evidence for water- and hydroxyl-bearing minerals on asteroids.

Hydrated Minerals on Asteroids: The Astronomical Record

NASA Technical Reports Server (NTRS)

Rivkin, A. S.; Howell, E. S.; Vilas, F.; Lebofsky, L. A.

2003-01-01

Knowledge of the hydrated mineral inventory on the asteroids is important for deducing the origin of Earth's water, interpreting the meteorite record, and unraveling the processes occurring during the earliest times in solar system history. Reflectance spectroscopy shows absorption features in both the 0.6-0.8 and 2.5-3.5-micron regions, which are diagnostic of or associated with hydrated minerals. Observations in those regions show that hydrated minerals are common in the mid-asteroid belt, and can be found in unexpected spectral groupings as well. Asteroid groups formerly associated with mineralogies assumed to have high-temperature formation, such as M- and E-class steroids, have been observed to have hydration features in their reflectance spectra. Some asteroids have apparently been heated to several hundred degrees Celsius, enough to destroy some fraction of their phyllosilicates. Others have rotational variation suggesting that heating was uneven. We summarize this work, and present the astronomical evidence for water- and Hydroxl-bearing minerals on asteroids.

Observations of mass fractionation of noble gases in synthetic methane hydrate

USGS Publications Warehouse

Hunt, Andrew G.; Pohlman, John; Stern, Laura A.; Ruppel, Carolyn D.; Moscati, Richard J.; Landis, Gary P.; Pinkston, John C.

2011-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings are presently dissociating and releasing methane and other gases to the oceanatmosphere system. A key challenge in assessing the susceptibility of gas hydrates to warming climate is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sublake and subseafloor sediments, coalbeds, and other sources. Carbon and deuterium stable isotopic data provide only a first-order characterization of methane sources, while gas hydrate can sequester any type of methane. Here, we investigate the possibility of exploiting the pattern of noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under careful laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates.

PubMed

Holzammer, Christine; Schicks, Judith M; Will, Stefan; Braeuer, Andreas S

2017-09-07

We present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO 2 ) gas hydrates using Raman spectroscopy. The CO 2 hydrates were formed from sodium chloride/water solutions with salinities of 0-10 wt %, which were pressurized with liquid CO 2 in a stirred vessel at 6 MPa and a subcooling of 9.5 K. The formation of the CO 2 hydrate resulted in a hydrate gel where the solid hydrate can be considered as the continuous phase that includes small amounts of a dispersed liquid water-rich phase that has not been converted to hydrate. During the hydrate formation process we quantified the fraction of solid hydrate, x H , and the fraction of the dispersed liquid water-rich phase, x L , from the signature of the hydroxyl (OH)-stretching vibration of the hydrate gel. We found that the fraction of hydrate x H contained in the hydrate gel linearly depends on the salinity of the initial liquid water-rich phase. In addition, the ratio of CO 2 and water was analyzed in the liquid water-rich phase before hydrate formation, in the hydrate gel during growth and dissociation, and after its complete dissociation again in the liquid water-rich phase. We observed a supersaturation of CO 2 in the water-rich phase after complete dissociation of the hydrate gel and were able to show that the excess CO 2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. These residual nano- and microdroplets could be a possible explanation for the so-called memory effect.

Overview: Nucleation of clathrate hydrates

NASA Astrophysics Data System (ADS)

Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

2016-12-01

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Communication: Quantitative Fourier-transform infrared data for competitive loading of small cages during all-vapor instantaneous formation of gas-hydrate aerosols

NASA Astrophysics Data System (ADS)

Uras-Aytemiz, Nevin; Abrrey Monreal, I.; Devlin, J. Paul

2011-10-01

A simple method has been developed for the measurement of high quality FTIR spectra of aerosols of gas-hydrate nanoparticles. The application of this method enables quantitative observation of gas hydrates that form on subsecond timescales using our all-vapor approach that includes an ether catalyst rather than high pressures to promote hydrate formation. The sampling method is versatile allowing routine studies at temperatures ranging from 120 to 210 K of either a single gas or the competitive uptake of different gas molecules in small cages of the hydrates. The present study emphasizes hydrate aerosols formed by pulsing vapor mixtures into a cold chamber held at 160 or 180 K. We emphasize aerosol spectra from 6 scans recorded an average of 8 s after "instantaneous" hydrate formation as well as of the gas hydrates as they evolve with time. Quantitative aerosol data are reported and analyzed for single small-cage guests and for mixed hydrates of CO2, CH4, C2H2, N2O, N2, and air. The approach, combined with the instant formation of gas hydrates from vapors only, offers promise with respect to optimization of methods for the formation and control of gas hydrates.

Overview: Nucleation of clathrate hydrates.

PubMed

Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

2016-12-07

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Geographical and Temporal Dynamics of Chaetocnema Pulicaria and Their Role in Stewart's Disease of Corn in Iowa

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

Esker, Paul David

2001-01-01

This thesis investigated the biology and importance of the corn flea beetle vector and its role in the Stewart's disease of corn pathosystem. This was accomplished by determining the number of corn flea beetle generations that occur in Iowa and by quantifying the proportions of those populations found to be infested with the causal agent of Stewart's disease, pantoea stewartii. In addition, a preliminary study was conducted to determine how soil temperature was influenced by air temperature and how this may be applied to forecasting for Stewart's disease of corn. Research using yellow sticky cards and sweep netting demonstrated thatmore » there are overwintering, first, and second field generations of the corn flea beetle in Iowa. It was also observed that there was a period during June of both 1999 and 2000 when corn flea beetles were not found, which is important new management information. This research has also demonstrated that the incidence of P. stewartii-infested corn flea beetles can be monitored by ELISA testing and that the incidence fluctuates greatly throughout the corn growing season. The initial level of inoculum (P. stewartii-infested corn flea beetles in the adult overwintering generation) does not remain static during the spring as was previously hypothesized. This signals that additional research is needed concerning the mechanisms of fluctuation in the proportion of beetles infested with P. stewartii.« less

Toxicity of methylmercury injected into eggs when dissolved in water versus corn oil

USGS Publications Warehouse

Heinz, G.H.; Hoffman, D.J.; Klimstra, J.D.; Stebbins, K.R.; Kondrad, S.L.

2011-01-01

In a previous study, the embryotoxicity of methylmercury dissolved in corn oil was compared among 26 species of birds. Corn oil is not soluble in the water-based matrix that constitutes the albumen of an egg. To determine whether the use of corn oil limited the usefulness of this earlier study, a comparison was made of the embryotoxicity of methylmercury dissolved in corn oil versus water. Mallard (Anas platyrhynchos) and chicken (Gallus gallus) eggs were injected with methylmercury chloride dissolved in corn oil or water to achieve concentrations of 0, 0.2, 0.4, 0.8, and 1.6??g/g mercury in the egg on a wet weight basis. Hatching success at each dose of mercury was compared between the two solvents. For mallards, 16.4% of the eggs injected with 1.6??g/g mercury dissolved in water hatched, which was statistically lower than the 37.6% hatch rate of eggs injected with 1.6??g/g mercury dissolved in corn oil, but no differences in hatching success were observed between corn oil and water at any of the other doses. With chicken eggs, no significant differences occurred in percentage hatch of eggs between corn oil and water at any of the mercury doses. Methylmercury dissolved in corn oil seems to have a toxicity to avian embryos similar to that of does methylmercury dissolved in water. Consequently, the results from the earlier study that described the toxicity of methylmercury dissolved in corn oil to avian embryos were probably not compromised by the use of corn oil as a solvent. ?? 2011 SETAC.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

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

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298–220 K). We interpret this change in terms of the dynamic transition previously discussed using othermore » probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.« less

Detection of innersphere interactions between magnesium hydrate and the phosphate backbone of the HDV ribozyme using Raman crystallography.

PubMed

Gong, Bo; Chen, Yuanyuan; Christian, Eric L; Chen, Jui-Hui; Chase, Elaine; Chadalavada, Durga M; Yajima, Rieko; Golden, Barbara L; Bevilacqua, Philip C; Carey, Paul R

2008-07-30

A Raman microscope and Raman difference spectroscopy are used to detect the vibrational signature of RNA-bound magnesium hydrate in crystals of hepatitis delta virus (HDV) ribozyme and to follow the effects of magnesium hydrate binding to the nonbridging phosphate oxygens in the phosphodiester backbone. There is a correlation between the Raman intensity of the innersphere magnesium hydrate signature peak, near 322 cm-1, and the intensity of the PO2- symmetric stretch, near 1100 cm-1, perturbed by magnesium binding, demonstrating direct observation of -PO2-...Mg2+(H2O)x innersphere complexes. The complexes may be pentahydrates (x = 5) and tetrahydrates (x = 4). The assignment of the Raman feature near 322 cm-1 to a magnesium hydrate species is confirmed by isotope shifts observed in D2O and H218O that are semiquantitatively reproduced by calculations. The standardized intensity changes in the 1100 cm-1 PO2- feature seen upon magnesium hydrate binding indicates that there are approximately 5 innersphere Mg2+...-O2P contacts per HDV molecule when the crystal is exposed to a solution containing 20 mM magnesium.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

NASA Astrophysics Data System (ADS)

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-01

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering.

PubMed

Yoshida, Koji; Baron, Alfred Q R; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-07

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Daley, Kim; Kubarych, Kevin J.

2014-06-01

The technique of two-dimensional infrared (2DIR) spectroscopy is used to expose the chemical dynamics of various concentrations of polymers and their monomers in heterogeneous mixtures. An environmentally relevant heterogeneous mixture, which inspires this study, is hydraulic fracturing liquid (HFL). Hydraulic fracking is a technique used to extract natural gas from shale deposits. HFL consists of mostly water, proppant (sand), an emulsifier (guar), and other chemicals specific to the drilling site. Utilizing a metal carbonyl as a probe, we observe the spectral dynamics of the polymer, guar, and its monomer, mannose, and compare the results to see how hydration dynamics change with varying concentration. Another polymer, Ficoll, and its monomer, sucrose, are also compared to see how polymer size affects hydration dynamics. The two results are as follows: (1) Guar experiences collective hydration at high concentrations, where as mannose experiences independent hydration; (2) no collective hydration is observed for Ficoll in the same concentration range as guar, possibly due to polymer shape and size. HFL experiences extremely high pressure during natural gas removal, so future studies will focus on how increased pressure affects the hydration dynamics of polymers and monomers.

Midwest agriculture and ENSO: A comparison of AVHRR NDVI3g data and crop yields in the United States Corn Belt from 1982 to 2014

NASA Astrophysics Data System (ADS)

Glennie, Erin; Anyamba, Assaf

2018-06-01

A time series of Advanced Very High Resolution Radiometer (AVHRR) derived normalized difference vegetation index (NDVI) data were compared to National Agricultural Statistics Service (NASS) corn yield data in the United States Corn Belt from 1982 to 2014. The main objectives of the comparison were to assess 1) the consistency of regional Corn Belt responses to El Niño/Southern Oscillation (ENSO) teleconnection signals, and 2) the reliability of using NDVI as an indicator of crop yield. Regional NDVI values were used to model a seasonal curve and to define the growing season - May to October. Seasonal conditions in each county were represented by NDVI and land surface temperature (LST) composites, and corn yield was represented by average annual bushels produced per acre. Correlation analysis between the NDVI, LST, corn yield, and equatorial Pacific sea surface temperature anomalies revealed patterns in land surface dynamics and corn yield, as well as typical impacts of ENSO episodes. It was observed from the study that growing seasons coincident with La Niña events were consistently warmer, but El Niño events did not consistently impact NDVI, temperature, or corn yield data. Moreover, the El Niño and La Niña composite images suggest that impacts vary spatially across the Corn Belt. While corn is the dominant crop in the region, some inconsistencies between corn yield and NDVI may be attributed to soy crops and other background interference. The overall correlation between the total growing season NDVI anomaly and detrended corn yield was 0.61(p = 0.00013), though the strength of the relationship varies across the Corn Belt.

Formation of a Structure II Hydrate by 1,4-Thioxane in Sea Water

NASA Astrophysics Data System (ADS)

Hester, K. C.; Mancillas, O.; Walz, P. M.; Peltzer, E. T.; Brewer, P. G.

2007-12-01

We have show that a sII clathrate hydrate containing 1,4-thioxane (TO) will form under the appropriate pressure and temperature conditions. The molecular size of TO poised it at the boundary between sII hydrate formation either as the sole cage occupant, or where a second help gas molecule is required to stabilize the small hydrate cages. In addition to its size, TO is chemical similar to cyclic ethers, such as tetrahydrofuran, which readily form clathrate hydrates. For the experimental temperatures in this study (all above 273.15 K), a pure TO hydrate was not observed to form. However, binary hydrates of TO and either CH4 and N2 were readily formed under moderate pressure conditions (33-158 bar). Both Raman spectroscopy and visual observations were used to verify that a solid hydrate formed and that TO was trapped in the cages. For TO + CH4, a pressure-temperature phase equilibria diagram was created. This showed that the addition of TO increased hydrate stability versus a pure CH4 system by approximately 10 degC, indicating that should CH4 gas be present a TO hydrate would readily form at shallow depths under typical oceanic temperature regimes. TO is of environmental interest as a breakdown product of mustard gas (1,1'-thiobis[2-chloroethane] as a result of hydrolysis in sea water, and has been shown to occur in seafloor chemical weapon disposal sites. In the years after World War II large quantities of chemical weapons were disposed of in the ocean at sites off the US east and west coasts, off Japan, in the Baltic and Adriatic Seas, and in the Russian Arctic, until the signing of the London Convention in 1972. Mustard gas represents the largest tonnage of weapons materiel and while the general scheme of breakdown by hydrolysis is known there is little information on the actual behavior of these breakdown products in marine sediments. This work illuminates such gaps in knowledge, and formation of a hydrate profoundly alters molecular mobility and diffusion away from a site. Simple calculations show that other help gases, such as H2S, should also form a mixed hydrate with TO with remarkable ease; thus, extending the range of possible hydrate formation with TO in anoxic marine sediments to shallow depths, if a second hydrate former is present.

Insights into a hydration regulating system in Cupressus pollen grains

PubMed Central

Danti, R.; Della Rocca, G.; Calamassi, R.; Mori, B.; Mariotti Lippi, M.

2011-01-01

Background and Aims Hydration, rupture and exine opening due to the sudden and large expansion of intine are typical of taxoid-type pollen grains. A hemispheric outgrowth external to the exine was observed on Cupressus and Juniperus pollen grains before the intine swelling and exine release. However, the actual existence of this permanent or temporary structure and its precise role in pollen hydration is still being debated. The aim of this paper is to collect information on the actual presence of this peculiar outgrowth on the surface of the Cupressus pollen grain, its structure, composition and function. Methods Pollen grains of several Cupressus species were observed using various techniques and methodologies, under light and fluorescence microscopy, phase-contrast microscopy, confocal microscopy, scanning electron microscopy, and an environmental scanning electron microscope. Observations were also performed on other species with taxoid-type pollen grains. Key Results A temporary structure located just above the pore was observed on Cupressus pollen grains, as well as on other taxoid-type pollens. It is hemispheric, layered, and consists of polysaccharides and proteins. The latter are confined to its inner part. Its presence seems to regulate the entrance of water into the grains at the beginning of pollen hydration. Conclusions The presence of a temporary structure over the pore of taxoid-type pollen grains was confirmed and its structure was resolved using several stains and observation techniques. This structure plays a role in the first phases of pollen hydration. PMID:21685430

Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.

PubMed

Bagherzadeh, S Alireza; Englezos, Peter; Alavi, Saman; Ripmeester, John A

2012-03-15

We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase. © 2012 American Chemical Society

Three types of gas hydrate reservoirs in the Gulf of Mexico identified in LWD data

USGS Publications Warehouse

Lee, Myung Woong; Collett, Timothy S.

2011-01-01

High quality logging-while-drilling (LWD) well logs were acquired in seven wells drilled during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II in the spring of 2009. These data help to identify three distinct types of gas hydrate reservoirs: isotropic reservoirs in sands, vertical fractured reservoirs in shale, and horizontally layered reservoirs in silty shale. In general, most gas hydratebearing sand reservoirs exhibit isotropic elastic velocities and formation resistivities, and gas hydrate saturations estimated from the P-wave velocity agree well with those from the resistivity. However, in highly gas hydrate-saturated sands, resistivity-derived gas hydrate-saturation estimates appear to be systematically higher by about 5% over those estimated by P-wave velocity, possibly because of the uncertainty associated with the consolidation state of gas hydrate-bearing sands. Small quantities of gas hydrate were observed in vertical fractures in shale. These occurrences are characterized by high formation resistivities with P-wave velocities close to those of water-saturated sediment. Because the formation factor varies significantly with respect to the gas hydrate saturation for vertical fractures at low saturations, an isotropic analysis of formation factor highly overestimates the gas hydrate saturation. Small quantities of gas hydrate in horizontal layers in shale are characterized by moderate increase in P-wave velocities and formation resistivities and either measurement can be used to estimate gas hydrate saturations.

The molecular mechanism of the inhibition effects of PVCaps on the growth of sI hydrate: an unstable adsorption mechanism.

PubMed

Xu, Jiafang; Li, Liwen; Liu, Jinxiang; Wang, Xiaopu; Yan, Youguo; Zhang, Jun

2018-03-28

The inhibition properties of kinetic hydrate inhibitor (KHI) molecules on the dynamic growth of a hydrate/water interface are investigated by using molecular dynamics simulations. The shape of the hydrate interface is transformed from laminar to funnel by PVCaps. Results indicate that the inhibition effects not only depend on the adsorption capacity which was believed to determine inhibition, but also on the fact that PVCaps must have some non-binding-hydrate sites that don't tend to combine with hydrate. By observing the time evolution of the distance between each component of PVCaps and hydrate, the heterocyclic ring of PVCaps mainly contributes to adsorption and can preferentially adjust itself to come into contact with a hydrate semi-large-cage. The distance between the amide of PVCaps and hydrate is about 4 Å and exceeds the range of a general hydrogen bond (3.5 Å), which proves that the non-binding-hydrate sites of PVCaps exist. On the other hand, the amide of PVCaps is at the intersection of the solid-liquid interface but has no adsorption affinity for hydrate, so this adsorption pattern indicates that the PVCaps at the hydrate interface are not stable. Due to this unstable adsorption, a repeated hydrate destruction phenomenon was revealed by the identification algorithm of hydrate and the calculation of the local number density of methane. The statistical evolution of water rings further proved the existence of non-binding-hydrate sites in PVCaps and the inhibition mechanism to destroy the hydrate cages by PVCaps. This unstable adsorption mechanism may shed light on the development of novel efficient KHIs.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Chand, Shyam; Minshull, Tim A.; Priest, Jeff A.; Best, Angus I.; Clayton, Christopher R. I.; Waite, William F.

2006-08-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L-38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

USGS Publications Warehouse

Chand, S.; Minshull, T.A.; Priest, J.A.; Best, A.I.; Clayton, C.R.I.; Waite, W.F.

2006-01-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L–38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

Studying methane migration mechanisms at Walker Ridge, Gulf of Mexico, via 3D methane hydrate reservoir modeling

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

Nole, Michael; Daigle, Hugh; Mohanty, Kishore

We have developed a 3D methane hydrate reservoir simulator to model marine methane hydrate systems. Our simulator couples highly nonlinear heat and mass transport equations and includes heterogeneous sedimentation, in-situ microbial methanogenesis, the influence of pore size contrast on solubility gradients, and the impact of salt exclusion from the hydrate phase on dissolved methane equilibrium in pore water. Using environmental parameters from Walker Ridge in the Gulf of Mexico, we first simulate hydrate formation in and around a thin, dipping, planar sand stratum surrounded by clay lithology as it is buried to 295mbsf. We find that with sufficient methane beingmore » supplied by organic methanogenesis in the clays, a 200x pore size contrast between clays and sands allows for a strong enough concentration gradient to significantly drop the concentration of methane hydrate in clays immediately surrounding a thin sand layer, a phenomenon that is observed in well log data. Building upon previous work, our simulations account for the increase in sand-clay solubility contrast with depth from about 1.6% near the top of the sediment column to 8.6% at depth, which leads to a progressive strengthening of the diffusive flux of methane with time. By including an exponentially decaying organic methanogenesis input to the clay lithology with depth, we see a decrease in the aqueous methane supplied to the clays surrounding the sand layer with time, which works to further enhance the contrast in hydrate saturation between the sand and surrounding clays. Significant diffusive methane transport is observed in a clay interval of about 11m above the sand layer and about 4m below it, which matches well log observations. The clay-sand pore size contrast alone is not enough to completely eliminate hydrate (as observed in logs), because the diffusive flux of aqueous methane due to a contrast in pore size occurs slower than the rate at which methane is supplied via organic methanogenesis. Therefore, it is likely that additional mechanisms are at play, notably bound water activity reduction in clays. Three-dimensionality allows for inclusion of lithologic heterogeneities, which focus fluid flow and subsequently allow for heterogeneity in the methane migration mechanisms that dominate in marine sediments at a local scale. Incorporating recently acquired 3D seismic data from Walker Ridge to inform the lithologic structure of our modeled reservoir, we show that even with deep adjective sourcing of methane along highly permeable pathways, local hydrate accumulations can be sourced either by diffusive or advective methane flux; advectively-sourced hydrates accumulate evenly in highly permeable strata, while diffusively-sourced hydrates are characterized by thin strata-bound intervals with high clay-sand pore size contrasts.« less

Structure-based analysis reveals hydration changes induced by arginine hydrochloride.

PubMed

Nakakido, Makoto; Tanaka, Yoshikazu; Mitsuhori, Mariko; Kudou, Motonori; Ejima, Daisuke; Arakawa, Tsutomu; Tsumoto, Kouhei

2008-10-01

Arginine hydrochloride has been used to suppress protein aggregation during refolding and in various other applications. We investigated the structure of hen egg-white lysozyme (HEL) and solvent molecules in arginine hydrochloride solution by X-ray crystallography. Neither the backbone nor side-chain structure of HEL was altered by the presence of arginine hydrochloride. In addition, no stably bound arginine molecules were observed. The number of hydration water molecules, however, changed with the arginine hydrochloride concentration. We suggest that arginine hydrochloride suppresses protein aggregation by altering the hydration structure and the transient binding of arginine molecules that could not be observed.

Transition mechanism of sH to filled-ice Ih structure of methane hydrate under fixed pressure condition

NASA Astrophysics Data System (ADS)

Kadobayashi, H.; Hirai, H.; Ohfuji, H.; Kojima, Y.; Ohishi, Y.; Hirao, N.; Ohtake, M.; Yamamoto, Y.

2017-10-01

The phase transition mechanism of methane hydrate from sH to filled-ice Ih structure was examined using a combination of time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device (CCD) camera observation under fixed pressure conditions. Prior to time-resolved Raman experiments, the typical C-H vibration modes and their pressure dependence of three methane hydrate structures, fluid methane and solid methane were measured using Raman spectroscopy to distinguish the phase transitions of methane hydrates from decomposition to solid methane and ice VI or VII. Experimental results by XRD, Raman spectroscopy and CCD camera observation revealed that the structural transition of sH to filled-ice Ih occurs through a collapse of the sH framework followed by the release of fluid methane that is then gradually incorporated into the filled-ice Ih to reconstruct its structure. These observations suggest that the phase transition of sH to filled-ice Ih takes place by a typical reconstructive mechanism.

Constraints of gas venting activity for the interstitial water geochemistry at the shallow gas hydrate site, eastern margin of the Japan Sea; results from high resolution time-series fluid sampling by OsmoSampler

NASA Astrophysics Data System (ADS)

Owari, S.; Tomaru, H.; Matsumoto, R.

2016-12-01

We have conducted ROV researches in the eastern margin of the Japan Sea where active gas venting and outcropping of gas hydrates were observed near the seafloor and have found the strength and location of venting had changed within a few days. These observations indicate the seafloor environments with the shallow gas hydrate system could have changed for short period compared to a geological time scale. We have applied a long-term osmotic fluid sampling system "OsmoSampler" on the active gas hydrate system for one year in order to document how the gas venting and gas hydrate activity have changed the geochemical environments near the seafloor. All the major ion concentrations in the interstitial water show synchronous increase and decrease repeatedly in three to five days, reflecting the incorporation and release of fresh water in gas hydrates in response to the gas concentration change near the sampling site. Dissolved methane concentration increases rapidly and excessively (over several mM) in the first 40 days corresponding to the active gas venting. The increases of methane concentration are often associated with high ion concentration during high water pressure period, indicating excess gas release from shallow gas pockets. Contrarily, enhanced gas hydrate growth may plug the fluid-gas paths in shallow sediment, reducing gas hydrate formation due to the decrease of methane flux. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

The effects of salt, particle and pore size on the process of carbon dioxide hydrate formation: A critical review

NASA Astrophysics Data System (ADS)

Ghaedi, Hosein; Ayoub, Muhammad; Bhat, A. H.; Mahmood, Syed Mohammad; Akbari, Saeed; Murshid, Ghulam

2016-11-01

Hydration is an alternative method for CO2 capture. In doing so, some researchers use porous media on an experimental scale. This paper tries to gather the researches on the formation of CO2 hydrate in different types of porous media such as silica sand, quartz sand, Toyoura, pumice, and fire hardened red clay. This review has attempted to examine the effects of salt and particle sizes as two major factors on the induction time, water to hydrate conversion, gas uptake (or gas consumption), and the rate of CO2 hydrate formation. By performing a critical assessment of previous research works, it was observed that the figure for the gas uptake (or gas consumption) and water to hydrate conversion in porous media was decreased by increasing the particle size provided that the pore size was constant. Although, salt can play a role in hydrate formation as the thermodynamic inhibitor, the results show that salt can be regarded as the kinetic growth inhibitor and kinetic promoter. Because of the fact that the gas uptake in seawater is lower than pure water at the end of experiment, the salt can act as a kinetic growth inhibitor. However, since gas uptake (after the nucleation period and for a short period) and the initial rate of hydrate formation in saline water were more than that of pure water, salt can play a promoter role in the kinetic reaction, too. Besides these, in the case of pure water and within a certain particle size, the amount of the hydrate formation rate has been seen to be greater in smaller particles (provided that the pore size is constant), however this has not been observed for seawater.

α-chymotrypsin in water-acetone and water-dimethyl sulfoxide mixtures: Effect of preferential solvation and hydration.

PubMed

Sirotkin, Vladimir A; Kuchierskaya, Alexandra A

2017-10-01

We investigated water/organic solvent sorption and residual enzyme activity to simultaneously monitor preferential solvation/hydration of protein macromolecules in the entire range of water content at 25°C. We applied this approach to estimate protein destabilization/stabilization due to the preferential interactions of bovine pancreatic α-chymotrypsin with water-acetone (moderate-strength H-bond acceptor) and water-DMSO (strong H-bond acceptor) mixtures. There are three concentration regimes for the dried α-chymotrypsin. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity values are close to 100%. At intermediate water content, the dehydrated α-chymotrypsin has a higher affinity for acetone/DMSO than for water. Residual enzyme activity is minimal in this concentration range. The acetone/DMSO molecules are preferentially excluded from the protein surface at the lowest water content, resulting in preferential hydration. The residual catalytic activity in the water-poor acetone is ∼80%, compared with that observed after incubation in pure water. This effect is very small for the water-poor DMSO. Two different schemes are operative for the hydrated enzyme. At high and intermediate water content, α-chymotrypsin exhibits preferential hydration. However, at intermediate water content, in contrast to the dried enzyme, the initially hydrated α-chymotrypsin possesses increased preferential hydration parameters. At low water content, no residual enzyme activity was observed. Preferential binding of DMSO/acetone to α-chymotrypsin was detected. Our data clearly demonstrate that the hydrogen bond accepting ability of organic solvents and the protein hydration level constitute key factors in determining the stability of protein-water-organic solvent systems. © 2017 Wiley Periodicals, Inc.

Gas Hydrate Formation Probability Distributions: The Effect of Shear and Comparisons with Nucleation Theory.

PubMed

May, Eric F; Lim, Vincent W; Metaxas, Peter J; Du, Jianwei; Stanwix, Paul L; Rowland, Darren; Johns, Michael L; Haandrikman, Gert; Crosby, Daniel; Aman, Zachary M

2018-03-13

Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min -1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2.

Development and characterization of morin hydrate-loaded micellar nanocarriers for the effective management of Alzheimer's disease.

PubMed

Singh, Manpreet; Thakur, Vandana; Deshmukh, Rahul; Sharma, Amit; Rathore, M S; Kumar, Ajay; Mishra, Neeraj

2018-03-01

The aim of this study was to prepare and characterise oral delivery of morin hydrate-loaded micellar nanocarriers using Pluronic P127 and Pluronic F123 for the effective management of Alzheimer's disease. After administration of formulation brain and blood drug concentration were found to be highest for optimised morin hydrate-loaded micellar nanocarriers as compared to plain morin hydrate. Significant (p < 0.05) reduction in assessed pharmacodynamic parameters was observed after administration of morin hydrate-loaded micellar nanocarriers as compared to disease control group. Chronic treatment with morin-loaded micelles significantly increased the memory in AlCl 3 induced Alzheimer's disease in Wistar rats.

NMR relaxometry study of cement hydration in the presence of different oxidic fine fraction materials.

PubMed

Nestle, Nikolaus

2004-01-01

NMR relaxometry has been applied to study hydrating cements for about 25 years now. The most important advantage over other experimental approaches is the possibility to conduct non-destructive measurements with a time resolution of minutes. NMR relaxometry data thus can help to identify details in the time course of cement hydration that possibly would be overlooked in other experiments with lower temporal resolution. Time-resolved information on cement hydration kinetics can provide interesting insights into the impact of oxidic additive materials on cement hydration. For PbO, a very strong delay was observed which then was systematically studied. An explanation for this delay is suggested.

Optothermal transient emission radiometry for studying the changes in epidermal hydration induced during ripening of tomato fruit mutants

NASA Astrophysics Data System (ADS)

Guo, X.; Bicanic, D.; Imhof, R.; Xiao, P.; Harbinson, J.

2004-10-01

Optothermal transient emission radiometry (OTTER) was used to determine the mean surface hydration and the hydration profile of three mutants (beefsteak, slicing and salad) of harvested tomatoes (Lycopersicon esculentum) that were kept under ambient conditions for as long as 51 days. Maximal sensitivity of OTTER to water in the samples was achieved by using 2.94 μm and 13.1 μm as excitation and emission wavelengths, respectively. The surface hydration increases rapidly and reaches a constant level during the remaining period. The hydrolysis of pectic substances that occur in tomatoes while ripening might be a possible cause for the observed change in hydration.

Treatment of corns by injectable silicone.

PubMed

Balkin, S W

1975-09-01

Corns and calluses are the most frequently encountered foot complaints. The choices of care range from self trimming and application of over-the-counter remedies to professional treatment, which may include tendon, skin, and bone surgery. A technique using fluid silicone injected subdermally to cushion corns is described. Twenty-nine patients with 71 digital pressure keratoses were injected between 1965 and 1970. Results of treatment of 77% of the corns were rated good to excellent after an average follow-up period of six years, and no serious reactions have been observed. The procedure offers an effective, nondisabling method of treatment, as opposed to lifelong palliation or surgical intervention.

Control of the geomorphology and gas hydrate extent on widespread gas emissions offshore Romania (Black Sea)

NASA Astrophysics Data System (ADS)

Riboulot, V.; Cattaneo, A.; Sultan, N.; Ker, S.; Scalabrin, C.; Gaillot, A.; Jouet, G.; Marsset, B.; Thomas, Y.; Ballas, G.; Marsset, T.; Garziglia, S.; Ruffine, L.; Boulart, C.

2016-12-01

The Romanian sector of the Black Sea deserves attention because the Danube deep-sea fan is one of the largest sediment depositional systems worldwide and is considered the world's most isolated sea, the largest anoxic water body on the planet and a unique energy-rich sea. Due to the high sediment accumulation rate, presence of organic matter and anoxic conditions, the Black sea sediment offshore the Danube delta is rich in gas and thus show BSR. The cartography of the BSR over the last 20 years, exhibits its widespread occurrence, indicative of extensive development of hydrate accumulations and a huge gas hydrate potential. By combining old and new datasets acquired in 2015 during the GHASS expedition, we performed a geomorphological analysis of the continental slope north-east of the Danube canyon that reveals the presence of several landslides inside and outside several canyons incising the seafloor. It is a complex study area presenting sedimentary processes such as seafloor erosion and instability, mass wasting, formation of gas hydrates, fluid migration, gas escape, where the imprint of geomorphology seems to dictate the location where gas seep occurs. . Some 1409 gas seeps within the water column acoustic records are observed between 200 m and 800 m water depth. No gas flares were detected in deeper areas where gas hydrates are stable. Overall, 93% of the all gas seeps observed are above geomorphological structures. 78% are right above escarpment induced by sedimentary destabilizations inside or outside canyons. The results suggest a geomorphological control of degassing at the seafloor and gas seeps are thus constrained by the gas hydrates stability zone. The stability of the gas hydrates is dependent on the salinity gradient through the sedimentary column and thus on the Black Sea recent geological history. The extent and the dynamics of gas hydrates have a probable impact on the sedimentary destabilization observed at the seafloor.

Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate

USGS Publications Warehouse

Winters, W.J.; Pecher, I.A.; Waite, W.F.; Mason, D.H.

2004-01-01

This paper presents results of shear strength and acoustic velocity (p-wave) measurements performed on: (1) samples containing natural gas hydrate from the Mallik 2L-38 well, Mackenzie Delta, Northwest Territories; (2) reconstituted Ottawa sand samples containing methane gas hydrate formed in the laboratory; and (3) ice-bearing sands. These measurements show that hydrate increases shear strength and p-wave velocity in natural and reconstituted samples. The proportion of this increase depends on (1) the amount and distribution of hydrate present, (2) differences, in sediment properties, and (3) differences in test conditions. Stress-strain curves from the Mallik samples suggest that natural gas hydrate does not cement sediment grains. However, stress-strain curves from the Ottawa sand (containing laboratory-formed gas hydrate) do imply cementation is present. Acoustically, rock physics modeling shows that gas hydrate does not cement grains of natural Mackenzie Delta sediment. Natural gas hydrates are best modeled as part of the sediment frame. This finding is in contrast with direct observations and results of Ottawa sand containing laboratory-formed hydrate, which was found to cement grains (Waite et al. 2004). It therefore appears that the microscopic distribution of gas hydrates in sediment, and hence the effect of gas hydrate on sediment physical properties, differs between natural deposits and laboratory-formed samples. This difference may possibly be caused by the location of water molecules that are available to form hydrate. Models that use laboratory-derived properties to predict behavior of natural gas hydrate must account for these differences.

Fumonisins B₁, B₂ and B₃ in corn products, wheat flour and corn oil marketed in Shandong province of China.

PubMed

Li, Fenghua; Jiang, Dafeng; Zheng, Fengjia; Chen, Jindong; Li, Wei

2015-01-01

In this study a total of 522 samples were collected from Shandong province of China in 2014 and analysed for the occurrence of fumonisin B1 (FB1), FB2 and FB3 by isotope dilution ultrahigh performance liquid chromatography-tandem mass spectrometry. Fumonisins were detected in 98.1% of the corn products, with the average total level of 369.2 μg kg(-1). The individual average values of FB1, FB2 and FB3 in corn products were 268.3, 53.7 and 47.2 μg kg(-1), respectively. The simultaneous occurrence of FB1, FB2 and FB3 was observed in 76.7% of the corn products. Especially, the results demonstrated that the difference in the contamination levels for fumonisins in these three types of corn products was apparent. In addition, 6.2% of the wheat flour samples were contaminated with FB1, with concentrations ranging from 0.3 to 34.6 µg kg(-1). No FB2 or FB3 was detected in wheat flour. In corn oil samples no fumonisins were detected.

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. I. Infrared spectra and ultrafast pump-probe observables.

PubMed

Gruenbaum, S M; Skinner, J L

2011-08-21

The vibrational spectroscopy of hydration water in dilauroylphosphatidylcholine lipid multi-bilayers is investigated using molecular dynamics simulations and a mixed quantum/classical model for the OD stretch spectroscopy of dilute HDO in H(2)O. FTIR absorption spectra, and isotropic and anisotropic pump-probe decay curves have been measured experimentally as a function of the hydration level of the lipid multi-bilayer, and our goal is to make connection with these experiments. To this end, we use third-order response functions, which allow us to include non-Gaussian frequency fluctuations, non-Condon effects, molecular rotations, and a fluctuating vibrational lifetime, all of which we believe are important for this system. We calculate the response functions using existing transition frequency and dipole maps. From the experiments it appears that there are two distinct vibrational lifetimes corresponding to HDO molecules in different molecular environments. In order to obtain these lifetimes, we consider a simple two-population model for hydration water hydrogen bonds. Assuming a different lifetime for each population, we then calculate the isotropic pump-probe decay, fitting to experiment to obtain the two lifetimes for each hydration level. With these lifetimes in hand, we then calculate FTIR spectra and pump-probe anisotropy decay as a function of hydration. This approach, therefore, permits a consistent calculation of all observables within a unified computational scheme. Our theoretical results are all in qualitative agreement with experiment. The vibrational lifetime of lipid-associated OD groups is found to be systematically shorter than that of the water-associated population, and the lifetimes of each population increase with decreasing hydration, in agreement with previous analysis. Our theoretical FTIR absorption spectra successfully reproduce the experimentally observed red-shift with decreasing lipid hydration, and we confirm a previous interpretation that this shift results from the hydrogen bonding of water to the lipid phosphate group. From the pump-probe anisotropy decay, we confirm that the reorientational motions of water molecules slow significantly as hydration decreases, with water bound in the lipid carbonyl region undergoing the slowest rotations. © 2011 American Institute of Physics

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. I. Infrared spectra and ultrafast pump-probe observables

PubMed Central

Gruenbaum, S. M.; Skinner, J. L.

2011-01-01

The vibrational spectroscopy of hydration water in dilauroylphosphatidylcholine lipid multi-bilayers is investigated using molecular dynamics simulations and a mixed quantum∕classical model for the OD stretch spectroscopy of dilute HDO in H2O. FTIR absorption spectra, and isotropic and anisotropic pump-probe decay curves have been measured experimentally as a function of the hydration level of the lipid multi-bilayer, and our goal is to make connection with these experiments. To this end, we use third-order response functions, which allow us to include non-Gaussian frequency fluctuations, non-Condon effects, molecular rotations, and a fluctuating vibrational lifetime, all of which we believe are important for this system. We calculate the response functions using existing transition frequency and dipole maps. From the experiments it appears that there are two distinct vibrational lifetimes corresponding to HDO molecules in different molecular environments. In order to obtain these lifetimes, we consider a simple two-population model for hydration water hydrogen bonds. Assuming a different lifetime for each population, we then calculate the isotropic pump-probe decay, fitting to experiment to obtain the two lifetimes for each hydration level. With these lifetimes in hand, we then calculate FTIR spectra and pump-probe anisotropy decay as a function of hydration. This approach, therefore, permits a consistent calculation of all observables within a unified computational scheme. Our theoretical results are all in qualitative agreement with experiment. The vibrational lifetime of lipid-associated OD groups is found to be systematically shorter than that of the water-associated population, and the lifetimes of each population increase with decreasing hydration, in agreement with previous analysis. Our theoretical FTIR absorption spectra successfully reproduce the experimentally observed red-shift with decreasing lipid hydration, and we confirm a previous interpretation that this shift results from the hydrogen bonding of water to the lipid phosphate group. From the pump-probe anisotropy decay, we confirm that the reorientational motions of water molecules slow significantly as hydration decreases, with water bound in the lipid carbonyl region undergoing the slowest rotations. PMID:21861584

Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

PubMed

Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

2015-08-03

We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea

USGS Publications Warehouse

Wang, Xiujuan; Hutchinson, Deborah R.; Wu, Shiguo; Yang, Shengxiong; Guo, Yiqun

2011-01-01

Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190–221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone.

Micromechanical measurements of the effect of surfactants on cyclopentane hydrate shell properties.

PubMed

Brown, Erika P; Koh, Carolyn A

2016-01-07

Investigating the effect of surfactants on clathrate hydrate growth and morphology, especially particle shell strength and cohesion force, is critical to advancing new strategies to mitigate hydrate plug formation. In this study, dodecylbenzenesulfonic acid and polysorbate 80 surfactants were included during the growth of cyclopentane hydrates at several concentrations above and below the critical micelle concentration. A novel micromechanical method was applied to determine the force required to puncture the hydrate shell using a glass cantilever (with and without surfactants), with annealing times ranging from immediately after the hydrate nucleated to 90 minutes after formation. It was shown that the puncture force was decreased by the addition of both surfactants up to a maximum of 79%. Over the entire range of annealing times (0-90 minutes), the thickness of the hydrate shell was also measured. However, there was no clear change in shell thickness with the addition of surfactants. The growth rate of the hydrate shell was found to vary less than 15% with the addition of surfactants. The cohesive force between two hydrate particles was measured for each surfactant and found to be reduced by 28% to 78%. Interfacial tension measurements were also performed. Based on these results, microscopic changes to the hydrate shell morphology (due to the presence of surfactants) were proposed to cause the decrease in the force required to break the hydrate shell, since no macroscopic morphology changes were observed. Understanding the hydrate shell strength can be critical to reducing the capillary bridge interaction between hydrate particles or controlling the release of unconverted water from the interior of the hydrate particle, which can cause rapid hydrate conversion.

Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates

PubMed Central

2017-01-01

We present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO2) gas hydrates using Raman spectroscopy. The CO2 hydrates were formed from sodium chloride/water solutions with salinities of 0–10 wt %, which were pressurized with liquid CO2 in a stirred vessel at 6 MPa and a subcooling of 9.5 K. The formation of the CO2 hydrate resulted in a hydrate gel where the solid hydrate can be considered as the continuous phase that includes small amounts of a dispersed liquid water-rich phase that has not been converted to hydrate. During the hydrate formation process we quantified the fraction of solid hydrate, xH, and the fraction of the dispersed liquid water-rich phase, xL, from the signature of the hydroxyl (OH)-stretching vibration of the hydrate gel. We found that the fraction of hydrate xH contained in the hydrate gel linearly depends on the salinity of the initial liquid water-rich phase. In addition, the ratio of CO2 and water was analyzed in the liquid water-rich phase before hydrate formation, in the hydrate gel during growth and dissociation, and after its complete dissociation again in the liquid water-rich phase. We observed a supersaturation of CO2 in the water-rich phase after complete dissociation of the hydrate gel and were able to show that the excess CO2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. These residual nano- and microdroplets could be a possible explanation for the so-called memory effect. PMID:28817275

Argentina corn yield model

NASA Technical Reports Server (NTRS)

Callis, S. L.; Sakamoto, C.

1984-01-01

A model based on multiple regression was developed to estimate corn yields for the country of Argentina. A meteorological data set was obtained for the country by averaging data for stations within the corn-growing area. Predictor variables for the model were derived from monthly total precipitation, average monthly mean temperature, and average monthly maximum temperature. A trend variable was included for the years 1965 to 1980 since an increasing trend in yields due to technology was observed between these years.

Evaluation of Thermal Evolution Profiles and Estimation of Kinetic Parameters for Pyrolysis of Coal/Corn Stover Blends Using Thermogravimetric Analysis

DOE PAGES

Bhagavatula, Abhijit; Huffman, Gerald; Shah, Naresh; ...

2014-01-01

The thermal evolution profiles and kinetic parameters for the pyrolysis of two Montana coals (DECS-38 subbituminous coal and DECS-25 lignite coal), one biomass sample (corn stover), and their blends (10%, 20%, and 30% by weight of corn stover) have been investigated at a heating rate of 5°C/min in an inert nitrogen atmosphere, using thermogravimetric analysis. The thermal evolution profiles of subbituminous coal and lignite coal display only one major peak over a wide temperature distribution, ~152–814°C and ~175–818°C, respectively, whereas the thermal decomposition profile for corn stover falls in a much narrower band than that of the coals, ~226–608°C. Themore » nonlinearity in the evolution of volatile matter with increasing percentage of corn stover in the blends verifies the possibility of synergistic behavior in the blends with subbituminous coal where deviations from the predicted yield ranging between 2% and 7% were observed whereas very little deviations (1%–3%) from predicted yield were observed in blends with lignite indicating no significant interactions with corn stover. In addition, a single first-order reaction model using the Coats-Redfern approximation was utilized to predict the kinetic parameters of the pyrolysis reaction. The kinetic analysis indicated that each thermal evolution profile may be represented as a single first-order reaction. Three temperature regimes were identified for each of the coals while corn stover and the blends were analyzed using two and four temperature regimes, respectively.« less

Evaluation of Thermal Evolution Profiles and Estimation of Kinetic Parameters for Pyrolysis of Coal/Corn Stover Blends Using Thermogravimetric Analysis

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

Bhagavatula, Abhijit; Huffman, Gerald; Shah, Naresh

The thermal evolution profiles and kinetic parameters for the pyrolysis of two Montana coals (DECS-38 subbituminous coal and DECS-25 lignite coal), one biomass sample (corn stover), and their blends (10%, 20%, and 30% by weight of corn stover) have been investigated at a heating rate of 5°C/min in an inert nitrogen atmosphere, using thermogravimetric analysis. The thermal evolution profiles of subbituminous coal and lignite coal display only one major peak over a wide temperature distribution, ~152–814°C and ~175–818°C, respectively, whereas the thermal decomposition profile for corn stover falls in a much narrower band than that of the coals, ~226–608°C. Themore » nonlinearity in the evolution of volatile matter with increasing percentage of corn stover in the blends verifies the possibility of synergistic behavior in the blends with subbituminous coal where deviations from the predicted yield ranging between 2% and 7% were observed whereas very little deviations (1%–3%) from predicted yield were observed in blends with lignite indicating no significant interactions with corn stover. In addition, a single first-order reaction model using the Coats-Redfern approximation was utilized to predict the kinetic parameters of the pyrolysis reaction. The kinetic analysis indicated that each thermal evolution profile may be represented as a single first-order reaction. Three temperature regimes were identified for each of the coals while corn stover and the blends were analyzed using two and four temperature regimes, respectively.« less

Do Pleistocene Glacial-Interglacial Cycles Control Methane Hydrate Formation? An Example from Green Canyon, Gulf of Mexico

NASA Astrophysics Data System (ADS)

Oryan, B.; Malinverno, A.; Goldberg, D.; Fortin, W.

2017-12-01

Well GC955-H was drilled in the Green Canyon region under the Gulf of Mexico Gas Hydrates Joint Industry Project in 2009. Logging-while-drilling resistivity logs obtained at the well indicate that the saturation of gas hydrate varies between high and low values in an alternating fashion. This trend is observed from 180 to 360mbsf, depths that correspond to the Late Pleistocene. Similar gas hydrate saturation patterns have been observed in other Gulf of Mexico locations (Walker Ridge sites WR313-G and 313-H) in Late Pleistocene sediments. Our hypothesis is that these variations in saturation can be explained by sea level changes through time during glacial-interglacial cycles. A higher amount of organic matter is deposited and buried in the sediment column during glacial intervals when sea level is low. Microbes in the sediment column degrade organic matter and produce methane gas as a byproduct. Higher availability of organic matter in the sediment column can increase the concentration of methane in the sediment pore water and in turn lead to the formation of gas hydrate. We use a time-dependent numerical model of the formation of gas hydrate to test this hypothesis. The model predicts the volume and distribution of gas hydrates using mass balance equations. Model inputs include in situ porosity determined from bulk density logs; local thermal gradient estimated from the depth of the bottom of the gas hydrate stability zone in proximity to the well; and sedimentation rate determined using the biostratigraphy of an industry well in the vicinity of GC955-H. Initial results show a good match between gas hydrate saturation predicted by the model and resistivity logs obtained in the well. We anticipate that this correlation will establish whether a causal link exists between the saturation of gas hydrate in this reservoir and glacioeustatic sea level changes in the Late Pleistocene.

Within-Plant Distribution of Adult Brown Stink Bug (Hemiptera: Pentatomidae) in Corn and Its Implications on Stink Bug Sampling and Management in Corn.

PubMed

Babu, Arun; Reisig, Dominic D

2018-05-29

Brown stink bug, Euschistus servus (Say) (Hemiptera: Pentatomidae), has emerged as a significant pest of corn, Zea mays L., in the southeastern United States. A 2-year study was conducted to quantify the within-plant vertical distribution of adult E. servus in field corn, to examine potential plant phenological characteristics associated with their observed distribution, and to select an efficient partial plant sampling method for adult E. servus population estimation. Within-plant distribution of adult E. servus was influenced by corn phenology. On V4- and V6-stage corn, most of the individuals were found at the base of the plant. Mean relative vertical position of adult E. servus population in corn plants trended upward between the V6 and V14 growth stages. During the reproductive corn growth stages (R1, R2, and R4), a majority of the adult E. servus were concentrated around developing ears. Based on the multiple selection criteria, during V4-V6 corn growth stages, either the corn stalk below the lowest green leaf or basal stratum method could employ for efficient E. servus sampling. Similarly, on reproductive corn growth stages (R1-R4), the plant parts between two leaves above and three leaves below the primary ear leaf were found to be areas to provide the most precise and cost-efficient sampling method. The results from our study successfully demonstrate that in the early vegetative and reproductive stages of corn, scouts can replace the current labor-intensive whole-plant search method with a more efficient, specific partial plant sampling method for E. servus population estimation.

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

PubMed

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-08-16

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

PubMed Central

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-01-01

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes. PMID:27526869

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

NASA Astrophysics Data System (ADS)

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-08-01

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Occurrence and structural characterization of gas hydrates associated with a cold vent field, offshore Vancouver Island

NASA Astrophysics Data System (ADS)

Lu, Hailong; Moudrakovski, Igor; Riedel, Michael; Spence, George; Dutrisac, Regent; Ripmeester, John; Wright, Fred; Dallimore, Scott

2005-10-01

Gas hydrate samples recovered from a cold vent field offshore Vancouver Island were studied in detail both by macroscopic observations and instrumental methods (powder X-ray diffraction method (PXRD), nuclear magnetic resonance (NMR), and Raman spectroscopy). It was found that gas hydrates were massive from 2.64 to 2.94 m below seafloor (mbsf), elongated, nodular and tabular from 4.60 to 4.81 mbsf, and vein-like from 5.48 to 5.68 mbsf, showing a trend of decreasing hydrate content with increasing depth. All samples were determined to be structure I hydrate from PXRD, NMR, and Raman spectroscopies. The hydration numbers were estimated to be 6.1 ± 0.2 on average as determined from the methane distribution over the cage sites from NMR and Raman analytical results. Estimates of conversion levels indicated that ˜78% of the water in the massive samples was hydrate, down to a low value of ˜0.4% for the pore hydrate samples. The results are compared with measurements on synthetic hydrates and samples recovered from below the permafrost on the Mallik site. Differences in methane content and lattice parameters for synthetic and natural samples are relatively minor. Additional work is needed to address the presence of minor gas components and the heterogeneity of natural hydrate samples.

A morel improved growth and suppressed Fusarium infection in sweet corn.

PubMed

Yu, Dan; Bu, Fangfang; Hou, Jiaojiao; Kang, Yongxiang; Yu, Zhongdong

2016-12-01

A post-fire morel collected from Populus simonii stands in Mt. Qingling was identified as Morchella crassipes Mes-20 by using nuclear ribosomal DNA internal transcribed spacer phylogeny. It was inoculated into sweet corn to observe colonized roots in purified culture and in greenhouse experiments. The elongation and maturation zones of sweet corn were remarkably colonized at the cortex intercellular and intracellular cells, vessel cells, and around the Casparian strip, forming ectendomycorrhiza-like structures. Colonization was also observed in the zone of cell division proximal to the root cap. Greenhouse assays with sweet corn showed that this morel stimulated the development of the root system and significantly increased the dry root biomass. M. crassipes also significantly reduced the incidence of Fusarium verticillioides in the kernels of mature ears when inoculated into young ears before Fusarium inoculation and prevented Fusarium infection in corn ears compared with that of the control in the greenhouse. When grown under axenic conditions, M. crassipes produced the phytohormones abscisic acid, indole-3-acetic acid, and salicylic acid. The benefits to plants elicited by M. crassipes may result from these phytohormones which may improve the drought resistance, biomass growth and resistance to Fusarium.

Colonization of Corn, Zea mays, by the Entomopathogenic Fungus Beauveria bassiana†

PubMed Central

Wagner, Bruce L.; Lewis, Leslie C.

2000-01-01

Light and electron microscopy were used to describe the mode of penetration by the entomopathogenic fungus Beauveria bassiana (Balsamo) Vuillemin into corn, Zea mays L. After inoculation with a foliar spray of conidia, germinating hyphae grew randomly across the leaf surface. Often a germ tube formed from a conidium and elongated only a short distance before terminating its growth. Not all developing hyphae on the leaf surface penetrated the cuticle. However, when penetration did occur, the penetration site(s) was randomly located, indicating that B. bassiana does not require specific topographic signals at an appropriate entry site as do some phytopathogenic fungi. Long hyphal structures were observed to follow the leaf apoplast in any direction from the point of penetration. A few hyphae were observed within xylem elements. Because vascular bundles are interconnected throughout the corn plant, this may explain how B. bassiana travels within the plant and ultimately provides overall insecticidal protection. Virulency bioassays demonstrate that B. bassiana does not lose virulence toward the European corn borer, Ostrinia nubilalis (Hübner), once it colonizes corn. This endophytic relationship between an entomopathogenic fungus and a plant suggests possibilities for biological control, including the use of indigenous fungal inocula as insecticides. PMID:10919808

FORAGES AND PASTURES SYMPOSIUM: Optimizing the use of fibrous residues in beef and dairy diets.

PubMed

Watson, A K; MacDonald, J C; Erickson, G E; Kononoff, P J; Klopfenstein, T J

2015-06-01

Increased corn prices over the past decade have altered land use away from traditional forage in favor of corn. Accordingly, beef and dairy producers have had to adopt nontraditional forage resources into their production systems, many of which have become available as a result of increased corn production. Corn residues have become more available due to increases in corn hectares and yield. The individual plant components (i.e., husk, leaf, and stem) vary in fiber digestibility (NDF digestibility estimates = 40.5, 31.4, and 0.6% ± 0.8 for husk, leaf, and stalk, respectively). Stocking cattle to consume 3.6 kg forage/25.5 kg of grain allows cattle to graze selectively; selection of husks and leaves improves cattle performance. Byproducts of the wet and dry milling industries can be supplemented to calves grazing corn residues to provide protein and energy. Optimal gains were observed when these byproducts were supplemented at approximately 2.5 kg/d to 250-kg growing calves. Gestating beef cows do not require supplemental inputs when grazing corn residue, if stocked appropriately. Alkaline treatment of crop residues improves their feeding value. Concentrations of up to 20% harvested corn residue treated with calcium oxide can be included in finishing diets with an average of 1.3% reduction in G:F when diets contain 40% wet or modified distillers grains. Conversely, when untreated corn residues are included in similar finishing diets, G:F is reduced by 13.4%. Calcium oxide-treated residues included in beef growing diets increases DMI and ADG without significant improvements in G:F. Calcium oxide treatment of corn residues has been evaluated in dairy diets by replacing corn or corn silage with variable results. Efficient use of nontraditional fiber sources, such as corn milling byproducts and corn residue, are critical to the future viability of ruminant animal production.

Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in sI methane hydrate

USGS Publications Warehouse

Waite, W.F.; Stern, L.A.; Kirby, S.H.; Winters, W.J.; Mason, D.H.

2007-01-01

Thermal conductivity, thermal diffusivity and specific heat of sI methane hydrate were measured as functions of temperature and pressure using a needle probe technique. The temperature dependence was measured between −20°C and 17°C at 31.5 MPa. The pressure dependence was measured between 31.5 and 102 MPa at 14.4°C. Only weak temperature and pressure dependencies were observed. Methane hydrate thermal conductivity differs from that of water by less than 10 per cent, too little to provide a sensitive measure of hydrate content in water-saturated systems. Thermal diffusivity of methane hydrate is more than twice that of water, however, and its specific heat is about half that of water. Thus, when drilling into or through hydrate-rich sediment, heat from the borehole can raise the formation temperature more than 20 per cent faster than if the formation's pore space contains only water. Thermal properties of methane hydrate should be considered in safety and economic assessments of hydrate-bearing sediment.

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

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

Radha, S.; Milius, Wolfgang; Breu, Josef, E-mail: josef.breu@uni-bayreuth.de

2013-08-15

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacingmore » evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.« less

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Evaluation of limit feeding corn and distillers dried grains with solubles in non-feed-withdrawal molt programs for laying hens.

PubMed

Mejia, L; Meyer, E T; Utterback, P L; Utterback, C W; Parsons, C M; Koelkebeck, K W

2010-03-01

An experiment was conducted using 504 Hy-Line W-36 Single Comb White Leghorn hens (69 wk of age) randomly assigned to 1 of 7 treatments. These treatments consisted of a 47% corn:47% soy hulls diet (C:SH) fed ad libitum; a 94% corn diet fed at a rate of 36.3, 45.4, or 54.5 g/hen per day (CORN 36, CORN 45, and CORN 54, respectively); and a 94% corn distillers dried grains with solubles (DDGS) diet fed at the same rates as the previous corn diets (DDGS 36, DDGS 45, and DDGS 54, respectively) during the molt period of 28 d. The intent was to feed the DDGS diets for 28 d; however, all hens on these diets had very low feed intakes and greater than anticipated BW loss. Thus, they were switched to a 16% CP corn-soybean meal layer diet on d 19 of the molt period. At d 28, hens on all treatments were fed the same corn-soybean meal layer diet for 39 wk (73 to 112 wk of age). All DDGS diets and the CORN 36 diet resulted in total cessation of egg production during the molt period and egg production of hens fed the CORN 45, CORN 54, and C:SH diets had decreased to 3 and 4%, respectively, by d 28. Body weight loss during the 28-d molt period ranged from 14% for the CORN 54 diet to approximately 23% for the 3 DDGS diets. Postmolt egg production (5 to 43 wk) was higher for hens fed the DDGS molt diets than those fed the corn diets. There were no consistent differences in egg mass, egg-specific gravity, feed efficiency, or layer feed consumption among molt treatments for the postmolt period. These results indicate that limit feeding corn diet and DDGS diet in non-feed-withdrawal molt programs will yield long-term postmolt performance that is comparable to that observed by ad libitum feeding a C:SH diet.

Simulating the effect of hydrate dissociation on wellhead stability during oil and gas development in deepwater

NASA Astrophysics Data System (ADS)

Li, Qingchao; Cheng, Yuanfang; Zhang, Huaiwen; Yan, Chuanliang; Liu, Yuwen

2018-02-01

It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development (OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.

Effect of steam explosion and microbial fermentation on cellulose and lignin degradation of corn stover.

PubMed

Chang, Juan; Cheng, Wei; Yin, Qingqiang; Zuo, Ruiyu; Song, Andong; Zheng, Qiuhong; Wang, Ping; Wang, Xiao; Liu, Junxi

2012-01-01

In order to increase nutrient values of corn stover, effects of steam explosion (2.5 MPa, 200 s) and Aspergillus oryzae (A. oryzae) fermentation on cellulose and lignin degradation were studied. The results showed the contents of cellulose, hemicellulose and lignin in the exploded corn stover were 8.47%, 50.45% and 36.65% lower than that in the untreated one, respectively (P<0.05). The contents of cellulose and hemicellulose in the exploded and fermented corn stover (EFCS) were decreased by 24.36% and 69.90%, compared with the untreated one (P<0.05); decreased by 17.35% and 38.59%, compared with the exploded one (P<0.05). The scanning electron microscope observations demonstrated that the combined steam explosion and fermentation destructed corn stover. The activities of enzymes in EFCS were increased. The metabolic experiment showed that about 8% EFCS could be used to replace corn meal in broiler diets, which made EFCS become animal feedstuff possible. Copyright © 2011 Elsevier Ltd. All rights reserved.

Potential of kenaf (Hibiscus cannabinus L.) and corn (Zea mays L.) for phytoremediation of dredging sludge contaminated by trace metals.

PubMed

Arbaoui, Sarra; Evlard, Aricia; Mhamdi, Mohamed El Wafi; Campanella, Bruno; Paul, Roger; Bettaieb, Taoufik

2013-07-01

The potential of kenaf (Hibiscus cannabinus L.) and corn (Zea mays L.) for accumulation of cadmium and zinc was investigated. Plants have been grown in lysimetres containing dredging sludge, a substratum naturally rich in trace metals. Biomass production was determined. Sludge and water percolating from lysimeters were analyzed by atomic absorption spectrometry. No visible symptoms of toxicity were observed during the three- month culture. Kenaf and corn tolerate trace metals content in sludge. Results showed that Zn and Cd were found in corn and kenaf shoots at different levels, 2.49 mg/kg of Cd and 82.5 mg/kg of Zn in kenaf shoots and 2.1 mg/kg of Cd and 10.19 mg/kg in corn shoots. Quantities of extracted trace metals showed that decontamination of Zn and Cd polluted substrates is possible by corn and kenaf crops. Tolerance and bioaccumulation factors indicated that both species could be used in phytoremediation.

Stochastic Approach to Determine CO2 Hydrate Induction Time in Clay Mineral Suspensions

NASA Astrophysics Data System (ADS)

Lee, K.; Lee, S.; Lee, W.

2008-12-01

A large number of induction time data for carbon dioxide hydrate formation were obtained from a batch reactor consisting of four independent reaction cells. Using resistance temperature detector(RTD)s and a digital microscope, we successfully monitored the whole process of hydrate formation (i.e., nucleation and crystal growth) and detected the induction time. The experiments were carried out in kaolinite and montmorillonite suspensions at temperatures between 274 and 277 K and pressures ranging from 3.0 to 4.0 MPa. Each set of data was analyzed beforehand whether to be treated by stochastic manner or not. Geochemical factors potentially influencing the hydrate induction time under different experimental conditions were investigated by stochastic analyses. We observed that clay mineral type, pressure, and temperature significantly affect the stochastic behavior of the induction times for CO2 hydrate formation in this study. The hydrate formation kinetics along with stochastic analyses can provide basic understanding for CO2 hydrate storage in deep-sea sediment and geologic formation, securing its stability under the environments.

Seepage from an arctic shallow marine gas hydrate reservoir is insensitive to momentary ocean warming

PubMed Central

Hong, Wei-Li; Torres, Marta E.; Carroll, JoLynn; Crémière, Antoine; Panieri, Giuliana; Yao, Haoyi; Serov, Pavel

2017-01-01

Arctic gas hydrate reservoirs located in shallow water and proximal to the sediment-water interface are thought to be sensitive to bottom water warming that may trigger gas hydrate dissociation and the release of methane. Here, we evaluate bottom water temperature as a potential driver for hydrate dissociation and methane release from a recently discovered, gas-hydrate-bearing system south of Spitsbergen (Storfjordrenna, ∼380 m water depth). Modelling of the non-steady-state porewater profiles and observations of distinct layers of methane-derived authigenic carbonate nodules in the sediments indicate centurial to millennial methane emissions in the region. Results of temperature modelling suggest limited impact of short-term warming on gas hydrates deeper than a few metres in the sediments. We conclude that the ongoing and past methane emission episodes at the investigated sites are likely due to the episodic ventilation of deep reservoirs rather than warming-induced gas hydrate dissociation in this shallow water seep site. PMID:28589962

Seepage from an arctic shallow marine gas hydrate reservoir is insensitive to momentary ocean warming

DOE PAGES

Hong, Wei-Li; Torres, Marta E.; Carroll, JoLynn; ...

2017-06-07

Arctic gas hydrate reservoirs located in shallow water and proximal to the sediment-water interface are thought to be sensitive to bottom water warming that may trigger gas hydrate dissociation and the release of methane. Here, we evaluate bottom water temperature as a potential driver for hydrate dissociation and methane release from a recently discovered, gas-hydrate-bearing system south of Spitsbergen (Storfjordrenna, ~380m water depth). Modelling of the non-steady-state porewater profiles and observations of distinct layers of methane-derived authigenic carbonate nodules in the sediments indicate centurial to millennial methane emissions in the region. The results of temperature modelling suggest limited impact ofmore » short-term warming on gas hydrates deeper than a few metres in the sediments. We conclude that the ongoing and past methane emission episodes at the investigated sites are likely due to the episodic ventilation of deep reservoirs rather than warming-induced gas hydrate dissociation in this shallow water seep site.« less

Joint inversion of acoustic and resistivity data for the estimation of gas hydrate concentration

USGS Publications Warehouse

Lee, Myung W.

2002-01-01

Downhole log measurements, such as acoustic or electrical resistivity logs, are frequently used to estimate in situ gas hydrate concentrations in the pore space of sedimentary rocks. Usually the gas hydrate concentration is estimated separately based on each log measurement. However, measurements are related to each other through the gas hydrate concentration, so the gas hydrate concentrations can be estimated by jointly inverting available logs. Because the magnitude of slowness of acoustic and resistivity values differs by more than an order of magnitude, a least-squares method, weighted by the inverse of the observed values, is attempted. Estimating the resistivity of connate water and gas hydrate concentration simultaneously is problematic, because the resistivity of connate water is independent of acoustics. In order to overcome this problem, a coupling constant is introduced in the Jacobian matrix. In the use of different logs to estimate gas hydrate concentration, a joint inversion of different measurements is preferred to the averaging of each inversion result.

Seepage from an arctic shallow marine gas hydrate reservoir is insensitive to momentary ocean warming.

PubMed

Hong, Wei-Li; Torres, Marta E; Carroll, JoLynn; Crémière, Antoine; Panieri, Giuliana; Yao, Haoyi; Serov, Pavel

2017-06-07

Arctic gas hydrate reservoirs located in shallow water and proximal to the sediment-water interface are thought to be sensitive to bottom water warming that may trigger gas hydrate dissociation and the release of methane. Here, we evaluate bottom water temperature as a potential driver for hydrate dissociation and methane release from a recently discovered, gas-hydrate-bearing system south of Spitsbergen (Storfjordrenna, ∼380 m water depth). Modelling of the non-steady-state porewater profiles and observations of distinct layers of methane-derived authigenic carbonate nodules in the sediments indicate centurial to millennial methane emissions in the region. Results of temperature modelling suggest limited impact of short-term warming on gas hydrates deeper than a few metres in the sediments. We conclude that the ongoing and past methane emission episodes at the investigated sites are likely due to the episodic ventilation of deep reservoirs rather than warming-induced gas hydrate dissociation in this shallow water seep site.

Seepage from an arctic shallow marine gas hydrate reservoir is insensitive to momentary ocean warming

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

Hong, Wei-Li; Torres, Marta E.; Carroll, JoLynn

Arctic gas hydrate reservoirs located in shallow water and proximal to the sediment-water interface are thought to be sensitive to bottom water warming that may trigger gas hydrate dissociation and the release of methane. Here, we evaluate bottom water temperature as a potential driver for hydrate dissociation and methane release from a recently discovered, gas-hydrate-bearing system south of Spitsbergen (Storfjordrenna, ~380m water depth). Modelling of the non-steady-state porewater profiles and observations of distinct layers of methane-derived authigenic carbonate nodules in the sediments indicate centurial to millennial methane emissions in the region. The results of temperature modelling suggest limited impact ofmore » short-term warming on gas hydrates deeper than a few metres in the sediments. We conclude that the ongoing and past methane emission episodes at the investigated sites are likely due to the episodic ventilation of deep reservoirs rather than warming-induced gas hydrate dissociation in this shallow water seep site.« less

Thermal conductivity of hydrate-bearing sediments

USGS Publications Warehouse

Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn D.

2009-01-01

A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

A calorimetric and microstructural study of solidified toxic wastes. Part 2: A model for poisoning of OPC hydration

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

Hills, C.D.; Sollars, C.J.; Perry, R.

1994-01-01

During cement-based processing of certain hazardous wastes the hydration reactions thought to be responsible for solidification can be poisoned and appear to be retarded indefinitely. A number of wastes known to be capable of poisoning hydration were added to ordinary Portland cement (OPC) and classified on the basis of interference effects observed. This paper reports the results from a characterization of these wastes and the subsequent addition to OPC of waste components identified as significant in single and combined additions. The effects of these additions were examined by conduction calorimetry and microstructural techniques. A comparison of results showed that itmore » was possible to reproduce the poisoning effects observed previously with real wastes by an addition of combined metal hydroxides only. These results suggest that poisoning results from the synergistic effects of compounds contained in the waste. A model, representing the early hydration of OPC, has been modified and is presented and its application in explaining poisoning of hydration is discussed.« less

Mapping hydration dynamics around a protein surface

PubMed Central

Zhang, Luyuan; Wang, Lijuan; Kao, Ya-Ting; Qiu, Weihong; Yang, Yi; Okobiah, Oghaghare; Zhong, Dongping

2007-01-01

Protein surface hydration is fundamental to its structure and activity. We report here the direct mapping of global hydration dynamics around a protein in its native and molten globular states, using a tryptophan scan by site-specific mutations. With 16 tryptophan mutants and in 29 different positions and states, we observed two robust, distinct water dynamics in the hydration layer on a few (≈1–8 ps) and tens to hundreds of picoseconds (≈20–200 ps), representing the initial local relaxation and subsequent collective network restructuring, respectively. Both time scales are strongly correlated with protein's structural and chemical properties. These results reveal the intimate relationship between hydration dynamics and protein fluctuations and such biologically relevant water–protein interactions fluctuate on picosecond time scales. PMID:18003912

Faulting of gas-hydrate-bearing marine sediments - contribution to permeability

USGS Publications Warehouse

Dillon, William P.; Holbrook, W.S.; Drury, Rebecca; Gettrust, Joseph; Hutchinson, Deborah; Booth, James; Taylor, Michael

1997-01-01

Extensive faulting is observed in sediments containing high concentrations of methane hydrate off the southeastern coast of the United States. Faults that break the sea floor show evidence of both extension and shortening; mud diapirs are also present. The zone of recent faulting apparently extends from the ocean floor down to the base of gas-hydrate stability. We infer that the faulting resulted from excess pore pressure in gas trapped beneath the gas hydrate-beating layer and/or weakening and mobilization of sediments in the region just below the gas-hydrate stability zone. In addition to the zone of surface faults, we identified two buried zones of faulting, that may have similar origins. Subsurface faulted zones appear to act as gas traps.

Multimodal approach to characterization of hydrophilic matrices manufactured by wet and dry granulation or direct compression methods.

PubMed

Kulinowski, Piotr; Woyna-Orlewicz, Krzysztof; Obrał, Jadwiga; Rappen, Gerd-Martin; Haznar-Garbacz, Dorota; Węglarz, Władysław P; Jachowicz, Renata; Wyszogrodzka, Gabriela; Klaja, Jolanta; Dorożyński, Przemysław P

2016-02-29

The purpose of the research was to investigate the effect of the manufacturing process of the controlled release hydrophilic matrix tablets on their hydration behavior, internal structure and drug release. Direct compression (DC) quetiapine hemifumarate matrices and matrices made of powders obtained by dry granulation (DG) and high shear wet granulation (HS) were prepared. They had the same quantitative composition and they were evaluated using X-ray microtomography, magnetic resonance imaging and biorelevant stress test dissolution. Principal results concerned matrices after 2 h of hydration: (i) layered structure of the DC and DG hydrated tablets with magnetic resonance image intensity decreasing towards the center of the matrix was observed, while in HS matrices layer of lower intensity appeared in the middle of hydrated part; (ii) the DC and DG tablets retained their core and consequently exhibited higher resistance to the physiological stresses during simulation of small intestinal passage than HS formulation. Comparing to DC, HS granulation changed properties of the matrix in terms of hydration pattern and resistance to stress in biorelevant dissolution apparatus. Dry granulation did not change these properties-similar hydration pattern and dissolution in biorelevant conditions were observed for DC and DG matrices. Copyright © 2015 Elsevier B.V. All rights reserved.

An Investigation into the Properties and Microstructure of Cement Mixtures Modified with Cellulose Nanocrystal

PubMed Central

Flores, Jessica; Kamali, Mahsa; Ghahremaninezhad, Ali

2017-01-01

This paper aims to examine the effect of cellulose nanocrystals (CNC) on the hydration, transport behavior, and microstructure of cement mixtures. The addition of CNC delayed hydration at an early age but improved hydration at later ages. A small increase in the electrical resistivity of the cement mixtures with CNC was observed. Statistical nanoindentation showed a small tendency to a larger volume fraction of high density calcium-silicate-hydrate (C-S-H) and a smaller volume fraction of low-density C-S-H in the mixture with CNC. PMID:28772857

Corn blight review: Sampling model and ground data measurements program

NASA Technical Reports Server (NTRS)

Allen, R. D.

1972-01-01

The sampling plan involved the selection of the study area, determination of the flightline and segment sample design within the study area, and determination of a field sample design. Initial interview survey data consisting of crop species acreage and land use were collected. On all corn fields, additional information such as seed type, row direction, population, planting date, ect. were also collected. From this information, sample corn fields were selected to be observed through the growing season on a biweekly basis by county extension personnel.

Effect of replacement of corn starch by whey protein isolate in biodegradable film blends obtained by extrusion.

PubMed

Azevedo, Viviane Machado; Borges, Soraia Vilela; Marconcini, José Manoel; Yoshida, Maria Irene; Neto, Alfredo Rodrigues Sena; Pereira, Tamara Coelho; Pereira, Camila Ferreira Gonçalves

2017-02-10

The aim of this study was to evaluate the effect of replacing corn starch by whey protein isolated (WPI) in biodegradable polymer blends developed by extrusion. X-ray diffraction showed the presence of a Vh-type crystalline arrangement. The films were homogeneous, indicating strong interfacial adhesion between the protein and the thermoplastic starch matrix (TPS) as observed in scanning electron microscopy. The addition of WPI on TPS matrix promoted an increase in the thermal stability of the materials. It was observed 58.5% decrease in the water vapor permeability. The effect of corn starch substitution by WPI on mechanical properties resulted in a more resistant and less flexible film when compared the TPS film. The addition of WPI caused greenish yellow color and less transparent films. The substitution of corn starch by WPI made it possible to obtain polymer blends with improved properties and represents an innovation for application as a packaging material. Copyright © 2016. Published by Elsevier Ltd.

Epithermal Neutron Evidence for a Diurnal Surface Hydration Process in the Moon's High Latitudes

NASA Technical Reports Server (NTRS)

McClanahan, T. P.; Mitrofanov, I. G.; Boynton, W. V.; Chin, G.; Parsons, A.; Starr, R. D.; Evans, L. G.; Sanin, A.; Litvak, M.; Livengood, T.

2015-01-01

We report evidence from epithermal neutron flux observations that show that the Moon's high latitude surfaces are being actively hydrated, dehydrated and rehydrated in a diurnal cycle. The near-surface hydration is indicated by an enhanced suppression of the lunar epithermal neutron leakage flux on the dayside of the dawn terminator on poleward-facing slopes (PFS). At 0600 to 0800 local-time, hydrogen concentrations within the upper 1 meter of PFS are observed to be maximized relative to equivalent equator-facing slopes (EFS). During the lunar day surface hydrogen concentrations diminish towards dusk and then rebuild overnight. Surface hydration is determined by differential comparison of the averaged EFS to PFS epithermal neutron count rates above +/- 75 deg latitude. At dawn the contrast bias towards PFS is consistent with at least 15 to 25 parts-per-million (ppm) hydrogen that dissipates by dusk. We review several lines of evidence derived from temperature and epithermal neutron data by a correlated analysis of observations from the Lunar Reconnaissance Orbiter's (LRO) Lunar Exploration Neutron Detector (LEND) that were mapped as a function of lunar local-time, Lunar Observing Laser Altimeter (LOLA) topography and Diviner (DLRE) surface temperature.

Infrared and swelling study of the hydration-induced phase transition of wet-spun hyaluronate films

NASA Astrophysics Data System (ADS)

Hoppe, A. D.; Marlowe, R. L.; Lee, S. A.; Powell, J. W.; Rupprecht, A.

1997-03-01

The hydration properties of wet-spun films of hyaluronate (HA) with four different counterions (Li^+, Cs^+, Mg^2+, and Ca^2+) have been studied using optical microscopy, optical birefringence and infrared (IR) spectroscopy. Small pieces of these films were found to be optically birefringent up to hydration levels near 90 % relative humidity (RH). All four kinds of films then became optically isotropic and display dramatic changes in size. These changes are consistent with the occurrence of an order-disorder (o-d) transition. IR spectroscopy of the backbone region (from 800 to 1000 cm-1) suggests that the Li^+, Cs^+ and Ca^2+ films are very similar. Two IR bands in this region are observed at low RH and show no dependence on hydration until the o-d transition. The IR spectra of CaHA show five bands in this region. These five bands are observed to 95 % RH.

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

PubMed

Prasad, Pinnelli S R; Sugahara, Takeshi; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-22

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

IR-UV spectroscopy of jet-cooled 1-indanol: Restriction of the conformational space by hydration

NASA Astrophysics Data System (ADS)

Bouchet, Aude; Altnöder, Jonas; Broquier, Michel; Zehnacker, Anne

2014-11-01

The effect of hydration on a flexible amphiphilic molecule has been studied on the example of 1-hydroxyindan (1-indanol). Studies in jet-cooled conditions by means of resonance-enhanced two-photon ionization and IR-UV double resonance experiments show that the mono-hydrate 1-indanol(H2O) is formed in a dominant isomer, as well as the di-hydrate 1-indanol(H2O)2. 1-Indanol(H2O) favors a cooperative hydrogen bond pattern with -OH⋯O(H)-H⋯π topology, while 1-indanol(H2O)2 forms a cyclic hydrogen bond network with three OH⋯O interactions. The single conformation observed for the hydrates contrasts with the bare molecule which shows two dominant conformations, with the hydroxyl in axial or in equatorial position, respectively. Hydration therefore results in a restriction of the conformational space and conformational locking.

Assessing submarine gas hydrate at active seeps on the Hikurangi Margin, New Zealand, using controlled source electromagnetic data with constraints from seismic, geochemistry, and heatflow data

NASA Astrophysics Data System (ADS)

Schwalenberg, K.; Haeckel, M.; Pecher, I. A.; Toulmin, S. J.; Hamdan, L. J.; Netzeband, G.; Wood, W.; Poort, J.; Jegen, M. D.; Coffin, R. B.

2009-12-01

Electrical resistivity is one of the key properties useful for evaluating submarine gas hydrate deposits. Gas hydrates are electrically insulating in contrast to the conductive pore fluid. Where they form in sufficient quantities the bulk resistivity of the sub-seafloor is elevated. CSEM data were collected in 2007 as part of the German - International “New Vents” project on R/V Sonne, cruise SO191, at three target areas on the Hikurangi subduction margin, New Zealand. The margin is characterized by widespread bottom simulating reflectors (BSR), seep structures, and active methane and fluid venting indicating the potential for gas hydrate formation. Opouawe Bank is one of the ridge and basin systems on the accretionary wedge and is located off the Wairarapa coast at water depths of 1000-1100 m. The first observed seep sites (North Tower, South Tower, Pukeko, Takahe, and Tui) were identified from individual gas flares in hydro-acoustic data and video observations during voyages on R/V Tangaroa. Seismic reflection data collected during SO191 subsequently identified more than 25 new seep structures. Two intersecting CSEM profiles have been surveyed across North Tower, South Tower, and Takahe. 1-D inversion of the data reveals anomalously high resistivities at North Tower and South Tower, moderately elevated resistivities at Takahe, and normal background resistivities away from the seeps. The high resistivities are attributed to gas hydrate layers at intermediate depths beneath the seeps. At South Tower the hydrate concentration could be possibly as much as 25% of the total sediment volume within a 50m thick layer. This conforms with geochemical pore water analyses which show a trend of increased methane flux towards South Tower. At Takahe, gas pockets and patchy gas hydrate, as well as sediment heterogeneities and carbonates, or temperature driven upward fluid flow indicated by the observed higher heat flow at this site may explain the resistivity pattern. Porangahau Ridge is located further north on the margin in water depths of 1900-2000m. A high amplitude reflection zone extending from the BSR around 700mbsf towards the seafloor has been observed at the western flank of the ridge. This is attributed to local shoaling at the base of the hydrate stability zone caused by upward migrating warm fluids. A CSEM profile was surveyed across the same seismic line. The data reveal a pronounced resistivity anomaly at the western rim suggesting a zone of concentrated gas hydrate above the reflection band. Heat flow and geochemistry data collected along the same transect show concave temperature profiles indicating mildly advective heat flow and massive gas and fluid transport on the western flank, particularly at the location where the resistivity anomaly has been observed.

Luminescence and ESR studies of relationships between O(-)-centres and structural iron in natural and synthetically hydrated kaolinites

NASA Technical Reports Server (NTRS)

Coyne, L. M.; Costanzo, P. M.; Theng, B. K.

1989-01-01

Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between hydration-induced luminescence and g = 2 ESR signals associated with O(-)-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 angstroms synthetically hydrated, kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O(-)-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 angstroms hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O(-)-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 angstroms hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

Corn silage from corn treated with foliar fungicide and performance of Holstein cows.

PubMed

Haerr, K J; Lopes, N M; Pereira, M N; Fellows, G M; Cardoso, F C

2015-12-01

Foliar fungicide application to corn plants is used in corn aimed for corn silage in the dairy industry, but questions regarding frequency of application and its effect on corn silage quality and feed conversion when fed to dairy cows remain prevalent. The objective of this study was to evaluate the effects of various foliar fungicide applications to corn on dry matter intake (DMI), milk production, and milk composition when fed to dairy cows. Sixty-four Holstein cows with parity 2.5±1.5, 653±80kg of body weight, and 161±51d in milk were blocked and randomly assigned to 1 of 4 corn silage treatments (total mixed ration with 35% of the dry matter as corn silage). Treatments were as follows: control (CON), corn silage with no applications of foliar fungicide; treatment 1 (1X), corn silage from corn that received 1 application of pyraclostrobin (PYR) foliar fungicide (Headline; BASF Corp.) at corn vegetative stage 5; treatment 2 (2X), corn silage from corn that received the same application as 1X plus another application of a mixture of PYR and metconazole (Headline AMP; BASF Corp.) at corn reproductive stage 1 ("silking"); and treatment 3 (3X), corn silage from corn that received the same applications as 2X as well as a third application of PYR and metconazole at reproductive stage 3 ("milky kernel"). Corn was harvested at about 32% dry matter and 3/4 milk line stage of kernel development and ensiled for 200d. Treatments were fed to cows for 5wk, with the last week being used for statistical inferences. Week -1 was used as a covariate in the statistical analysis. Dry matter intake tended to be lower for cows fed corn silage treated with fungicide than CON (23.8, 23.0, 19.5, and 21.3kg for CON, 1X, 2X, and 3X, respectively). A linear treatment effect for DMI was observed, with DMI decreasing as foliar fungicide applications increased. Treatments CON, 1X, 2X, and 3X did not differ for milk yield (34.5, 34.5, 34.2, and 34.4kg/d, respectively); however, a trend for increased feed conversion represented by fat-corrected milk/DMI (1.65 vs. 1.47) and energy-corrected milk/DMI (1.60 vs. 1.43) was noted for cows fed corn silage with fungicide compared with CON. In conclusion, cows receiving corn silage treated with foliar fungicide had better conversion of feed dry matter to milk than those receiving CON silage. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Influence of the corn resistance gene Mv on the fitness of Peregrinus maidis (Hemiptera: Delphacidae) and on the transmission of maize mosaic virus (Rhabdoviridae: Nucleorhabdovirus).

PubMed

Higashi, C H V; Brewbaker, J L; Bressan, A

2013-08-01

Crops that are resistant to pests and pathogens are cost-effective for the management of pests and diseases. A corn (Zea mays L.) breeding program conducted in Hawaii has identified a source of heritable resistance to maize mosaic virus (MMV) (Rhabdoviridae: Nucleorhabdovirus). This resistance is controlled by the gene Mv, which has been shown to have a codominant action. To date, no studies have examined whether the resistance associated with this gene affects only MMV or whether it also affects the insect vector, the corn planthopper Peregrinus maidis (Ashmead) (Hemiptera: Delphacidae). Here, we examined the life history of the corn planthopper and its ability to transmit MMV on near isogenic lines that were homozygous dominant (Mv/Mv), homozygous recessive (mv/mv), or heterozygous (Mv/mv) for the gene. A field trial was also conducted to study the colonization of the corn plants with different genotypes by the planthopper. Although field observations revealed slightly lower densities ofplanthoppers on corn with the genotype Mv/Mv than on the inbreds with the genotype mv/mv and their hybrids with the genotype Mv/mv, laboratory assays showed no effects of the gene on planthopper development, longevity, or fecundity. In the field, the corn lines Mv/Mv had a lower incidence of MMV-infected plants. However, in the greenhouse, the transmission of MMV to corn seedlings did not differ across the near isogenic lines, although the corn lines Mv/Mv showed a delayed onset of symptoms compared with the corn lines mv/mv and Mv/mv. The acquisition of MMV by corn planthoppers on the corn genotypes Mv/Mv and Mv/mv averaged 0.2, whereas the acquisition on the corn genotypes mv/mv averaged > 0.3. Our results show that the Mv gene does not influence the fitness of the planthopper vector, suggesting that it may confer resistance by other means, possibly by limiting virus replication or movement within the host plant.

Silica-rich deposits and hydrated minerals at Gusev Crater, Mars: Vis-NIR spectral characterization and regional mapping

USGS Publications Warehouse

Rice, M.S.; Bell, J.F.; Cloutis, E.A.; Wang, A.; Ruff, S.W.; Craig, M.A.; Bailey, D.T.; Johnson, J. R.; De Souza, P.A.; Farrand, W. H.

2010-01-01

The Mars Exploration Rover (MER) Spirit has discovered surprisingly high concentrations of amorphous silica in soil and nodular outcrops in the Inner Basin of the Columbia Hills. In Pancam multispectral observations, we find that an absorption feature at the longest Pancam wavelength (1009 nm) appears to be characteristic of these silica-rich materials; however, spectral analyses of amorphous silica suggest that the ???1009 nm spectral feature is not a direct reflection of their silica-rich nature. Based on comparisons with spectral databases, we hypothesize that the presence of H2O or OH, either free (as water ice), adsorbed or bound in a mineral structure, is responsible for the spectral feature observed by Pancam. The Gertrude Weise soil, which is nearly pure opaline silica, may have adsorbed water cold-trapped on mineral grains. The origin of the ???1009 nm Pancam feature observed in the silica-rich nodular outcrops may result from the presence of additional hydrated minerals (specific sulfates, halides, chlorides, sodium silicates, carbonates or borates). Using the ???1009 nm feature with other spectral parameters as a "hydration signature" we have mapped the occurrence of hydrated materials along the extent of Spirit's traverse across the Columbia Hills from West Spur to Home Plate (sols 155-1696). We have also mapped this hydration signature across large panoramic images to understand the regional distribution of materials that are spectrally similar to the silica-rich soil and nodular outcrops. Our results suggest that hydrated materials are common in the Columbia Hills. ?? 2009 Elsevier Inc.

Observation of hydration of single, modified carbon aerosols

NASA Technical Reports Server (NTRS)

Wyslouzil, B. E.; Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Arnold, S.

1994-01-01

We have compared the hydration behavior of single carbon particles that have been treated by exposure to gaseous H2SO4 with that of untreated particles. Untreated carbon particles did not hydrate as the relative humidity varied from 0 to 80% at 23 C. In contrast, treated particles hydrated under subsaturation conditions; mass increases of up to 30% were observed. The mass increase is consistent with sulfuric acid equilibration with the ambient relative humidity in the presence of inert carbon. For the samples studied, the average amount of absorbed acid was 14% +/- 6% by weight, which corresponds to a surface coverage of approximately 0.1 monolayer. The mass fraction of surface-absorbed acid is comparable to the soluble mass fraction observed by Whitefield et al. (1993) in jet aircraft engine aerosols. Estimates indicate this mass fraction corresponds to 0.1% of the available SO2 exiting an aircraft engine ending up as H2SO4 on the carbon aerosol. If this heterogeneous process occurs early enough in the exhaust plume, it may compete with homogeneous nucleation as a mechanism for producing sulfuric acid rich aerosols.

High pressure micromechanical force measurements of the effects of surface corrosion and salinity on CH4/C2H6 hydrate particle-surface interactions.

PubMed

Wang, Shenglong; Hu, Sijia; Brown, Erika P; Nakatsuka, Matthew A; Zhao, Jiafei; Yang, Mingjun; Song, Yongchen; Koh, Carolyn A

2017-05-24

In order to investigate the mechanism of gas hydrate deposition and agglomeration in gas dominated flowlines, a high-pressure micromechanical force (MMF) apparatus was applied to directly measure CH 4 /C 2 H 6 hydrate adhesion/cohesion forces under low temperature and high pressure conditions. A CH 4 /C 2 H 6 gas mixture was used as the hydrate former. Adhesion forces between hydrate particles and carbon steel (CS) surfaces were measured, and the effects of corrosion on adhesion forces were analyzed. The influences of NaCl concentration on the cohesion force between CH 4 /C 2 H 6 hydrate particles were also studied for gas-dominated systems. It was observed that there was no measurable adhesion force for pristine (no corrosion) and corroded surfaces, when there was no condensed water or water droplet on these surfaces. With water on the surface (the estimated water amount was around 1.7 μg mm -2 ), a hydrate film growth process was observed during the measurement. CS samples were soaked in NaCl solution to obtain different extents of corrosion on surfaces, and adhesion measurements were performed on both pristine and corroded samples. The adhesion force was found to increase with increasing soak times in 5 wt% NaCl (resulting in more visual corrosion) by up to 500%. For the effect of salinity on cohesion forces, it was found that the presence of NaCl decreased the cohesion force between hydrate particles, and a possible explanation of this phenomenon was given based on the capillary liquid bridge model.

Permeability studies of redox-sensitive nitroxyl spin probes in corn oil using an L-band ESR spectrometer

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

Jebaraj, D. David; Utsumi, Hideo; Asath, R. Mohamed

Electron spin resonance (ESR) studies were carried out for 2mM {sup 14}N labeled {sup 2}H enriched 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) and 3–carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy (carboxy-PROXYL) in pure water and various concentrations of corn oil. The ESR parameters, such as the line width, hyperfine coupling constant, g-factor, rotational correlation time, partition parameter and permeability were reported for the samples. The line width broadening was observed for both nitroxyl radicals in corn oil solutions. The partition parameter for permeable MC-PROXYL in corn oil increases with increasing concentration of corn oil, which reveals that the nitroxyl spin probe permeates into the oil phase. From the results, themore » corn oil concentration was optimized as 50 % for phantom studies. The rotational correlation time also increases with increasing concentration of corn oil. The permeable and impermeable nature of nitroxyl spin probes was demonstrated. These results will be useful for the development of ESR/OMR imaging modalities in in vivo and in vitro studies.« less

Evaluation of the correlation between Scoring Feline Allergic Dermatitis and Feline Extent and Severity Index and skin hydration in atopic cats.

PubMed

Szczepanik, Marcin P; Wilkołek, Piotr M; Adamek, Łukasz R; Zając, Marcin; Gołyński, Marcin; Sitkowski, Wiesław; Taszkun, Iwona

2018-02-01

Evaluation of the severity of clinical signs of cats with allergic skin diseases has used two scoring systems: Scoring Feline Allergic Dermatitis (SCORFAD) and the Feline Extent and Severity Index (FeDESI). The integrity of the cutaneous barrier can also be evaluated by measuring skin hydration. A correlation between the clinical score and skin hydration has been observed in humans and dogs with atopic dermatitis (AD). To demonstrate a correlation between the clinical score and skin hydration of cats affected with presumed AD. European short hair cats (n = 18): 11 females and seven males with a confirmed diagnosis of AD. SCORFAD and FeDESI scores were calculated and the measurements of skin hydration were assessed from seven body sites using corneometry. The correlation between the SCORFAD and FeDESI systems and skin hydration of each site, and the average skin hydration was calculated. There was a positive correlation between the SCORFAD score and skin hydration for the axilla, thorax and forelimb; for FeDESI and axilla and lumbar sites. There was a negative correlation between the FeDESI and skin hydration for the pinna (r = -0.47). Measurements of skin hydration could be a useful tool for the evaluation of allergic cats. There is limited evidence of any useful correlation between clinical scoring systems and measurements of hydration. The pinna may be a suitable region for the assessment of skin barrier function in normal and allergic cats. © 2017 ESVD and ACVD.

Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

2017-12-01

A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

Effects of feeding corn naturally contaminated with aflatoxin B1 and B2 on hepatic functions of broilers.

PubMed

Yang, J; Bai, F; Zhang, K; Bai, S; Peng, X; Ding, X; Li, Y; Zhang, J; Zhao, L

2012-11-01

The purpose of this study was to evaluate the effects of feeding corn naturally contaminated with aflatoxin B(1) (AFB(1)) and aflatoxin B(2) (AFB(2)) on serum biochemical parameters, hepatic antioxidant enzyme activities, and pathological lesions of broilers. In total, 1,200 Cobb male broilers were randomly allocated into 5 treatments, with 8 replicates per treatment and 30 birds per replicate, in a 42-d experiment. The dietary treatments were as follows: control, 25, 50, 75, and 100% contaminated corn groups. Results showed that serum aspartate aminotransferase activity in the 75 and 100% contaminated groups were higher than that in the control group on d 21 (P < 0.05). Decreased content of hepatic total protein and increased activities of hepatic glutathione reductase and glutathione-S-transferase were observed as the percentage of contaminated corn increased (P < 0.05). The activity of superoxide dismutase and the content of hepatic malondialdehyde increased when the broilers were fed with more than 50% contaminated corn (P < 0.05). A reduction in glutathione peroxidase level was observed in the AFB(1)- and AFB(2)-contaminated groups on d 21 (P < 0.05). The average pathological lesion scores and apoptosis rate of liver cells increased as the concentration of dietary AFB(1) and AFB(2) increased. Ultrastructural changes were found in the livers of broilers fed 100% contaminated corn. In conclusion, diets containing AFB(1) and AFB(2) could induce pathological lesions in the livers, slightly change the serum biochemical parameters, and damage the hepatic antioxidant functions when the inclusion of AFB(1)- and AFB(2)-contaminated corn reached or exceeded 50%.

A blinded randomized controlled trial evaluating the usefulness of a novel diet (aminoprotect care) in dogs with spontaneous food allergy.

PubMed

Olivry, Thierry; Kurata, Keigo; Paps, Judy S; Masuda, Kenichi

2007-10-01

Aminoprotect Care (APC) is a novel diet composed of aminoacids, potato proteins and corn starch. The objectives of this study were to determine whether Maltese-Beagle atopic (MBA) dogs hypersensitive to corn exhibited clinical signs and changes in immunological markers after being fed APC. The study was designed as a blinded randomized controlled crossover experiment. Ten MBA dogs with signs of allergy within five days of ingesting corn were selected. Dogs were randomized to be fed either their maintenance diet with corn or APC for five days. After a washout of two weeks, diets were switched. Before and daily during each intervention, skin lesions were graded by an investigator while pruritus was assessed by another. Before and at the end of each intervention, the percentage of circulating CD4+CCR4+, corn-activated CD4+ T-lymphocytes and serum corn-specific IgE levels were measured and ratios of post:pre values calculated. During this trial, pruritus and skin lesions increased significantly in MBA dogs when ingesting corn while no such increase occurred when fed APC. Total, median and maximal pruritus values were significantly higher in MBA dogs ingesting corn compared to APC. There were no significant differences between interventions in the immunological parameters assessed. In summary, even though APC contains corn starch to which corn-sensitive MBA dogs often react, the ingestion of APC did not lead to significant increases in skin lesions or pruritus. Aminoprotect Care might prove valuable for management of food allergies. These experimental observations must be validated in large field studies.

Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores

NASA Astrophysics Data System (ADS)

Yang, Guomin; Neretnieks, Ivars; Holmboe, Michael

2017-08-01

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ˜5.0 Å from the clay basal-plane), observed in the MD simulations.

Selecting the Right Varieties in Riau Main Island: Sweet Corn Context

NASA Astrophysics Data System (ADS)

Surtinah; Nurwati, Niken

2018-05-01

The Riau Main island long way known has a unique geographic location and minerals contains in its soils. To help in selecting the best varieties that can help to sustain the food security plan in Riau main island is the aims of this study. Corn is a one of the local food that support the coastal and highland community in Riau and Sumatera Islands. Therefore corn was selected to be the object of this study. This experiment was conducted experimentally using a complete randomized environmental design and the treatment design with eight varieties of sweet corns. Data analysis uses Sidik variety and Duncan 5 % distance tes. The parameter observed is sweet corn which deals with the weight of cobs with cornhusk, the weight of cobs without cornhusk, the length of cobs without cornhusk and the sugar content of the seeds. The result shows that the best varieties are Sweet boy, sweet lady and bonanza.

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Kinetics of methane hydrate replacement with carbon dioxide and nitrogen gas mixture using in situ NMR spectroscopy.

PubMed

Cha, Minjun; Shin, Kyuchul; Lee, Huen; Moudrakovski, Igor L; Ripmeester, John A; Seo, Yutaek

2015-02-03

In this study, the kinetics of methane replacement with carbon dioxide and nitrogen gas in methane gas hydrate prepared in porous silica gel matrices has been studied by in situ (1)H and (13)C NMR spectroscopy. The replacement process was monitored by in situ (1)H NMR spectra, where about 42 mol % of the methane in the hydrate cages was replaced in 65 h. Large amounts of free water were not observed during the replacement process, indicating a spontaneous replacement reaction upon exposing methane hydrate to carbon dioxide and nitrogen gas mixture. From in situ (13)C NMR spectra, we confirmed that the replacement ratio was slightly higher in small cages, but due to the composition of structure I hydrate, the amount of methane evolved from the large cages was larger than that of the small cages. Compositional analysis of vapor and hydrate phases was also carried out after the replacement reaction ceased. Notably, the composition changes in hydrate phases after the replacement reaction would be affected by the difference in the chemical potential between the vapor phase and hydrate surface rather than a pore size effect. These results suggest that the replacement technique provides methane recovery as well as stabilization of the resulting carbon dioxide hydrate phase without melting.

The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

PubMed

Zhang, Zhengcai; Guo, Guang-Jun

2017-07-26

Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

A comparison of hydration effect on body fluid and temperature regulation between Malaysian and Japanese males exercising at mild dehydration in humid heat.

PubMed

Wakabayashi, Hitoshi; Wijayanto, Titis; Lee, Joo-Young; Hashiguchi, Nobuko; Saat, Mohamed; Tochihara, Yutaka

2014-02-04

This study investigated the effect of hydration differences on body fluid and temperature regulation between tropical and temperate indigenes exercising in the heat. Ten Japanese and ten Malaysian males with matched physical characteristics (height, body weight, and peak oxygen consumption) participated in this study. Participants performed exercise for 60 min at 55% peak oxygen uptake followed by a 30-min recovery at 32°C and 70% relative air humidity with hydration (4 times each, 3 mL per kg body weight, 37°C) or without hydration. Rectal temperature, skin temperature, heart rate, skin blood flow, and blood pressure were measured continuously. The percentage of body weight loss and total sweat loss were calculated from body weight measurements. The percentage change in plasma volume was estimated from hemoglobin concentration and hematocrit. Malaysian participants had a significantly lower rectal temperature, a smaller reduction in plasma volume, and a lower heart rate in the hydrated condition than in the non-hydrated condition at the end of exercise (P <0.05), whereas Japanese participants showed no difference between the two hydration conditions. Hydration induced a greater total sweat loss in both groups (P <0.05), and the percentage of body weight loss in hydrated Malaysians was significantly less than in hydrated Japanese (P <0.05). A significant interaction between groups and hydration conditions was observed for the percentage of mean cutaneous vascular conductance during exercise relative to baseline (P <0.05). The smaller reduction in plasma volume and percentage body weight loss in hydrated Malaysians indicated an advantage in body fluid regulation. This may enable Malaysians to reserve more blood for circulation and heat dissipation and thereby maintain lower rectal temperatures in a hydrated condition.

Towards a universal method for calculating hydration free energies: a 3D reference interaction site model with partial molar volume correction.

PubMed

Palmer, David S; Frolov, Andrey I; Ratkova, Ekaterina L; Fedorov, Maxim V

2010-12-15

We report a simple universal method to systematically improve the accuracy of hydration free energies calculated using an integral equation theory of molecular liquids, the 3D reference interaction site model. A strong linear correlation is observed between the difference of the experimental and (uncorrected) calculated hydration free energies and the calculated partial molar volume for a data set of 185 neutral organic molecules from different chemical classes. By using the partial molar volume as a linear empirical correction to the calculated hydration free energy, we obtain predictions of hydration free energies in excellent agreement with experiment (R = 0.94, σ = 0.99 kcal mol (- 1) for a test set of 120 organic molecules).

Velocities and Attenuations of Gas Hydrate-Bearing Sediments

USGS Publications Warehouse

Lee, Myung W.

2007-01-01

Monopole and dipole logging data at the Mallik 5L-38, Mackenzie Delta, Canada, provide a challenge for sonic velocity and attenuation models used to remotely estimate pore-space gas hydrate content. Velocity and attenuation are linked, with velocity dispersion causing increased attenuation. Sonic waveforms for Mallik 5L-38, however, show no velocity dispersion in gas hydrate-bearing layers, yet are highly attenuated. Attenuation models applied to Mallik 5L-38 data are shown to be inconsistent with the observed velocity measurements, and therefore are suspect in their ability to predict gas hydrate content. A model explicitly linking velocity and attenuation data is presented, accurately predicting gas hydrate content from velocity data alone while demonstrating that the attenuation mechanisms at the Mallik 5L-38 site have not yet been identified.

Proton affinities of hydrated molecules

NASA Astrophysics Data System (ADS)

Valadbeigi, Younes

2016-09-01

Proton affinities (PA) of non-hydrated, M, and hydrated forms, M(H2O)1,2,3, of 20 organic molecules including alcohols, ethers, aldehydes, ketones and amines were calculated by the B3LYP/6-311++G(d,p) method. For homogeneous families, linear correlations were observed between PAs of the M(H2O)1,2,3 and the PAs of the non-hydrated molecules. Also, the absolute values of the hydration enthalpies of the protonated molecules decreased linearly with the PAs. The correlation functions predicted that for an amine with PA < 1100 kJ/mol the PA(M(H2O)) is larger than the corresponding PA, while for an amine with PA > 1100 kJ/mol the PA(M(H2O)) is smaller than the PA.

Phase diagram and high-pressure boundary of hydrate formation in the carbon dioxide-water system.

PubMed

Manakov, Andrej Yu; Dyadin, Yuriy A; Ogienko, Andrey G; Kurnosov, Alexander V; Aladko, Eugeny Ya; Larionov, Eduard G; Zhurko, Fridrih V; Voronin, Vladimir I; Berger, Ivan F; Goryainov, Sergei V; Lihacheva, Anna Yu; Ancharov, Aleksei I

2009-05-21

Experimental investigation of the phase diagram of the system carbon dioxide-water at pressures up to 2.7 GPa has been carried out in order to explain earlier controversial results on the decomposition curves of the hydrates formed in this system. According to X-ray diffraction data, solid and/or liquid phases of water and CO2 coexist in the system at room temperature within the pressure range from 0.8 to 2.6 GPa; no clathrate hydrates are observed. The results of neutron diffraction experiments involving the samples with different CO2/H2O molar ratios, and the data on the phase diagram of the system carbon dioxide-water show that CO2 hydrate of cubic structure I is the only clathrate phase present in this system under studied P-T conditions. We suppose that in the cubic structure I hydrate of CO2 multiple occupation of the large hydrate cavities with CO2 molecules takes place. At pressure of about 0.8 GPa this hydrate decomposes into components indicating the presence of the upper pressure boundary of the existence of clathrate hydrates in the system.

Investigation of C3S hydration by environmental scanning electron microscope.

PubMed

Sakalli, Y; Trettin, R

2015-07-01

Tricalciumsilicate (C(3)S, Alite) is the major component of the Portland cement clinker, The hydration of the Alite is decisive for the properties of the resulting material due to the high content in cement. The mechanism of the hydration of C(3)S is very complicated and not yet fully understood. There are some models that describe the hydration of C(3)S in various ways. The Environmental Scanning Electron Microscopy (ESEM) working in gaseous atmosphere enables high-resolution dynamic observations of structure of materials, from micrometre to nanometre scale. This provides a new perspective in material research. ESEM significantly allows imaging of specimen in their natural state without the need for special preparation (coating, drying, etc.) that can alter the physical properties. This paper presents the results of our experimental studies of hydration of C(3)S using ESEM. The ESEM turned out to be an important extension of the conventional scanning microscopy. The purpose of these investigations is to gain insight of hydration mechanism to determine which hydration products are formed and to analyze if there are any differences in the composition of the hydration products. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

Relationship of gas hydrate concentration to porosity and reflection amplitude in a research well, Mackenzie Delta, Canada

USGS Publications Warehouse

Jin, Y.K.; Lee, M.W.; Collett, T.S.

2002-01-01

Well logs acquired at the Mallik 2L-38 gas hydrate research well. Mackenzie Delta, Canada, reveal a distinct trend showing that the resistivity of gas-hydrate-bearing sediments increases with increases in density porosities. This trend, opposite to the general trend of decrease in resistivity with porosity, implies that gas hydrates are more concentrated in the higher porosity. Using the Mallik 2L-38 well data, a proportional gas hydrate concentration (PGHC) model, which states that the gas hydrate concentration in the sediment's pore space is linearly proportional to porosity, is proposed for the general habitat of gas hydrate in sediments. Anomalous data (less than 6% of the total data) outside the dominant observed trend can be explained by local geological characteristics. The anomalous data analysis indicates that highly concentrated gas-hydrate-bearing layers would be expected where sediments have high proportions of gravel and coarse sand. Using the parameters in the PGHC model determined from resistivity-porosity logs, it is possible to qualitatively predict the degree of reflection amplitude variations in seismic profiles. Moderate-to-strong reflections are expected for the Mallik 2L-38 well. ?? 2002 Elsevier Science Ltd. All rights reserved.

Acute and Subacute Toxicity Evaluation of Corn Silk Extract

PubMed Central

Ha, Ae Wha; Kang, Hyeon Jung; Kim, Sun Lim; Kim, Myung Hwan

2018-01-01

Many studies have reported therapeutic efficacy of corn silk extract. However, research on its toxicity and safe dose range is limited. Thus, the objective of this study was to determine the acute and subacute toxicity of corn silk extract in ICR mice. To determine acute toxicity, corn silk extract containing high levels of maysin was orally administered to mice at a dose of 0 or 2,000 mg/kg. Clinical symptoms, mortality, and body weight changes were recorded for 14 days. To determine subacute toxicity, corn silk extract was orally administered to mice over a 4-week period, and then body weight, water and food consumption, and organ weight were determined. In addition, urine and serum analyses were performed. In the acute toxicity study, no death or abnormal symptoms was observed in all treatment groups during the study period. Body weights did not show any significant change compared to those of the control group. Lethal dose of corn silk extract was estimated to be more than 2,000 mg/kg. In the 4-week subacute toxicity study, there was no corn silk extract related toxic effect on body weight, water intake, food consumption, urine parameters, clinical chemistry, or organ weight. Histopathological examination showed no abnormality related to the administration of corn silk extract at 500 mg/kg. The maximum non-toxic dose of corn silk extract containing high levels of maysin was found to be more than 500 mg/kg. PMID:29662850

Acute and Subacute Toxicity Evaluation of Corn Silk Extract.

PubMed

Ha, Ae Wha; Kang, Hyeon Jung; Kim, Sun Lim; Kim, Myung Hwan; Kim, Woo Kyoung

2018-03-01

Many studies have reported therapeutic efficacy of corn silk extract. However, research on its toxicity and safe dose range is limited. Thus, the objective of this study was to determine the acute and subacute toxicity of corn silk extract in ICR mice. To determine acute toxicity, corn silk extract containing high levels of maysin was orally administered to mice at a dose of 0 or 2,000 mg/kg. Clinical symptoms, mortality, and body weight changes were recorded for 14 days. To determine subacute toxicity, corn silk extract was orally administered to mice over a 4-week period, and then body weight, water and food consumption, and organ weight were determined. In addition, urine and serum analyses were performed. In the acute toxicity study, no death or abnormal symptoms was observed in all treatment groups during the study period. Body weights did not show any significant change compared to those of the control group. Lethal dose of corn silk extract was estimated to be more than 2,000 mg/kg. In the 4-week subacute toxicity study, there was no corn silk extract related toxic effect on body weight, water intake, food consumption, urine parameters, clinical chemistry, or organ weight. Histopathological examination showed no abnormality related to the administration of corn silk extract at 500 mg/kg. The maximum non-toxic dose of corn silk extract containing high levels of maysin was found to be more than 500 mg/kg.

Purple corn color inhibition of prostate carcinogenesis by targeting cell growth pathways.

PubMed

Long, Ne; Suzuki, Shugo; Sato, Shinya; Naiki-Ito, Aya; Sakatani, Keisuke; Shirai, Tomoyuki; Takahashi, Satoru

2013-03-01

Purple corn color is a widely used food colorant that was reported to have attenuating effects on hypertension, diabetes, and to have anti-cancer effects on colon and breast cancer. Our study is the first on its possible chemoprevention effects against prostate cancer. For this purpose an androgen-dependent prostate cancer cell line, LNCaP, was used to examine effects in vitro. Purple corn color inhibited the proliferation of LNCaP cells by decreasing the expression of Cyclin D1 and inhibiting the G1 stage of the cell cycle. Thirty-six male transgenic rats for adenocarcinoma of prostate were fed basic diet or diet with purple corn color for 8 weeks. Purple corn color decreased the incidence of adenocarcinoma in the lateral prostate and slowed down the progression of prostate cancer. A lower Ki67 positive rate, a decrease of the expression of Cyclin D1, and downregulation of the activation of Erk1/2 and p38 MAPK were observed in the group consuming purple corn color in the diet. Since purple corn color is a mixture, determining its active component should help in the understanding and usage of purple corn color for prostate cancer chemoprevention. Therefore, the three major anthocyanins in purple corn color, cyanidin-3-glucoside, pelargonidin-3-glucoside and peonidin-3-glucoside, were tested with LNCaP cells. The results suggested that cyanidin-3-glucoside and pelargonidin-3-glucoside are the active compounds. © 2012 Japanese Cancer Association.

Assesment of PM2.5 emission from corn stover burning determining in chamber combustion

NASA Astrophysics Data System (ADS)

Hafidawati; Lestari, P.; Sofyan, A.

2018-04-01

Chamber measurement were conducted to determine Particulate Matter (PM2.5) emission from open burning of corn straw at Garut District, West Java. The of this study is to estimate the concentration of PM2.5 for two types of corn (corncobs and cornstover) for five varieties (Bisma, P29, NK, Bisma, NW). Corn residues were collected and then burned in the chamber combustion. The chamber was designed to simulate the burning in the field, which was observed in the field experiment that meteorological condition was calm wind. The samples were collected using a minivol air sampler. The assessment results of PM2.5 concentrations (mg/m3) from open burning experiment in the chamber for five varieties of corn cobs (Bisma, P29, NK, Bisi, NW) was 9.187; 2.843; 7.409; 3.781; 1.895 respectively. Concentration for corn stover burn was 2.060; 5.283; 4.048; 5.306 and 5.697 respectively. Fluctuations in the value of concentration among these varieties reflect variations in combustion conditions (combustion efficiency) and other parameters including water content, biomass conditions and the meteorological conditions. The combustion efficiency (MCE) of the combustion chamber simulation of corncobs ia lower than the MCE of corn stover, that the concentration PM2.5 more emitted from the burning of corn stover. The results of this study presented provide useful information for the development of local emission factors for PM2.5 from open burning of corn stover in Indonesia.

Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea

USGS Publications Warehouse

Wang, X.; Hutchinson, D.R.; Wu, S.; Yang, S.; Guo, Y.

2011-01-01

Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190-221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone. Copyright 2011 by the American Geophysical Union.

Supporting Climatic Trends of Corn and Soybean Production in the USA

NASA Astrophysics Data System (ADS)

Mishra, V.; Cherkauer, K. A.; Verdin, J. P.

2010-12-01

The United States of America (USA) is a major source of corn and soybeans, producing about 39 percent of the world’s corn and 50 percent of world’s soybean supply. The north central states, including parts of the Midwestern US and the Great Plains form what is commonly described as the “Corn Belt” and consist of the most productive grain growing region in the United States. Changes in climate, including precipitation and temperature, are being observed throughout the world, and the Corn Belt region of the US is not immune posing a potential threat to global food security. We conducted a retrospective analysis of observed climate variables and crop production statistics to evaluate if observed climatic trends are having a positive or negative effect on corn and soybean production in the US. We selected climate indices based on gridded daily precipitation, maximum and minimum air temperature data from the National Climatic Data Center (NCDC) for the period of 1920-2009 and for 13 states in the Corn Belt region. We used the standardized precipitation index (SPI) and standardized precipitation evapotranspiration index (SPEI) for different periods overlapping the important seasons for crop growths, such as the planting (April-May), grain-filling (June-August), and harvesting (September -October) seasons. We estimated the seasonal average of maximum and minimum daily temperatures to identify the historic trends and variability in air temperature during the key crop-growth seasons. Extreme warm temperatures can affect crop growth and yields adversely; therefore, cumulative maximum air temperature above the 90th percentiles (e.g. Cumulative Heat Index) was estimated for each growing period. We evaluated historic trends and variability of areal extents of severe or extreme droughts along with the areal extents facing the high cumulative heat stress. Our results showed that climatic extremes (e.g. droughts and heat stress) that occurred during the period of June - August (JJA), affected the yields of corn and soybeans most severely. High moisture and low heat stress during the JJA period favored crop yields, while low moisture and high heat conditions during the planting season (April-May) increased yields. Results also indicated that this part of the US is trending towards lower heat stress and drought extents, and higher moisture conditions during the JJA period. Therefore, in future, if the present trends persist, we expect the climate will more supportive of increased corn and soybean yields.

CORN AND TUNA DIET--REPORT OF OBSERVATIONS ON NUTRITION: RADIATION AND STERILIZATION OF FOODS FOR HAZELTON LABORATORIES, FALLS CHURCH, VIRGINIA

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

Ross, M.A.

1963-09-15

No evidence was found to suggest that the consumption of irradiated corn or tuna fish produced lesions in rats significantly different in incidence or type than was found in animals that consumed the unirradiated products. (C.H.)

LONG-TERM FEEDING STUDIES ON IRRADIATED CORN AND TUNA FISH. Progress Report No. 5 for September 12, 1958 to March 9, 1959

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

Paynter, O.E.

1959-10-31

No significant changes were observed in body weight gains, food consumption general physical condition, behavior, or survival of rats maintained for 77 weeks on a diet containing irradiated corn and tuna fish. (C.H.)

L band brightness temperature observations over a corn canopy during the entire growth cycle

USDA-ARS?s Scientific Manuscript database

During a field campaign covering the 2002 corn growing season, a dual polarized tower mounted L-band (1.4 GHz) radiometer (LRAD) provided brightness temperature (T¬B) measurements at preset intervals, incidence and azimuth angles. These radiometer measurements were supported by an extensive characte...

Phosphorus export from artificially drained fields across the Eastern corn belt

USDA-ARS?s Scientific Manuscript database

Field observations that quantify agricultural phosphorus (P) losses are critical for the development of P reduction strategies across the Eastern Corn Belt region of North America. Within this region, surface water bodies including Lake Erie are sensitive to non-point P loadings. It is therefore imp...

21 CFR 137.270 - Self-rising white corn meal.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 45 cc. acid used in the decomposition). Observe the temperature of the air surrounding the apparatus... is an intimate mixture of white corn meal, sodium bicarbonate, and one or both of the acid-reacting... dioxide is evolved. The acid-reacting substance is added in sufficient quantity to neutralize the sodium...

21 CFR 137.270 - Self-rising white corn meal.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 45 cc. acid used in the decomposition). Observe the temperature of the air surrounding the apparatus... is an intimate mixture of white corn meal, sodium bicarbonate, and one or both of the acid-reacting... dioxide is evolved. The acid-reacting substance is added in sufficient quantity to neutralize the sodium...

21 CFR 137.270 - Self-rising white corn meal.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 45 cc. acid used in the decomposition). Observe the temperature of the air surrounding the apparatus... is an intimate mixture of white corn meal, sodium bicarbonate, and one or both of the acid-reacting... dioxide is evolved. The acid-reacting substance is added in sufficient quantity to neutralize the sodium...

Hydration Experiments and Physical Observations at 193 K and 243 K for Mg-Sulfates Relevant to Mars

NASA Astrophysics Data System (ADS)

Vaniman, D. T.; Chipera, S. J.; Carey, J. W.

2006-03-01

Hydration of kieserite and amorphous Mg-sulfate at 243 K progresses along simple pathways involving only hexahydrite and kieserite. Kieserite forms a duricrust-like cement, but the anhydrous precursor does not.

Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

PubMed

Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

2016-11-01

Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

Gas hydrate occurrences in the Danube Delta, Western Black Sea: Results from 2D and 3D controlled source electromagnetics

NASA Astrophysics Data System (ADS)

Schwalenberg, Katrin; Hölz, Sebastian; Gehrmann, Romina; Rippe, Dennis; Dannowski, Anke; Zander, Timo; Duan, Shuangmin; Jegen, Marion; Bialas, Jörg

2017-04-01

Marine controlled source electromagnetic (CSEM) data have been collected over gas hydrate targets in the Danube Delta off the coasts of Bulgaria and Romania in early 2014 during voyage MSM35 on R/V Maria S. MERIAN. The cruise was part of the German SUGAR Project, a joint venture project with the goal to study submarine gas hydrates as a source of methane. Within European waters the Black Sea is one of the most prospective hydrocarbon areas. Thick sedimentary basins, the existence of an extended gas hydrate stability zone and the observation of multiple bottom simulating reflectors (BSR) in the western part indicate a huge gas hydrate potential in sandy sediments. Low pore-water salinities between 1 and 4 ppt have been observed in borehole data at depths below 30 mbsf, and are attributed to sea level low stands in the past. 2D and 3D CSEM data sets have been collected over one of the channel levee systems of the Danube Delta fan. High-resolution 2D and 3D seismic, and OBS data are available in the same target area providing structural information and porosity profiles from seismic velocity data. Analysis of subsets of the 3D CSEM data reveal pore-water salinities around 4 ppt for the shallow sediment section, thus are not as low as suggested by the borehole data. The inversion of both 2D and 3D CSEM data sets reveal highly anomalous resistivities within the gas hydrate stability field. We believe that high gas hydrate saturations are the likely cause, as low pore-water salinities are not sufficient to explain the high resistivities, seismic data indicate no clear gas migration pathways through the stability field, nor do hydro-acoustic data show areas of gas seepage which are confined to the landward edge of the stability field. Estimates of the gas hydrate saturation are commonly derived from Archie's Law, and strongly depend on the proper choice of input parameters. We apply porosities from seismic velocity profiles, pore-water resistivities derived from salinity and temperature profiles, and Archie coefficients a, m, and n derived from laboratory studies with various sands and porosities. Gas hydrate saturation estimates vary between 20 and 60 % due to the wide range of input parameter, but are generally higher than estimates from seismic velocity data, an outcome also observed in other gas hydrate areas.

Physical properties of repressurized samples recovered during the 2006 National Gas Hydrate Program expedition offshore India

USGS Publications Warehouse

Winters, William J.; Waite, William F.; Mason, David H.; Kumar, P.

2008-01-01

As part of an international cooperative research program, the U.S. Geological Survey (USGS) and researchers from the National Gas Hydrate Program (NGHP) of India are studying the physical properties of sediment recovered during the NGHP-01 cruise conducted offshore India during 2006. Here we report on index property, acoustic velocity, and triaxial shear test results for samples recovered from the Krishna-Godavari Basin. In addition, we discuss the effects of sample storage temperature, handling, and change in structure of fine-grained sediment. Although complex, sub-vertical planar gas-hydrate structures were observed in the silty clay to clayey silt samples prior to entering the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI), the samples yielded little gas post test. This suggests most, if not all, gas hydrate dissociated during sample transfer. Mechanical properties of hydrate-bearing marine sediment are best measured by avoiding sample depressurization. By contrast, mechanical properties of hydrate-free sediments, that are shipped and stored at atmospheric pressure can be approximated by consolidating core material to the original in situ effective stress.

Relation of submarine landslide to hydrate occurrences in Baiyun Depression, South China Sea

NASA Astrophysics Data System (ADS)

Sun, Yunbao; Zhang, Xiaohua; Wu, Shiguo; Wang, Lei; Yang, Shengxiong

2018-02-01

Submarine landslides have been observed in the Baiyun Depression of the South China Sea. The occurrence of hydrates below these landslides indicates that these slope instabilities may be closely related to the massive release of methane. In this study, we used a simple Monte-Carlo model to determine the first-order deformation pattern of a gravitationally destabilizing slope. The results show that a stress concentration occurs due to hydrate dissociation on the nearby glide surface and on top of a gas chimney structure. Upon the dissolution of the gas hydrate, slope failure occurs due to the excess pore pressure generated by the dissociation of the gas hydrates. When gas hydrates dissociate at shallow depths, the excess pore pressure generated can be greater than the total stress acting at those points, along with the forces that resist sliding. Initially, the failure occurs at the toe of the slope, then extends to the interior. Although our investigation focused only on the contribution of hydrate decomposition to submarine landslide, this process is also affected by both the slope material properties and topography.

Generation of transgenic corn-derived Actinobacillus pleuropneumoniae ApxIIA fused with the cholera toxin B subunit as a vaccine candidate

PubMed Central

Shin, Min-Kyoung; Jung, Myung Hwan; Lee, Won-Jung; Choi, Pil Son; Jang, Yong-Suk

2011-01-01

Corn, one of the most important forage crops worldwide, has proven to be a useful expression vehicle due to the availability of established transformation procedures for this well-studied plant. The exotoxin Apx, a major virulence factor, is recognized as a common antigen of Actinobacillus (A.) pleuropneumoniae, the causative agent of porcine pleuropneumonia. In this study, a cholera toxin B (CTB)-ApxIIA#5 fusion protein and full-size ApxIIA expressed in corn seed, as a subunit vaccine candidate, were observed to induce Apx-specific immune responses in mice. These results suggest that transgenic corn-derived ApxIIA and CTB-ApxIIA#5 proteins are potential vaccine candidates against A. pleuropneumoniae infection. PMID:22122907

The examination of biophysical parameters of skin (transepidermal water loss, skin hydration and pH value) in different body regions of normal cats of both sexes.

PubMed

Szczepanik, Marcin P; Wilkołek, Piotr M; Adamek, Lukasz R; Pomorski, Zbigniew J H

2011-04-01

The purpose of this study was to evaluate transepidermal water loss (TEWL), skin hydration and skin pH in normal cats. Twenty shorthaired European cats of both sexes were examined in the study. Measurements were taken from five different sites: the lumbar region, the axillary fossa, the inguinal region, the ventral abdominal region and the left thoracic region. In each of the regions, TEWL, skin hydration and skin pH were measured. The highest TEWL value was observed in the axillary fossa (18.22g/h/m(2)) and the lowest in the lumbar region (10.53g/h/m(2)). The highest skin hydration was found in the inguinal region (18.29CU) and the lowest in the lumbar region (4.62CU). The highest skin pH was observed in the inguinal region (6.64) and the lowest in the lumbar region (6.39). Statistically significant differences in TEWL were observed between the lumbar region and the left side of the thorax region (P=0.016), the axillary fossa (P=0.0004), the ventral region (P=0.005), and the inguinal region (P=0.009). There were significant differences in skin hydration between the lumbar region and the left thorax (P=0.000003), the axillary fossa (P=0.002), the ventral abdomen (P=0.03), and the inguinal region (P=0.0003) as well as between the thorax and the ventral abdomen (P=0.005). TEWL was higher in females (15g/h/m(2)) than in males (4.57g/h/m(2)). Skin hydration was higher in females (13.89CU) than in males (12.28CU). Significant differences were not found between males and females for TEWL and skin hydration. Skin pH was higher in males (6.94) than in females (6.54), which was significant (P=0.004). Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

Effect of incorporation of corn byproducts on quality of baked and extruded products from wheat flour and semolina.

PubMed

Sharma, Savita; Gupta, Jatinder Pal; Nagi, H P S; Kumar, Rakesh

2012-10-01

The effect of blending level (0, 5, 10, 15 and 20%) of corn bran, defatted germ and gluten with wheat flour on the physico-chemical properties (protein, crude fiber, phosphorus, iron and calcium), baking properties of bread, muffins and cookies, and extrusion properties of noodles and extruded snacks prepared from semolina were examined. Blending of wheat flour and corn byproducts significantly increased the protein, crude fiber, phosphorus, iron and calcium contents. Breads from gluten blends had higher loaf volume as compared to bran and germ breads. Among corn byproducts, gluten cookies were rated superior with respect to top grain. Muffins from germ blends and gluten blends had higher acceptability scores than the bran muffins. Blending of corn bran, defatted germ and gluten at 5 and 10% with wheat flour resulted in satisfactory bread, cookie, and muffin score. Quality of noodles was significantly influenced by addition of corn byproducts and their levels. Corn byproducts blending had significant influence on cooking time, however, gruel solid loss affected non-significantly in case of noodles. Expansion ratio and density of extruded snacks was affected non significantly by blending source and blending level. However, significant effect was observed on amperage, pressure, yield and overall acceptability of extruded snacks. Acceptable extruded products (noodles and extruded snacks) could be produced by blending corn byproducts with semolina upto 10% level.

Giant seafloor craters formed by hydrate-controlled large-scale methane expulsion from the Arctic seafloor after ice sheet retreat

NASA Astrophysics Data System (ADS)

Andreassen, K.; Hubbard, A.; Patton, H.; Vadakkepuliyambatta, S.; Winsborrow, M.; Plaza-Faverola, A. A.; Serov, P.

2017-12-01

Large-scale methane releases from thawing Arctic gas hydrates is a major concern, yet the processes and fluxes involved remain elusive. We present geophysical data indicating two contrasting processes of natural methane emissions from the seafloor of the northern Barents Sea, Polar North Atlantic. Abundant gas flares, acoustically imaged in the water column reveal slow, gradual release of methane bubbles, a process that is commonly documented from nearby areas, elsewhere in the Arctic and along continental margins worldwide. Conversely, giant craters across the study area indicate a very different process. We propose that these are blow-out craters, formed through large-scale, abrupt methane expulsion induced when gas hydrates destabilized after the Barents Sea Ice Sheet retreated from the area. The data reveal over 100 giant seafloor craters within an area of 440 km2. These are up to 1000 m in diameter, 30 m deep and with a semi-circular to elliptical shape. We also identified numerous large seafloor mounds, which we infer to have formed by the expansion of gas hydrate accumulations within the shallow subsurface, so-called gas hydrate pingos. These are up to 1100 m wide and 20 m high. Smaller craters and mounds < 200 m wide and with varying relief are abundant across the study site. The empirical observations and analyses are combined with numerical modelling of ice sheet, isostatic and gas hydrate evolution and indicate that during glaciation, natural gas migrating from underlying hydrocarbon reservoirs was stored as subglacial gas hydrates. On ice sheet retreat, methane from these hydrate reservoirs and underlying free gas built up and abruptly released, forming the giant mounds and craters observed in the study area today. Petroleum basins are abundant beneath formerly and presently glaciated regions. We infer that episodes of subglacial sequestration of gas hydrates and underlying free gas and subsequent abrupt expulsions were common and widespread throughout Quaternary glacial cycles. The presented conceptual model for the evolution of giant craters can also serve as an analogue for future destabilization of glacially influenced hydrate reservoirs.

Digestible, metabolizable, and net energy of camelina cake fed to growing pigs and additivity of energy in mixed diets.

PubMed

Kim, J W; Koo, B; Nyachoti, C M

2017-09-01

This experiment was conducted to determine the DE, ME, and NE contents of camelina cake (CC) and to test the hypothesis that dietary glucosinolates originating from CC will affect the additivity of energy in mixed diets containing different inclusion levels of corn, soybean meal (SBM), and CC. A total of 30 growing barrows ([Yorkshire × Landrace] × Duroc) with a mean BW of 16.8 kg (SD 1.4) were randomly allotted to 1 of 5 treatments with 6 replicates per treatment. Pigs were fed experimental diets for 16 d, including 10 d for adaptation and 6 d for total collection of feces and urine. The 5 experimental diets consisted of 3 corn-based diets to determine the DE, ME, and NE of the 3 ingredients (corn, SBM, and CC) and 2 mixed diets to test the additivity of DE, ME, and NE. The corn diet contained 97.52% corn; the SBM diet contained 67.52% corn and 30.0% SBM; the CC diet contained 67.52% corn and 30.0% CC; the Mixed diet 1 contained 67.52% corn, 20.0% SBM, and 10.0% CC; and the Mixed diet 2 contained 67.25% corn, 10.0% SBM, and 20.0% CC. Vitamins and minerals were included in the diets to meet or exceed the requirements for growing pigs (). Pigs were fed their assigned diets at 550 kcal ME/kg BW per day on the basis of BW on d 1, 5, and 10, which was close to ad libitum intake. Pigs had free access to water. Determined DE, ME, and NE contents of corn were 3,348, 3,254, and 2,579 kcal/kg, respectively; those of SBM were 3,626, 3,405, and 2,129 kcal/kg, respectively; and those of CC were 3,755, 3,465, and 2,383 kcal/kg, respectively. No differences between the predicted and determined DE, ME, and NE were observed in the 2 mixed diets. In conclusion, DE, ME, and calculated NE content of CC fed to growing pigs were 3,755, 3,465, and 2,383 kcal/kg (as-fed basis), respectively. In addition, additivity of DE, ME, and calculated NE was observed in the mixed diets containing corn, SBM, and CC, which indicates that dietary glucosinolates originating from up to 30% of CC inclusion do not affect DE, ME, and calculated NE of diets.

Magnetic resonance microscopy for assessment of morphological changes in hydrating hydroxypropylmethylcellulose matrix tablets in situ-is it possible to detect phenomena related to drug dissolution within the hydrated matrices?

PubMed

Kulinowski, Piotr; Młynarczyk, Anna; Jasiński, Krzysztof; Talik, Przemysław; Gruwel, Marco L H; Tomanek, Bogusław; Węglarz, Władysław P; Dorożyński, Przemysław

2014-09-01

So far, the hydrated part of the HPMC matrix has commonly been denoted as a "gel" or "pseudogel" layer. No MRI-based results have been published regarding observation of internal phenomena related to drug dissolution inside swelling polymeric matrices during hydration. The purpose of the study was to detect such phenomena. Multiparametric, spatially and temporally resolved T2 MR relaxometry, in situ, was applied to study formation of the hydration progress in HPMC matrix tablets loaded with L-dopa and ketoprofen using a 11.7 T MRI system. Two spin-echo based pulse sequences were used, one of them specifically designed to study short T2 signals. Two components in the T2 decay envelope were estimated and spatial distributions of their parameters, i.e. amplitudes and T2 values, were obtained. Based on the data, different region formation patterns (i.e. multilayer structure) were registered depending on drug presence and solubility. Inside the matrix with incorporated sparingly soluble drug a specific layer formation due to drug dissolution was detected, whereas a matrix with very slightly soluble drug does not form distinct external "gel-like" layer. We have introduced a new paradigm in the characterization of hydrating matrices using (1)H MRI methods. It reflects molecular mobility and concentration of water inside the hydrated matrix. For the first time, drug dissolution related phenomena, i.e. particular front and region formation, were observed by MRI methods.

Seismic evidence of gas hydrates, multiple BSRs and fluid flow offshore Tumbes Basin, Peru

NASA Astrophysics Data System (ADS)

Auguy, Constance; Calvès, Gérôme; Calderon, Ysabel; Brusset, Stéphane

2017-12-01

Identification of a previously undocumented hydrate system in the Tumbes Basin, localized off the north Peruvian margin at latitude of 3°20'—4°10'S, allows us to better understand gas hydrates of convergent margins, and complement the 36 hydrate sites already identified around the Pacific Ocean. Using a combined 2D-3D seismic dataset, we present a detailed analysis of seismic amplitude anomalies related to the presence of gas hydrates and/or free gas in sediments. Our observations identify the occurrence of a widespread bottom simulating reflector (BSR), under which we observed, at several sites, the succession of one or two BSR-type reflections of variable amplitude, and vertical acoustic discontinuities associated with fluid flow and gas chimneys. We conclude that the uppermost BSR marks the current base of the hydrate stability field, for a gas composition comprised between 96% methane and 4% of ethane, propane and pure methane. Three hypotheses are developed to explain the nature of the multiple BSRs. They may refer to the base of hydrates of different gas composition, a remnant of an older BSR in the process of dispersion/dissociation or a diagenetically induced permeability barrier formed when the active BSR existed stably at that level for an extended period. The multiple BSRs have been interpreted as three events of steady state in the pressure and temperature conditions. They might be produced by climatic episodes since the last glaciation associated with tectonic activity, essentially tectonic subsidence, one of the main parameters that control the evolution of the Tumbes Basin.

The association of hydrogen with sulfur on Mars across latitudes, longitudes, and compositional extremes

NASA Astrophysics Data System (ADS)

Karunatillake, Suniti; Wray, James J.; Gasnault, Olivier; McLennan, Scott M.; Deanne Rogers, A.; Squyres, Steven W.; Boynton, William V.; Skok, J. R.; Button, Nicole E.; Ojha, Lujendra

2016-07-01

Midlatitudinal hydrated sulfates on Mars may influence brine pH, atmospheric humidity, and collectively water activity. These factors affect the habitability of the planetary subsurface and the preservation of relict biomolecules. Regolith at grain sizes smaller than gravel, constituting the bulk of the Martian subsurface at regional scales, may be a primary repository of chemical alteration, mechanical alteration, and biosignatures. The Mars Odyssey Gamma Ray Spectrometer with hundreds of kilometers of lateral resolution and compositional sensitivity to decimeter depth provides unique insight into this component of the regolith, which we call soil. Advancing the globally compelling association between H2O and S established by our previous work, we characterize latitudinal variations in the association between H and S, as well as in the hydration state of soil. Represented by H2O:S molar ratios, the hydration state of candidate sulfates increases with latitude in the northern hemisphere. In contrast, hydration states generally decrease with latitude in the south. Furthermore, we observe that H2O concentration may affect the degree of sulfate hydration more than S concentration. Limited H2O availability in soil-atmosphere exchange and in subsurface recharge could explain such control exerted by H2O on salt hydration. Differences in soil thickness, ground ice table depths, atmospheric circulation, and insolation may contribute to hemispheric differences in the progression of hydration with latitude. Our observations support chemical association of H2O with S in the southern hemisphere as suggested by Karunatillake et al. (2014), including the possibility of Fe sulfates as a key mineral group.

Hydrate Formation in Gas-Rich Marine Sediments: A Grain-Scale Model

NASA Astrophysics Data System (ADS)

Holtzman, R.; Juanes, R.

2009-12-01

We present a grain-scale model of marine sediment, which couples solid- and multiphase fluid-mechanics together with hydrate kinetics. The model is applied to investigate the spatial distribution of the different methane phases - gas and hydrate - within the hydrate stability zone. Sediment samples are generated from three-dimensional packs of spherical grains, mapping the void space into a pore network by tessellation. Gas invasion into the water-saturated sample is simulated by invasion-percolation, coupled with a discrete element method that resolves the grain mechanics. The coupled model accounts for forces exerted by the fluids, including cohesion associated with gas-brine surface tension. Hydrate growth is represented by a hydrate film along the gas-brine interface, which increases sediment cohesion by cementing the grain contacts. Our model of hydrate growth includes the possible rupture of the hydrate layer, which leads to the creation of new gas-water interface. In previous work, we have shown that fine-grained sediments (FGS) exhibit greater tendency to fracture, whereas capillary invasion is the preferred mode of methane gas transport in coarse-grained sediments (CGS). The gas invasion pattern has profound consequences on the hydrate distribution: a larger area-to-volume ratio of the gas cluster leads to a larger drop in gas pressure inside the growing hydrate shell, causing it to rupture. Repeated cycles of imbibition and hydrate growth accompanied by trapping of gas allow us to determine the distribution of hydrate and gas within the sediment as a function of time. Our pore-scale model suggests that, even when film rupture takes place, the conversion of gas to hydrate is slow. This explains two common field observations: the coexistence of gas and hydrate within the hydrate stability zone in CGS, and the high methane fluxes through fracture conduits in FGS. These results demonstrate the importance of accounting for the strong coupling among multiphase flow, sediment mechanics, and hydrate formation. Our model explains the remarkable differences in hydrate distribution and saturation between fine- and coarse-grained sediments, and promotes the quantitative understanding of the role of methane hydrate in seafloor stability and the global carbon cycle, including the size of the hydrate energy resource, and estimates of methane fluxes into the ocean and the atmosphere.

Types and Evolution of Gas Hydrate System along the Tectonically Active Zones of the Western Pacific: Nankai Trough vs. Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Tomaru, H.; Takeuchi, L.; Hiruta, A.; Ishizaki, O.; Aoyama, C.; Machiyama, H.; Goto, T.

2007-12-01

A series of sea-going surveys of marine gas hydrates around Japan Islands for more than a decade has revealed characteristic and contrasting features and evolution of gas hydrate system between the Nankai subduction zone and the Joetsu Basin of Japan Sea. Gas hydrate of the Nankai trough largely occurs as pore-filling type, laterally extending in turbidites. Methane is depleted in C-13, mostly derived from microbial brake-down of organic matters. Strong and continuous BSRs occur at around 270 mbsf, corresponding to the base of gas hydrate stability (BGHS). Furthermore, double BSRs with weak reflector (BSR-2) 20-30 m below BSR appear in uplifting knolls. BSR-2 is explained as a relic BSR, which coincides with BGHS. Combination effects of uplifting of gas hydrate bearing sediments and sea-level fall are likely to have caused shoaling of BGHS and BSRs, dissociation of gas hydrate between old and new BRSs, and further accumulation of gas hydrates above BSR. Thus the recycling of methane at BGHS triggered by glacial sea level fall contributed for the development of subsurface gas hydrate deposits. Joetsu basin is located on a newly formed convergent boundary between Eurasia and Philippine Sea Plates. Well-defined circular pockmarks with ca.500 m in diameter develop on the folded and faulted Umitaka spur and Joetsu knoll in the basin. A number of circular swells and mounds, 200-500 m in diameter, have been also recognized nearby the pockmarks. Thus the Umitaka spur and perhaps Joetsu knoll are characterized by rough topography of pockmarks and mounds. Methane of plumes and gas hydrate originates in deep-seated thermogenic gases with relatively heavy carbon. 3D seismic profiles clearly depict gas chimney structures below pockmark-mound zones, and gigantic methane plumes stand on the mounds not in the pockmarks. Pockmarks are often considered as vent holes, however, those of the Joestu Basin are quite. BSRs occur at about 150 mbsr, corresponding to very high heat flow, and are widely distributed throughout the area, while no double BSRs are observed. BSRs within gas chimneys are very strong and often exhibit pull-up structure. A number of piston corers have recovered chunks of massive gas hydrate from the mounds. ROV dives observed gas hydrates exposed atop the mounds. Furthermore, electric ocean floor survey has revealed that sediments below the pockmark-mound zones were not conductive. These lines of evidence suggest that the mounds are more-or-less composed of or at least contain significant amounts of methane. Sea-level fall during the last glacial, 120 m in Japan Sea, should have caused instability of gas hydrate, in particular, those within pockmarks. Pull-up structures within the chimney seem to support the model that the mounds are gas hydrate dome and the pockmark, probably a relic hydrate mound. Glacial sea level fall should have caused massive dissociation of subsurface methane hydrate as in case of the Nankai trough. However the methane from the dissociation of massive hydrate in the chimney should escape to seawater to form a crater-like depression pockmarks. Considering active venting, gigantic plumes, inferred violent venting and perhaps floating of massive gas hydrates, gas hydrate deposits are to be formed during warmer, high-sea level periods, and episodic dissociation and massive emission of methane to ocean/atmosphere system.

Characterization of Methane Hydrate Growth from Aqueous Solution by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Chou, I.; Lu, W.; Yuan, S.; Li, J.; Burruss, R. C.

2009-12-01

We observed the growth of methane hydrate from aqueous solution in fused silica capillaries near room temperature (RT) in two different experiments. In the first, we sealed methane together with ~2 wt% Na2SO4 solution in a fused silica capillary (0.3x0.3 mm cross-section with 0.05x0.05 mm cavity, and ~6 cm long), using the method of Chou et al. (2008, Geochim. Cosmochim. Acta, 72, 2517). The hydrate, liquid, and vapor coexist at ~23 °C and ~36.5 MPa. The behavior of two methane bubbles, one of which was enclosed by a hydrate crystal and the other near a small hydrate crystal, was monitored. These two bubbles are the only methane sources near the hydrate crystals. The system was slowly cooled to RT (~21 °C), and images were recorded continuously for a period of ~1.5 hours, together with temperature and time information. The images show the exposed bubble decreased in size, while both of the hydrate crystals increased in size, which was caused by the transfer of methane in solution. According to our previous report (Fig. 8 of Lu et al., 2008, Geochim. Cosmochim. Acta, 72, 412), the concentrations of methane in the solution near the exposed bubble are higher than those near the hydrate crystals. Most of the dissolved methane, transferred down the concentration gradient, was consumed and encaged in the nearby crystal, with only a small fraction of methane being consumed by the more distant crystal. Eventually, the exposed vapor bubble was totally consumed, but the bubble shielded by the hydrate crystal remained. This shows hydrate can grow from dissolved methane in the solution far away from free gas. In the 2nd experiment, we sealed methane, together with pure H2O and glass beads (0.04 to 0.07 mm in dia.), in a fused silica capillary (0.3 mm OD, 0.1 mm ID, and ~6 cm long) using the method cited above. We separated the vapor phase from the solution and glass beads by centrifuging the sealed capsule, then imposed a T gradient to the sample by cooling the solution end of the capsule to ~0 °C. It is difficult to recognize the nucleation and growth of hydrate crystals under a microscope, but Raman spectroscopy was used to identify and map the distribution of hydrate crystals along the capsule. Near the original vapor-aqueous phase boundary (V-A B), Raman signals show 100% methane hydrate. However, the lack of dissolved methane in the solution further away from the V-A B limited the growth of hydrate, as indicated by the increase in water/hydrate ratio when the Raman spectrum, which combines signals from both water and hydrate, was collected further away from the V-A B. We are investigating other possible ways to map the distribution of hydrate crystals around the glass beads, including x-ray computed tomography, to understand the nature of methane hydrate crystals that grow around grains in marine sediments from pore water. These observations will improve our ability to interpret the geophysical responses (e.g., electric and acoustic signals) obtained from hydrate-bearing sediments in the field.

Estimation of gas hydrate saturation using isotropic and anisotropic models at the location selected after measurement of seismic quality factor

NASA Astrophysics Data System (ADS)

Mundhra, A.; Sain, K.; Shankar, U.

2012-12-01

The Indian National Gas Hydrate Program Expedition (NGHP) 01 discovered gas hydrate in unconsolidated sediments at several drilling sites along the continental margins of Krishna-Godavari Basin, India. Presence of gas hydrate reduces the attenuation of travelling seismic waves which can be measured by estimation of seismic quality factor (Dasgupta and Clark, 1998). Here, we use log spectral ratio method (Sain et al, 2009) to compute quality factor at three locations, among which two have strong and one has no bottom simulating reflector (BSR), along seismic cross-line near one of the drilling site. Interval quality factor for three submarine sedimentary layers bounded by seafloor, BSR, one reflector above and another reflector below the BSR has been measured. To compute quality factor, unprocessed pre-stack seismic data has been used to avoid any influence of processing sequence. We have estimated that interval quality factor lies within 200-220 in the interval having BSR while it varies within 90-100 in other intervals. Thereby, high interval quality factor ascertains that observed BSR is due to presence of gas hydrates. We have performed rock physics modelling by using isotropic and anisotropic models, to quantitatively estimate gas hydrate saturation at one of the location where an interval has high quality factor. Abruptly high measured resistivity and high P-wave velocity in the interval, leads to towering hydrate saturation (Archie,1942 and Helegrud et al, 1999) in comparison to lower gas hydrate saturations estimated by pressure core and chlorinity measurements. Overestimation of saturation is attributed to presence of near vertical fractures that are identified from logging-while-drilling resistivity images. We have carried out anisotropic modeling (Kennedy and Herrick, 2004 and Lee,2009) by incorporating fracture volume and fracture porosity to estimate hydrate saturation and have observed that modeled gas hydrate saturations agree with the lower gas hydrate saturations obtained from pressure core and chlorinity measurements. Therefore, we find that 1) quality factor is significantly higher in the interval bearing gas hydrates and is a useful tool to discover hydrate deposits, 2) anisotropy due to presence of near vertical hydrate filled fractures translates into elevated saturation because of high measured resistivity and velocity and 3) anisotropic model greatly corrects the saturation estimates in fractured medium. References: Archie, G.E., 1942. Petroleum Transactions of AIME, 146, 54-62. Dasgupta, R., Clark, R.A., 1998. Geophysics 63, 2120-2128. Kennedy, W.D., Herrick, D.C., 2004. Petrophysics 45, 38-58. Lee, M.W., 2009. U.S. Geological Survey Scientific Investigations Report 2009-5141, 13. Sain, K., Singh, A.K., Thakur, N.K., Khanna, R.K., 2009.Marine Geophysical Researches 30, 137-145.

Gender- and hydration- associated differences in the physiological response to spinning.

PubMed

Ramos-Jiménez, Arnulfo; Hernández-Torres, Rosa Patricia; Wall-Medrano, Abraham; Torres-Durán, Patricia Victoria; Juárez-Oropeza, Marco Antonio; Viloria, María; Villalobos-Molina, Rafael

2014-03-01

There is scarce and inconsistent information about gender-related differences in the hydration of sports persons, as well as about the effects of hydration on performance, especially during indoor sports. To determine the physiological differences between genders during in indoor physical exercise, with and without hydration. 21 spinning sportspeople (12 men and 9 women) participated in three controlled, randomly assigned and non-sequential hydration protocols, including no fluid intake and hydration with plain water or a sports drink (volume adjusted to each individual every 15 min), during 90 min of spinning exercise. The response variables included body mass, body temperature, heart rate and blood pressure. During exercise without hydration, men and women lost ~2% of body mass, and showed higher body temperature (~0.2°C), blood pressure (~4 mmHg) and heart rate (~7 beats/min) compared to exercises with hydration. Body temperature and blood pressure were higher for men than for women during exercise without hydration, differences not observed during exercise with hydration. Between 42-99% of variance in body temperature, blood pressure and heart rate could be explained by the physical characteristics of subjects and the work done. During exercise with hydration (either with water or sport drink), the physiological response was similar for both genders. Exercise without hydration produced physical stress, which could be prevented with either of the fluids (plain water was sufficient). Gender differences in the physiological response to spinning (body temperature, mean blood pressure and heart rate) can be explained in part by the distinct physical characteristics of each individual. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

USGS Publications Warehouse

Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

2004-01-01

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

In Situ Raman Detection of Gas Hydrates Exposed on the Seafloor of the South China Sea

NASA Astrophysics Data System (ADS)

Zhang, Xin; Du, Zengfeng; Luan, Zhendong; Wang, Xiujuan; Xi, Shichuan; Wang, Bing; Li, Lianfu; Lian, Chao; Yan, Jun

2017-10-01

Gas hydrates are usually buried in sediments. Here we report the first discovery of gas hydrates exposed on the seafloor of the South China Sea. The in situ chemical compositions and cage structures of these hydrates were measured at the depth of 1,130 m below sea level using a Raman insertion probe (RiP-Gh) that was carried and controlled by a remotely operated vehicle (ROV) Faxian. This in situ analytical technique can avoid the physical and chemical changes associated with the transport of samples from the deep sea to the surface. Natural gas hydrate samples were analyzed at two sites. The in situ spectra suggest that the newly formed hydrate was Structure I but contains a small amount of C3H8 and H2S. Pure gas spectra of CH4, C3H8, and H2S were also observed at the SCS-SGH02 site. These data represent the first in situ proof that free gas can be trapped within the hydrate fabric during rapid hydrate formation. We provide the first in situ confirmation of the hydrate growth model for the early stages of formation of crystalline hydrates in a methane-rich seafloor environment. Our work demonstrates that natural hydrate deposits, particularly those in the early stages of formation, are not monolithic single structures but instead exhibit significant small-scale heterogeneities due to inclusions of free gas and the surrounding seawater, there inclusions also serve as indicators of the likely hydrate formation mechanism. These data also reinforce the importance of correlating visual and in situ measurements when characterizing a sampling site.

3-D basin-scale reconstruction of natural gas hydrate system of the Green Canyon, Gulf of Mexico

NASA Astrophysics Data System (ADS)

Burwicz, Ewa; Reichel, Thomas; Wallmann, Klaus; Rottke, Wolf; Haeckel, Matthias; Hensen, Christian

2017-05-01

Our study presents a basin-scale 3-D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin reconstruction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics, and associated multistage fault development. The resulting 3-D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (>80 vol %) at the base of the gas hydrate stability zone (GHSZ) is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intrasalt minibasins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upward to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ˜3256 Mt of gas hydrate, which is equivalent to ˜340 Mt of carbon (˜7 × 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Methane Hydrate Formation in Thick Sand Reservoirs: Long-range Gas Transport or Short-range Methane Diffusion?

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2016-12-01

We developed two 2-D numerical models to simulate hydrate formation by long range methane gas transport and short-range methane diffusion. We interpret that methane hydrates in thick sands are most likely formed by long range gas transport where methane gas is transported upward into the hydrate stability zone (HSZ) under buoyancy and locally forms hydrate to its stability limit. In short-range methane diffusion, methane is generated locally by biodegradation of organic matter in mud and diffused into bounding sands where it forms hydrate. We could not simulate enough methane transport by diffusion to account for its observed concentration in thick sands. In our models, we include the capillary effect on dissolved methane solubility and on the hydrate phase boundary, sedimentation and different compaction in sand and mud, fracture generation as well as the fully coupled multiphase flow and multicomponent transport. We apply our models to a 12 meter-thick hydrate-bearing sand layer at Walker Ridge 313, Northern Gulf of Mexico. With the long-range gas transport, hydrate saturation is greater than 90% and salinity is increased from seawater to about 8 wt.% through the entire sand. With short-range diffusion, hydrate saturation is more than 90% at the sand base and is less than 10% in the overlying section; salinity is close to seawater when sand is deposited to 800 meter below seafloor by short-range methane diffusion. With short-range diffusion, the amount of hydrate formed is much less than that interpreted from the well log data. Two transient gas layers separated by a hydrate layer are formed from short-range diffusion caused by capillary effect. This could be interpreted as a double bottom simulating reflector. This study provides further insights into different hydrate formation mechanisms, and could serve as a base to confirm the hydrate formation mechanism in fields.

Concentration of Natural Gas Hydrate Beneath the Permafrost Zone: Implications for Geochemical and Hydrologic Investigations

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Namikawa, T.

2004-12-01

Gas hydrates are ice-like solids made of water molecules containing various gas molecules. The geological evaluations have suggested worldwide methane contents of gas hydrate beneath deep sea floors as well as permafrost-related zones to about twice the total reserves of conventional and unconventional hydrocarbon. Scientific and economic interests are increasing in gas hydrate as a new energy resource and a potential greenhouse gas. In 1998 and 2002 Mallik wells were drilled in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data, anomalies of chloride contents in pore waters, core temperature depression as well as visible gas hydrates have confirmed the highly saturated pore-space hydrate as intergranular pore filling within sandy layers, whose saturations are higher than 70% in pore volume. Muddy sediments scarcely contain gas hydrate. The Nankai Trough runs along the Japanese Island, where forearc basins and accretionary prisms developed extensively and BSRs (bottom simulating reflectors) have been recognized widely. The METI Nankai Trough wells in 2000 also revealed the presence of pore-space hydrate filling intergranular pore of sandy layers. It is remarked that there are many similar features in appearance and characteristics between the Mallik and Nankai Trough areas with observations of well-interconnected and highly saturated pore-space hydrate. It is necessary for evaluating subsurface fluid flow behaviors to know both porosity and permeability of gas hydrate-bearing sandy sediments, and measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sands revealed important geologic and sedimentologic controls on the formation and concentration of gas hydrate. It is suggested that the distribution of a porous and coarser-grained sandy sediments is one of the most important factors to control the occurrence of gas hydrates, as well as physicochemical conditions.

Effect of Temperature and Hydration Level on Purple Membrane Dynamics Studied Using Broadband Dielectric Spectroscopy from Sub-GHz to THz Regions.

PubMed

Yamamoto, Naoki; Ito, Shota; Nakanishi, Masahiro; Chatani, Eri; Inoue, Keiichi; Kandori, Hideki; Tominaga, Keisuke

2018-02-01

To investigate the effects of temperature and hydration on the dynamics of purple membrane (PM), we measured the broadband complex dielectric spectra from 0.5 GHz to 2.3 THz using a vector network analyzer and terahertz time-domain spectroscopy from 233 to 293 K. In the lower temperature region down to 83 K, the complex dielectric spectra in the THz region were also obtained. The complex dielectric spectra were analyzed through curve fitting using several model functions. We found that the hydrated states of one relaxational mode, which was assigned as the coupled motion of water molecules with the PM surface, began to overlap with the THz region at approximately 230 K. On the other hand, the relaxational mode was not observed for the dehydrated state. On the basis of this result, we conclude that the protein-dynamical-transition-like behavior in the THz region is due to the onset of the overlap of the relaxational mode with the THz region. Temperature hysteresis was observed in the dielectric spectrum at 263 K when the hydration level was high. It is suggested that the hydration water behaves similarly to supercooled liquid at that temperature. The third hydration layer may be partly formed to observe such a phenomenon. We also found that the relaxation time is slower than that of a globular protein, lysozyme, and the microscopic environment in the vicinity of the PM surface is suggested to be more heterogeneous than lysozyme. It is proposed that the spectral overlap of the relaxational mode and the low-frequency vibrational mode is necessary for the large conformational change of protein.

Antioxidant and antiproliferative activity of blue corn and tortilla from native maize.

PubMed

Herrera-Sotero, Mónica Y; Cruz-Hernández, Carlos D; Trujillo-Carretero, Carolina; Rodríguez-Dorantes, Mauricio; García-Galindo, Hugo S; Chávez-Servia, José L; Oliart-Ros, Rosa M; Guzmán-Gerónimo, Rosa I

2017-10-30

Blue corn is a cereal rich in phenolic compounds used to make blue tortillas. Tortillas are an important part of the Mexican diet. Blue corn and tortilla represent an important source of the natural antioxidants anthocyanins. However, studies on their biological activity on cancer cell lines are limited. The goal of this study was to evaluate the antioxidant and antiproliferative activity of blue corn and tortilla on different cancer cell lines. Total polyphenol content, monomeric anthocyanins, and antioxidant activity by the DPPH and TBARS methods of blue corn and tortilla were determined. The anthocyanin profile of tortilla was obtained by means of HPLC-ESI-MS. The antiproliferative activity of blue corn and tortilla extract on HepG2, H-460, Hela, MCF-7 and PC-3 was evaluated by the MTT assay. Blue corn had higher content of total polyphenols and monomeric anthocyanins as well as lower percentage of polymeric color than tortilla; however, both showed similar antioxidant activity by DPPH. In addition, although a higher degradation of anthocyanins was observed on tortilla extract, both extracts inhibited lipid peroxidation (IC50) at a similar concentration. The anthocyanin profile showed 28 compounds which are primarily derived from cyanidin, including acylated anthocyanins and proanthocyanidins. Blue corn and tortilla extracts showed antiproliferative effects against HepG2, H-460, MCF-7 and PC-3 cells at 1000 μg/mL, however Hela cells were more sensitive at this concentration. This is the first report to demonstrate anticancer properties in vitro of tortilla derived from blue corn, suggesting that this product has beneficial health effects. In addition, blue corn could be a potential source of nutraceuticals with anticancer activity.

Elastic velocity models for gas-hydrate-bearing sediments-a comparison

NASA Astrophysics Data System (ADS)

Chand, Shyam; Minshull, Tim A.; Gei, Davide; Carcione, José M.

2004-11-01

The presence of gas hydrate in oceanic sediments is mostly identified by bottom-simulating reflectors (BSRs), reflection events with reversed polarity following the trend of the seafloor. Attempts to quantify the amount of gas hydrate present in oceanic sediments have been based mainly on the presence or absence of a BSR and its relative amplitude. Recent studies have shown that a BSR is not a necessary criterion for the presence of gas hydrates, but rather its presence depends on the type of sediments and the in situ conditions. The influence of hydrate on the physical properties of sediments overlying the BSR is determined by the elastic properties of their constituents and on sediment microstructure. In this context several approaches have been developed to predict the physical properties of sediments, and thereby quantify the amount of gas/gas hydrate present from observed deviations of these properties from those predicted for sediments without gas hydrate. We tested four models: the empirical weighted equation (WE); the three-phase effective-medium theory (TPEM); the three-phase Biot theory (TPB) and the differential effective-medium theory (DEM). We compared these models for a range of variables (porosity and clay content) using standard values for physical parameters. The comparison shows that all the models predict sediment properties comparable to field values except for the WE model at lower porosities and the TPB model at higher porosities. The models differ in the variation of velocity with porosity and clay content. The variation of velocity with hydrate saturation is also different, although the range is similar. We have used these models to predict velocities for field data sets from sediment sections with and without gas hydrates. The first is from the Mallik 2L-38 well, Mackenzie Delta, Canada, and the second is from Ocean Drilling Program (ODP) Leg 164 on Blake Ridge. Both data sets have Vp and Vs information along with the composition and porosity of the matrix. Models are considered successful if predictions from both Vp and Vs match hydrate saturations inferred from other data. Three of the models predict consistent hydrate saturations of 60-80 per cent from both Vp and Vs from log and vertical seismic profiling data for the Mallik 2L-38 well data set, but the TPEM model predicts 20 per cent higher saturations, as does the DEM model with a clay-water starting medium. For the clay-rich sediments of Blake Ridge, the DEM, TPEM and WE models predict 10-20 per cent hydrate saturation from Vp data, comparable to that inferred from resistivity data. The hydrate saturation predicted by the TPB model from Vp is higher. Using Vs data, the DEM and TPEM models predict very low or zero hydrate saturation while the TPB and WE models predict hydrate saturation very much higher than those predicted from Vp data. Low hydrate saturations are observed to have little effect on Vs. The hydrate phase appears to be connected within the sediment microstructure even at low saturations.

Impact of welan gum on tricalcium aluminate-gypsum hydration

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

Ma Lei, E-mail: malei198713@163.com; Zhao Qinglin, E-mail: zhaoqinglin@whut.edu.cn; Yao Chukang

The retarding effect of welan gum on tricalcium aluminate-gypsum hydration, as a partial system of ordinary Portland cement (OPC) hydration, was investigated with several methods. The tricalcium aluminate-gypsum hydration behavior in the presence or absence of welan gum was researched by field emission gun scanning electron microscopy, X-ray diffraction and zeta potential analysis. Meanwhile, we studied the surface electrochemical properties and adsorption characteristics of welan gum by utilizing a zeta potential analyzer and UV-VIS absorption spectrophotometer. By adding welan gum, the morphology change of ettringite and retardation of hydration stages in tricalcium aluminate-gypsum system was observed. Moreover, we detected themore » adsorption behavior and zeta potential inversion of tricalcium aluminate and ettringite, as well as a rapid decrease in the zeta potential of tricalcium aluminate-gypsum system. The reduction on nucleation rate of ettringite and hydration activity of C{sub 3}A was also demonstrated. Thus, through the adsorption effect, welan gum induces a retarding behavior in tricalcium aluminate-gypsum hydration. Highlights: Black-Right-Pointing-Pointer Adsorption characteristics of welan gum on C{sub 3}A and ettringite have been studied. Black-Right-Pointing-Pointer C{sub 3}A-gypsum hydration behavior and the hydration products are examined in L/S = 3. Black-Right-Pointing-Pointer Welan gum retards the process of C{sub 3}A-gypsum hydration. Black-Right-Pointing-Pointer The addition of welan gum changes the nucleation growth of ettringite.« less

Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces.

PubMed

Smith, Benjamin J; Rawal, Aditya; Funkhouser, Gary P; Roberts, Lawrence R; Gupta, Vijay; Israelachvili, Jacob N; Chmelka, Bradley F

2011-05-31

Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state (1)H, (13)C, (29)Si, and (27)Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications.

Hydration properties of regioselectively etherified celluloses monitored by 2H and 13C solid-state MAS NMR spectroscopy.

PubMed

Larsen, Flemming H; Schöbitz, Michael; Schaller, Jens

2012-06-20

The hydration properties of 2,3-O-hydroxypropylcellulose (HPC) and 2,3-O-hydroxyethylcellulose (HEC) were analyzed by multi-nuclear solid-state MAS NMR spectroscopy. By 13C single-pulse (SP) MAS and cross-polarization (CP) MAS NMR, differences between the immobile regions and all parts of the polysaccharides were detected as a function of hydration. Complementary information about the water environments was observed by 2H MAS NMR. By this approach it was demonstrated that side chains in 2,3-O-HPC and 2,3-O-HEC were easier to hydrate than the cellulose backbone. Furthermore the motion of water was more restricted (slower) in 2,3-O-HPC than in 2,3-O-HEC. For both polysaccharides the hydration could be explained by a two-step process: in step one increased ordering of the immobile regions occurs after which the entire polymer is hydrated in step two. Copyright © 2012 Elsevier Ltd. All rights reserved.

Microscopic character of marine sediment containing disseminated gas hydrate. Examples from the Blake Ridge and the Middle America Trench

USGS Publications Warehouse

Lorenson, T.D.

2000-01-01

The presence of disseminated gas hydrate was inferred based on pore fluid geochemistry and downhole logging data, but was rarely observed at Ocean Drilling Program (ODP) Leg 164 (Blake Ridge), and Leg 170 (Middle America Trench, offshore from Costa Rica) drilling sites. Gas hydrate nucleation is likely to occur first in larger voids rather than in constricted pore space, where capillary forces depress the temperature-pressure stability field for gas hydrate formation. Traditional macroscopic descriptions of sediment fail to detect the microscopic character of primary and secondary porosity in sediment hosting disseminated gas hydrate. Light transmission and scanning electron microscopy of sediments within and below the depth of gas hydrate occurrences reveal at least four general types of primary and secondary porosity: (1) microfossils (diatoms, foraminifera, and spicules) void of infilling sediment, but commonly containing small masses of pyrite framboids; (2) infauna burrows filled with unconsolidated sand and or microfossil debris; (3) irregularly shaped pods of nonconsolidated framboidial pyrite; and (4) nonlithified volcanic ash.

Hydration Repulsion between Carbohydrate Surfaces Mediated by Temperature and Specific Ions

PubMed Central

Chen, Hsieh; Cox, Jason R.; Ow, Hooisweng; Shi, Rena; Panagiotopoulos, Athanassios Z.

2016-01-01

Stabilizing colloids or nanoparticles in solution involves a fine balance between surface charges, steric repulsion of coating molecules, and hydration forces against van der Waals attractions. At high temperature and electrolyte concentrations, the colloidal stability of suspensions usually decreases rapidly. Here, we report a new experimental and simulation discovery that the polysaccharide (dextran) coated nanoparticles show ion-specific colloidal stability at high temperature, where we observed enhanced colloidal stability of nanoparticles in CaCl2 solution but rapid nanoparticle-nanoparticle aggregation in MgCl2 solution. The microscopic mechanism was unveiled in atomistic simulations. The presence of surface bound Ca2+ ions increases the carbohydrate hydration and induces strongly polarized repulsive water structures beyond at least three hydration shells which is farther-reaching than previously assumed. We believe leveraging the binding of strongly hydrated ions to macromolecular surfaces represents a new paradigm in achieving absolute hydration and colloidal stability for a variety of materials, particularly under extreme conditions. PMID:27334145

Enhanced Hydrate Nucleation Near the Limit of Stability.

PubMed

Jimenez-Angeles, Felipe; Firoozabadi, Abbas

2015-03-30

Clathrate hydrates are crystalline structures composed of small guest molecules trapped into cages formed by hydrogen-bonded water molecules. In hydrate nucleation, water and the guest molecules may stay in a metastable fluid mixture for a long period. Metastability is broken if the concentration of the guest is above certain limit. We perform molecular dynamics (MD) simulations of supersaturated water-propane solutions close to the limit of stability. We show that hydrate nucleation can be very fast in a very narrow range of composition at moderate temperatures. Propane density fluctuations near the fluid-fluid demixing are coupled with crystallization producing en- hanced nucleation rates. This is the first report of propane-hydrate nucleation by MD simulations. We observe motifs of the crystalline structure II in line with experiments and new hydrate cages not reported in the literature. Our study relates nucleation to the fluid-fluid spinodal decomposition and demonstration that the enhanced nucleation phenomenon is more general than short range attractive interactions as suggested in nucleation of proteins.

Hydration Repulsion between Carbohydrate Surfaces Mediated by Temperature and Specific Ions

NASA Astrophysics Data System (ADS)

Chen, Hsieh; Cox, Jason R.; Ow, Hooisweng; Shi, Rena; Panagiotopoulos, Athanassios Z.

2016-06-01

Stabilizing colloids or nanoparticles in solution involves a fine balance between surface charges, steric repulsion of coating molecules, and hydration forces against van der Waals attractions. At high temperature and electrolyte concentrations, the colloidal stability of suspensions usually decreases rapidly. Here, we report a new experimental and simulation discovery that the polysaccharide (dextran) coated nanoparticles show ion-specific colloidal stability at high temperature, where we observed enhanced colloidal stability of nanoparticles in CaCl2 solution but rapid nanoparticle-nanoparticle aggregation in MgCl2 solution. The microscopic mechanism was unveiled in atomistic simulations. The presence of surface bound Ca2+ ions increases the carbohydrate hydration and induces strongly polarized repulsive water structures beyond at least three hydration shells which is farther-reaching than previously assumed. We believe leveraging the binding of strongly hydrated ions to macromolecular surfaces represents a new paradigm in achieving absolute hydration and colloidal stability for a variety of materials, particularly under extreme conditions.

Implications of observed and simulated soil carbon sequestration for management options in corn-based rotations

USDA-ARS?s Scientific Manuscript database

Managing cropping systems to sequester soil organic carbon (SOC) improves soil health and a system’s resiliency to impacts of changing climate. Our objectives were to 1) monitor SOC from a bio-energy cropping study in central Pennsylvania that included a corn-soybean-alfalfa rotation, switchgrass, a...

Implications of observed and simulated soil carbon sequestration for management options in corn-based rotations

USDA-ARS?s Scientific Manuscript database

Managing cropping systems to sequester soil organic carbon (SOC) improves soil health and a system’s resiliency to impacts of changing climate. Our objectives were to 1) monitor SOC from a bio-energy cropping study in central Pennsylvania that included a corn-soybean-alfalfa rotation, switchgrass, ...

Thermogenic methane injection via bubble transport into the upper Arctic Ocean from the hydrate-charged Vestnesa Ridge, Svalbard

NASA Astrophysics Data System (ADS)

Smith, Andrew J.; Mienert, Jürgen; Bünz, Stefan; Greinert, Jens

2014-05-01

We use new gas-hydrate geochemistry analyses, echosounder data, and three-dimensional P-Cable seismic data to study a gas-hydrate and free-gas system in 1200 m water depth at the Vestnesa Ridge offshore NW Svalbard. Geochemical measurements of gas from hydrates collected at the ridge revealed a thermogenic source. The presence of thermogenic gas and temperatures of ˜3.3°C result in a shallow top of the hydrate stability zone (THSZ) at ˜340 m below sea level (mbsl). Therefore, hydrate-skinned gas bubbles, which inhibit gas-dissolution processes, are thermodynamically stable to this shallow water depth. This was confirmed by hydroacoustic observations of flares in 2010 and 2012 reaching water depths between 210 and 480 mbsl. At the seafloor, bubbles are released from acoustically transparent zones in the seismic data, which we interpret as regions where free gas is migrating through the hydrate stability zone (HSZ). These intrusions result in vertical variations in the base of the HSZ (BHSZ) of up to ˜150 m, possibly making the shallow hydrate reservoir more susceptible to warming. Such Arctic gas-hydrate and free-gas systems are important because of their potential role in climate change and in fueling marine life, but remain largely understudied due to limited data coverage in seasonally ice-covered Arctic environments.

Shallow Methane Hydrates: Rates, Mechanisms of Formation and Environmental Significance.

NASA Astrophysics Data System (ADS)

Torres, M. E.; Trehu, A. M.

2005-05-01

Shallow gas hydrates have been identified at more than 20 locations worldwide, and are commonly associated with observations of bubble discharge at the seafloor. These deposits are host to active chemosynthetic communities and are likely to play a predominant role in energy, climate and carbon cycle issues associated with hydrate processes. Because seafloor gas hydrates are not in equilibrium with seawater, these deposits require a constant supply of methane to replace loss by continuous diffusion to bottom water. We will summarize evidence documenting that at the shallow deposits on Hydrate Ridge (OR) methane must be delivered in the free gas phase and present simple models used to infer formation rates, which are orders of magnitude higher than those for hydrates formed deeper in the sediment column (Torres et al., 2004). At Hydrate Ridge, methane gas is channeled from deep accretionary margin sequences to the gas hydrate stability zone (GHSZ) through a permeable layer that has been mapped seismically (Horizon A). High gas pressure in this horizon can drive gas through the GHSZ to the seafloor (Trehu et al., 2004). We will review current ideas that address mechanisms whereby gas migrates from Horizon A to the seafloor, including inhibition by capillary effects and the development of a high salinity front that can shift the hydrate stability field enough to allow for methane transport as a gas phase.

Pore-Scale Determination of Gas Relative Permeability in Hydrate-Bearing Sediments Using X-Ray Computed Micro-Tomography and Lattice Boltzmann Method

NASA Astrophysics Data System (ADS)

Chen, Xiongyu; Verma, Rahul; Espinoza, D. Nicolas; Prodanović, Maša.

2018-01-01

This work uses X-ray computed micro-tomography (μCT) to monitor xenon hydrate growth in a sandpack under the excess gas condition. The μCT images give pore-scale hydrate distribution and pore habit in space and time. We use the lattice Boltzmann method to calculate gas relative permeability (krg) as a function of hydrate saturation (Shyd) in the pore structure of the experimental hydrate-bearing sand retrieved from μCT data. The results suggest the krg - Shyd data fit well a new model krg = (1-Shyd)·exp(-4.95·Shyd) rather than the simple Corey model. In addition, we calculate krg-Shyd curves using digital models of hydrate-bearing sand based on idealized grain-attaching, coarse pore-filling, and dispersed pore-filling hydrate habits. Our pore-scale measurements and modeling show that the krg-Shyd curves are similar regardless of whether hydrate crystals develop grain-attaching or coarse pore-filling habits. The dispersed pore filling habit exhibits much lower gas relative permeability than the other two, but it is not observed in the experiment and not compatible with Ostwald ripening mechanisms. We find that a single grain-shape factor can be used in the Carman-Kozeny equation to calculate krg-Shyd data with known porosity and average grain diameter, suggesting it is a useful model for hydrate-bearing sand.

The hydration structure at yttria-stabilized cubic zirconia (110)-water interface with sub-Ångström resolution

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-06-15

The interfacial hydration structure of yttria-stabilized cubic zirconia (110) surface in contact with water was determined with ~0.5 Å resolution by high-resolution X-ray reflectivity measurement. The terminal layer shows a reduced electron density compared to the following substrate lattice layers, which indicates there are additional defects generated by metal depletion as well as intrinsic oxygen vacancies, both of which are apparently filled by water species. Above this top surface layer, two additional adsorbed layers are observed forming a characteristic interfacial hydration structure. The first adsorbed layer shows abnormally high density as pure water and likely includes metal species, whereas themore » second layer consists of pure water. The observed interfacial hydration structure seems responsible for local equilibration of the defective surface in water and eventually regulating the long-term degradation processes. As a result, the multitude of water interactions with the zirconia surface results in the complex but highly ordered interfacial structure constituting the reaction front.« less

Impact of Compound Hydrate Dynamics on Phase Boundary Changes

NASA Astrophysics Data System (ADS)

Osegovic, J. P.; Max, M. D.

2006-12-01

Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed systems include pipeline blockages and natural hydrate concentrations associated with upwelling fluids in marine sediments. 3) In open systems, mass can either flow into or out of a system. In such situations compound hydrate will form or decompose to re-establish chemical equilibrium. This is accomplished by 1) loading/consuming a preferred hydrate former to/from the surroundings, 2) lowering/raising the temperature of the system, and 3) increasing the local pressure. Examples of this type of system include hydrate produced for low pressure transport, depressurized or superheated hydrate settings (pipeline remediation or energy recovery), or in an industrial process where formation of compound hydrates may be used to separate and concentrate gases from a mixture. The relationship between composition and the phase boundary is as important as pressure and temperature effects. Composition is less significant for simple hydrates where the hydrate behaves as a one-component mineral, but for compound hydrate, feedback between pressure, temperature, and composition can result in complex system behavior.

Low-frequency ESR studies on permeable and impermeable deuterated nitroxyl radicals in corn oil solution.

PubMed

David Jebaraj, D; Utsumi, Hideo; Milton Franklin Benial, A

2018-04-01

Low-frequency electron spin resonance studies were performed for 2 mM concentration of deuterated permeable and impermeable nitroxyl spin probes, 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl and 3-carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy in pure water and various concentrations of corn oil solution. The electron spin resonance parameters such as the line width, hyperfine coupling constant, g factor, rotational correlation time, permeability, and partition parameter were estimated. The broadening of line width was observed for nitroxyl radicals in corn oil mixture. The rotational correlation time increases with increasing concentration of corn oil, which indicates the less mobile nature of spin probe in corn oil mixture. The membrane permeability and partition parameter values were estimated as a function of corn oil concentration, which reveals that the nitroxyl radicals permeate equally into the aqueous phase and oil phase at the corn oil concentration of 50%. The electron spin resonance spectra demonstrate the permeable and impermeable nature of nitroxyl spin probes. From these results, the corn oil concentration was optimized as 50% for phantom studies. In this work, the corn oil and pure water mixture phantom models with various viscosities correspond to plasma membrane, and whole blood membrane with different hematocrit levels was studied for monitoring the biological characteristics and their interactions with permeable nitroxyl spin probe. These results will be useful for the development of electron spin resonance and Overhauser-enhanced magnetic resonance imaging modalities in biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.

Establishment of Striacosta albicosta (Lepidoptera: Noctuidae) as a Primary Pest of Corn in the Great Lakes Region.

PubMed

Smith, J L; Baute, T S; Sebright, M M; Schaafsma, A W; DiFonzo, C D

2018-05-30

Western bean cutworm, Striacosta albicosta Smith (Lepidoptera: Noctuidae), is a pest of corn, Zea maize L., and dry edible beans, Phaseolus sp. L., native to the western United States. Following the range expansion into the U.S. Corn Belt, pheromone trap monitoring began in the Great Lakes region in 2006. The first S. albicosta was captured in Michigan in 2006 and in Ontario, Canada in 2008. Pheromone traps were used to document spread and increasing captures of S. albicosta across Michigan and Ontario until 2012. Trapping confirmed the univoltine life cycle of S. albicosta in this region and identified peak flight, typically occurring in late July. Overwintering of S. albicosta in this region was confirmed by emergence from infested fields and overwintering experiments. Multiple soil textures were infested with prepupae, and recovery was assessed throughout the winter. Overwintering success was not affected by soil texture; however, prepupae were found at greater depths in coarse-textured soils. Soil temperatures at overwintering depths did not reach the supercooling point. Injury to corn by S. albicosta increased in incidence, severity and geographic range from 2010 to 2014 in field plots. Decreasing control of injury by Cry1F corn hybrids was observed over time. These findings show that S. albicosta has established as a perennial corn pest in the Great Lakes region due to observations of overwintering success and unmanaged injury. We recommend S. albicosta obtain primary pest status in this region within regulatory framework and a resistance management plan be required for traits targeting this pest.

Properties of Cement Mortar and Ultra-High Strength Concrete Incorporating Graphene Oxide Nanosheets.

PubMed

Lu, Liulei; Ouyang, Dong

2017-07-20

In this work, the effect of graphene oxide nanosheet (GONS) additives on the properties of cement mortar and ultra-high strength concrete (UHSC) is reported. The resulting GONS-cement composites were easy to prepare and exhibited excellent mechanical properties. However, their fluidity decreased with increasing GONS content. The UHSC specimens were prepared with various amounts of GONSs (0-0.03% by weight of cement). Results indicated that using 0.01% by weight of cement GONSs caused a 7.82% in compressive strength after 28 days of curing. Moreover, adding GONSs improved the flexural strength and deformation ability, with the increase in flexural strength more than that of compressive strength. Furthermore, field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of the hardened cement paste and UHSC samples. FE-SEM observations showed that the GONSs were well dispersed in the matrix and the bonding of the GONSs and the surrounding cement matrix was strong. Furthermore, FE-SEM observation indicated that the GONSs probably affected the shape of the cement hydration products. However, the growth space for hydrates also had an important effect on the morphology of hydrates. The true hydration mechanism of cement composites with GONSs needs further study.

Importance of the rate of hydration of pharmaceutical preparations of guar gum; a new in vitro monitoring method.

PubMed

Ellis, P R; Morris, E R

1991-05-01

Dietary supplements of guar gum are known to improve blood glucose control in diabetic patients. The efficacy of guar is probably dependent mainly upon its capacity to hydrate rapidly and thus to increase viscosity in the small intestine post-prandially. Measurement of the rate of hydration in vitro might therefore be a useful index of the effectiveness of guar formulations. A simple method for monitoring the hydration rate of guar gum has been developed, which involves measuring the changes in viscosity at discrete time intervals over a period of 5 h using a Brookfield RVT rotoviscometer. Six different samples of guar gum (four pharmaceutical preparations and two food grades of guar flour) were hydrated in sealed glass jars rotated at 6 rev min-1 in order to prevent particle aggregation. Marked differences in hydration rate and ultimate (maximum) viscosity between the different guar samples were observed. Three of the four pharmaceutical preparations were lower in viscosity than the food grades of guar flour during the first 60 min of hydration. Two of the preparations hydrated so slowly that even after 5 h they attained viscosity levels of only 60% of their ultimate viscosity. These results may explain why some guar gum preparations are clinically ineffective.

Formation of Structured Water and Gas Hydrate by the Use of Xenon Gas in Vegetable Tissue

NASA Astrophysics Data System (ADS)

Ando, Hiroko; Suzuki, Toru; Kawagoe, Yoshinori; Makino, Yoshio; Oshita, Seiichi

Freezing is a valuable technique for food preservation. However, vegetables are known to be softening remarkably after freezing and thawing process. It is expected to find alternative technique instead of freezing. Recently, the application of structured water and/or gas hydrate had been attempted to prolong the preservation of vegetable. In this study, the formation process of structure water and/or gas hydrate in pure water and carrot tissue was investigated by using NMR relaxation times, T1 and T2, of which applying condition was up to 0.4MPa and 0.8MPa at 5oC. Under the pressure of 0.4MPa, no gas hydrate was appeared, however, at 0.8MPa, formation of gas hydrate was recognized in both water and carrot tissue. Once the gas hydrate formation process in carrot tissue started, T1 and T2 increased remarkably. After that, as the gas hydrate developed, then T1 and T2 turned to decrease. Since this phenomenon was not observed in pure water, it is suggested that behavior of NMR relaxation time just after the formation of gas hydrate in carrot tissue may be peculiar to compartment system such as inter and intracellular spaces.

Computation on free gas seepage and associated seabed pockmark formation

NASA Astrophysics Data System (ADS)

Su, Z.; Cathles, Lawrence M.; Chen, D. F.; Wu, N. Y.

2010-03-01

Seabed pockmarks formed by seepage of subsurface fluids are very commonly located in areas where gas is present in near-surface sediments. Especially, they are widely observed on the seafloor at hydrate regions around the world. In this paper we consider that capillary sealing is the crucial mechanism for gas entrapment, gas escape, and pockmark formation. In the hydrate system, free gas is trapped beneath the hydrate layer. The gas overpressure increases as the gas accumulates beneath the hydrate. the hydrate layer is a capillary seal. Capillary seals have the property that they fail completely when the gas pressure reaches the point that they are invaded by gas. The release of gas is thus episodic and sudden. We imagine in our model that when it occurs the venting gas will push the overlying water upward at increasingly higher velocities as the gas pipe approaches the seafloor. As the water velocity increases, the near surface sediments will become quick at a depth that is a function of the thickness of free gas column under the hydrate seal and the depth of hydrate seal, leaving a pockmark on the seafloor. The model shows that at least a 22-m-thick free gas layer beneath the hydrate at Blake Ridge is needed to form the 4-m-deep pockmark at the seabed.

Overview of the science activities for the 2002 Mallik gas hydrate production research well program, Mackenzie Delta, N.W.T., Canada

NASA Astrophysics Data System (ADS)

Dallimore, S. R.; Collett, T. S.; Uchida, T.; Weber, M.

2003-04-01

With the completion of scientific studies undertaken as part of the 1998 Mallik 2L-38 gas hydrate research well, an international research site was established for the study of Arctic natural gas hydrates in the Mackenzie Delta of northwestern Canada. Quantitative well log analysis and core studies reveal multiple gas hydrate layers from 890 m to 1106 m depth, exceeding 110 m in total thickness. High gas hydrate saturation values, which in some cases exceed 80% of the pore volume, establish the Mallik gas hydrate field as one of the most concentrated gas hydrate reservoirs in the world. Beginning in December 2001 and continuing to the middle of March 2002, two 1188 m deep science observation wells were drilled and instrumented and a 1166 m deep production research well program was carried out. The program participants include 8 partners; The Geological Survey of Canada (GSC), The Japan National Oil Corporation (JNOC), GeoForschungsZentrum Potsdam (GFZ), United States Geological Survey (USGS), United States Department of the Energy (USDOE), India Ministry of Petroleum and Natural Gas (MOPNG)/Gas Authority of India (GAIL) and the Chevron-BP-Burlington joint venture group. In addition the project has been accepted as part of the International Scientific Continental Drilling Program. The Geological Survey of Canada is coordinating the science program for the project and JAPEX Canada Ltd. acted as the designated operator for the fieldwork. Primary objectives of the research program are to advance fundamental geological, geophysical and geochemical studies of the Mallik gas hydrate field and to undertake advanced production testing of a concentrated gas hydrate reservoir. Full-scale field experiments in the production well monitored the physical behavior of the hydrate deposits in response to depressurization and thermal stimulation. The observation wells facilitated cross-hole tomography and vertical seismic profile experiments (before and after production) as well as the measurement of in situ formation conditions. A wide- ranging science and engineering research program included the collection of gas-hydrate-bearing core samples and downhole geophysical logging. Laboratory and modeling studies undertaken during the field program, and subsequently as part of a post-field research program, will document the sedimentology, physical/petrophysical properties, geochemistry, geophysics, reservoir characteristics and production behavior of the Mallik gas hydrate accumulation. The research team, including some 100 participant scientists from over 20 institutes in 7 countries, expects to publish the scientific results in 2004.

Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

NASA Astrophysics Data System (ADS)

Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

2012-12-01

While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the "onion-skin" texture observed in weathered obsdians, with large hydration stresses leading to spheroidal fracture. Long-term experiments derived from archaeological samples, however, suggest that there remain significant uncertainties. Analysis of younger samples (< 2500 years) from the Chalco site in Mexico yield results consistent with laboratory experients where diffusion rates are proportional to t0.4235, and suggest small changes in the average paleo-hydration temperature. Older samples, however, from the complexly stratified site of Çatalhöyük, central Anatolia, Turkey, suggest near linear-with-time rates. This is consistent with other observations of realtively old samples. The two trends observed in the latter, however, do not necessarily correlate with sourcing data. The origin of these differences remains unexplained. Effort by LMA and DRC was supported by research sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy.

Substitution of Wheat for Corn in Beef Cattle Diets: Digestibility, Digestive Enzyme Activities, Serum Metabolite Contents and Ruminal Fermentation.

PubMed

Liu, Y F; Zhao, H B; Liu, X M; You, W; Cheng, H J; Wan, F C; Liu, G F; Tan, X W; Song, E L; Zhang, X L

2016-10-01

The objective of this study was to evaluate the effect of diets containing different amounts of wheat, as a partial or whole substitute for corn, on digestibility, digestive enzyme activities, serum metabolite contents and ruminal fermentation in beef cattle. Four Limousin×LuXi crossbred cattle with a body weight (400±10 kg), fitted with permanent ruminal, proximal duodenal and terminal ileal cannulas, were used in a 4×4 Latin square design with four treatments: Control (100% corn), 33% wheat (33% substitution for corn), 67% wheat (67% substitution for corn), and 100% wheat (100% substitution for corn) on a dry matter basis. The results showed that replacing corn with increasing amounts of wheat increased the apparent digestibility values of dry matter, organic matter, and crude protein (p<0.05). While the apparent digestibility of acid detergent fiber and neutral detergent fiber were lower with increasing amounts of wheat. Digestive enzyme activities of lipase, protease and amylase in the duodenum were higher with increasing wheat amounts (p<0.05), and showed similar results to those for the enzymes in the ileum except for amylase. Increased substitution of wheat for corn increased the serum alanine aminotransferase concentration (p<0.05). Ruminal pH was not different between those given only corn and those given 33% wheat. Increasing the substitution of wheat for corn increased the molar proportion of acetate and tended to increase the acetate-to-propionate ratio. Cattle fed 100% wheat tended to have the lowest ruminal NH3-N concentration compared with control (p<0.05), whereas no differences were observed among the cattle fed 33% and 67% wheat. These findings indicate that wheat can be effectively used to replace corn in moderate amounts to meet the energy and fiber requirements of beef cattle.

Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

PubMed

Ghaani, Mohammad Reza; English, Niall J

2018-03-21

Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis

NASA Astrophysics Data System (ADS)

Ghaani, Mohammad Reza; English, Niall J.

2018-03-01

Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

Sedimentological Control on Hydrate Saturation Distribution in Arctic Gas-Hydrate-Bearing Deposits

NASA Astrophysics Data System (ADS)

Behseresht, J.; Peng, Y.; Bryant, S. L.

2010-12-01

Grain size variations along with the relative rates of fluid phases migrating into the zone of hydrate stability, plays an important role in gas-hydrate distribution and its morphologic characteristics. In the Arctic, strata several meters thick containing large saturations of gas hydrate are often separated by layers containing small but nonzero hydrate saturations. Examples are Mt. Elbert, Alaska and Mallik, NW Territories. We argue that this sandwich type hydrate saturation distribution is consistent with having a gas phase saturation within the sediment when the base of gas hydrate stability zone (BGHSZ) was located above the sediment package. The volume change during hydrate formation process derives movement of fluid phases into the GHSZ. We show that this fluid movement -which is mainly governed by characteristic relative permeability curves of the host sediment-, plays a crucial role in the amount of hydrate saturation in the zone of major hydrate saturation. We develop a mechanistic model that enables estimating the final hydrate saturation from an initial gas/water saturation in sediment with known relative permeability curves. The initial gas/water saturation is predicted using variation of capillary entry pressure with depth, which in turn depends on the variation in grain-size distribution. This model provides a mechanistic approach for explaining large hydrate saturations (60%-75%) observed in zones of major hydrate saturation considering the governing characteristic relative permeability curves of the host sediments. We applied the model on data from Mount Elbert well on the Alaskan North Slope. It is shown that, assuming a cocurrent flow of gas and water into the GHSZ, such large hydrate saturations (up to 75%) cannot result from large initial gas saturations (close to 1-Sw,irr) due to limitations on water flux imposed by typical relative permeability curves. They could however result from modest initial gas saturations (ca. 40%) at which we have reasonable phase mobility ratios required for appropriate relative rates of gas and water transporting into GHSZ to form large hydrate saturations. Nevertheless, from the profile of capillary entry pressure vs. depth, we expect large initial gas saturations and thus the final high hydrate saturation suggests another form of water flow: water moves down through accumulated hydrate from the unfrozen water above. For this to happen the water phase must remain connected within the hydrate-bearing sediment. This seems plausible in hydrate bearing sediments because hydrate formation will be stopped before water saturation gets to very low values (lower than Sw,irr) due to salinity build up. The location of small hydrate saturations (10-15%) is consistent with the location of the residual gas phase established during water imbibition into these locations while they serve as a gas source to the layers above.

A comparison of hydration effect on body fluid and temperature regulation between Malaysian and Japanese males exercising at mild dehydration in humid heat

PubMed Central

2014-01-01

Background This study investigated the effect of hydration differences on body fluid and temperature regulation between tropical and temperate indigenes exercising in the heat. Methods Ten Japanese and ten Malaysian males with matched physical characteristics (height, body weight, and peak oxygen consumption) participated in this study. Participants performed exercise for 60 min at 55% peak oxygen uptake followed by a 30-min recovery at 32°C and 70% relative air humidity with hydration (4 times each, 3 mL per kg body weight, 37°C) or without hydration. Rectal temperature, skin temperature, heart rate, skin blood flow, and blood pressure were measured continuously. The percentage of body weight loss and total sweat loss were calculated from body weight measurements. The percentage change in plasma volume was estimated from hemoglobin concentration and hematocrit. Results Malaysian participants had a significantly lower rectal temperature, a smaller reduction in plasma volume, and a lower heart rate in the hydrated condition than in the non-hydrated condition at the end of exercise (P <0.05), whereas Japanese participants showed no difference between the two hydration conditions. Hydration induced a greater total sweat loss in both groups (P <0.05), and the percentage of body weight loss in hydrated Malaysians was significantly less than in hydrated Japanese (P <0.05). A significant interaction between groups and hydration conditions was observed for the percentage of mean cutaneous vascular conductance during exercise relative to baseline (P <0.05). Conclusions The smaller reduction in plasma volume and percentage body weight loss in hydrated Malaysians indicated an advantage in body fluid regulation. This may enable Malaysians to reserve more blood for circulation and heat dissipation and thereby maintain lower rectal temperatures in a hydrated condition. PMID:24490869

L Band Brightness Temperature Observations over a Corn Canopy during the Entire Growth Cycle

PubMed Central

Joseph, Alicia T.; van der Velde, Rogier; O’Neill, Peggy E.; Choudhury, Bhaskar J.; Lang, Roger H.; Kim, Edward J.; Gish, Timothy

2010-01-01

During a field campaign covering the 2002 corn growing season, a dual polarized tower mounted L-band (1.4 GHz) radiometer (LRAD) provided brightness temperature (TB) measurements at preset intervals, incidence and azimuth angles. These radiometer measurements were supported by an extensive characterization of land surface variables including soil moisture, soil temperature, vegetation biomass, and surface roughness. In the period May 22 to August 30, ten days of radiometer and ground measurements are available for a corn canopy with a vegetation water content (W) range of 0.0 to 4.3 kg m−2. Using this data set, the effects of corn vegetation on surface emissions are investigated by means of a semi-empirical radiative transfer model. Additionally, the impact of roughness on the surface emission is quantified using TB measurements over bare soil conditions. Subsequently, the estimated roughness parameters, ground measurements and horizontally (H)-polarized TB are employed to invert the H-polarized transmissivity (γh) for the monitored corn growing season. PMID:22163585

Degradation of carbohydrates during dilute sulfuric acid pretreatment can interfere with lignin measurements in solid residues.

PubMed

Katahira, Rui; Sluiter, Justin B; Schell, Daniel J; Davis, Mark F

2013-04-03

The lignin content measured after dilute sulfuric acid pretreatment of corn stover indicates more lignin than could be accounted for on the basis of the untreated corn stover lignin content. This phenomenon was investigated using a combination of (13)C cross-polarization/magic-angle spinning (CP/MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy and lignin removal using acid chlorite bleaching. Only minimal contamination with carbohydrates and proteins was observed in the pretreated corn stover. Incorporating degradation products from sugars was also investigated using (13)C-labeled sugars. The results indicate that sugar degradation products are present in the pretreatment residue and may be intimately associated with the lignin. Studies comparing whole corn stover (CS) to extractives-free corn stover [CS(Ext)] clearly demonstrated that extractives are a key contributor to the high-lignin mass balance closure (MBC). Sugars and other low molecular weight compounds present in plant extractives polymerize and form solids during pretreatment, resulting in apparent Klason lignin measurements that are biased high.

Physicochemical properties of nixtamalized corn flours with and without germ.

PubMed

Vega Rojas, Lineth J; Rojas Molina, Isela; Gutiérrez Cortez, Elsa; Rincón Londoño, Natalia; Acosta Osorio, Andrés A; Del Real López, Alicia; Rodríguez García, Mario E

2017-04-01

This research studied the influence of the germ components on the physicochemical properties of cooked corn and nixtamalized corn flours as a function of the calcium hydroxide content (from 0 to 2.1 w/w) and steeping time (between 0 and 9h). A linear relationship was found between calcium content in germ and steeping time used during nixtamalization process. X-ray diffraction analysis showed that calcium carbonate is formed into the germ structure to 2.1 w/w of calcium hydroxide and 9h steeping time. The presence of the germ improves the development of peak viscosity in flours, and it is related to the increases in calcium concentration in germ and the formation of amylose-lipid complexes. No significant changes were observed in palmitic, stearic, oleic and linoleic acids of corn oil. The levels of further corn oil deterioration were 2.1 w/w of calcium hydroxide concentration and 9h of steeping time. Copyright © 2016 Elsevier Ltd. All rights reserved.

Scanning electron microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Circone, S.; Durham, W.B.

2004-01-01

Scanning electron microscopy (SEM) was used to investigate grain texture and pore structure development within various compositions of pure sI and sII gas hydrates synthesized in the laboratory, as well as in natural samples retrieved from marine (Gulf of Mexico) and permafrost (NW Canada) settings. Several samples of methane hydrate were also quenched after various extents of partial reaction for assessment of mid-synthesis textural progression. All laboratory-synthesized hydrates were grown under relatively high-temperature and high-pressure conditions from rounded ice grains with geometrically simple pore shapes, yet all resulting samples displayed extensive recrystallization with complex pore geometry. Growth fronts of mesoporous methane hydrate advancing into dense ice reactant were prevalent in those samples quenched after limited reaction below and at the ice point. As temperatures transgress the ice point, grain surfaces continue to develop a discrete "rind" of hydrate, typically 5 to 30 ??m thick. The cores then commonly melt, with rind microfracturing allowing migration of the melt to adjacent grain boundaries where it also forms hydrate. As the reaction continues under progressively warmer conditions, the hydrate product anneals to form dense and relatively pore-free regions of hydrate grains, in which grain size is typically several tens of micrometers. The prevalence of hollow, spheroidal shells of hydrate, coupled with extensive redistribution of reactant and product phases throughout reaction, implies that a diffusion-controlled shrinking-core model is an inappropriate description of sustained hydrate growth from melting ice. Completion of reaction at peak synthesis conditions then produces exceptional faceting and euhedral crystal growth along exposed pore walls. Further recrystallization or regrowth can then accompany even short-term exposure of synthetic hydrates to natural ocean-floor conditions, such that the final textures may closely mimic those observed in natural samples of marine origin. Of particular note, both the mesoporous and highly faceted textures seen at different stages during synthetic hydrate growth were notably absent from all examined hydrates recovered from a natural marine-environment setting.

Effects of Repeated Intraperitoneal Injection of Pharmaceutical-grade and Nonpharmaceutical-grade Corn Oil in Female C57BL/6J Mice.

PubMed

Hubbard, Jennifer S; Chen, Patty H; Boyd, Kelli L

2017-11-01

Due to potential adverse effects on animal wellbeing, the use of nonpharmaceutical-grade substances in animal research must be scientifically justified in cases where a pharmaceutical-grade version of the substance exists. This requirement applies to all substances, including vehicles used to solubilize experimental drugs. To date, no studies have evaluated the direct effect of the pharmaceutical classification of a compound on animal wellbeing. In this study, we evaluated intraperitoneal administration of pharmaceutical-grade corn oil, nonpharmaceutical-grade corn oil, and saline in female C57BL/6J mice. Compounds were administered every 48 h for a total of 4 injections. Mice were evaluated clinically by using body weight, body condition score, visual assessment score, CBC, and serum chemistries. Animals were euthanized at 24 h and 14 d after the final injection. Inflammation of the peritoneal wall and mesenteric fat was assessed microscopically by using a semiquantitative scoring system. Saline-dosed groups had lower pathology scores at both time points. At day 21, pharmaceutical-grade corn oil had a significantly higher pathology score compared with nonpharmaceutical-grade corn oil. No other significant differences between the corn oil groups were observed. The use of nonpharmaceutical grade corn oil did not result in adverse clinical consequences and is presumed safe to use for intraperitoneal injection in mice. Differences in inflammation between the 2 groups suggest that the use of either pharmaceutical-grade or nonpharmaceutical-grade corn oil should be consistent within a study.

Weed manipulation for insect pest management in corn

NASA Astrophysics Data System (ADS)

Altieri, M. A.; Whitcomb, W. H.

1980-11-01

Populations of insect pests and associated predaceous arthropods were sampled by direct observation and other relative methods in simple and diversified corn habitats at two sites in north Florida during 1978 and 1979. Through various cultural manipulations, characteristic weed communities were established selectively in alternate rows within corn plots. Fall armyworm ( Spodoptera frugiperda J. E. Smith) incidence was consistently higher in the weed-free habitats than in the corn habitats containing natural weed complexes or selected weed associations. Corn earworm ( Heliothis zea Boddie) damage was similar in all weed-free and weedy treatments, suggesting that this insect is not affected greatly by weed diversity. Only the diversification of corn with a strip of soybean significantly reduced corn earworm damage. In one site, distance between plots was reduced. Because predators moved freely between habitats, it was difficult to identify between-treatment differences in the composition of predator communities. In the other site, increased distances between plots minimized such migrations, resulting in greater population densities and diversity of common foliage insect predators in the weed-manipulated corn systems than in the weed-free plots. Trophic relationships in the weedy habitats were more complex than food webs in monocultures. Predator diversity (measured as mean number of species per area) and predator density was higher in com plots surrounded by mature, complex vegetation than at those surrounded by annual crops. This suggests that diverse adjacent areas to crops provide refuge for predators, thus acting as colonization sources.

Gas hydrate saturation and distribution in the Kumano Forearc Basin of the Nankai Trough

NASA Astrophysics Data System (ADS)

Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi

2017-02-01

The Kumano Forearc Basin is located to the south-east of the Kii Peninsula, Japan, overlying the accretionary prism in the Nankai Trough. The presence of gas hydrate in submarine sediments of the forearc basin has resulted in the widespread occurrence of bottom simulating reflectors (BSRs) on seismic profiles, and has caused distinct anomalies in logging data in the region. We estimated the in situ gas hydrate saturation from logging data by using three methods: effective rock physics models, Archie's equation, and empirical relationships between acoustic impedance (AI) and water-filled porosity. The results derived from rock physics models demonstrate that gas hydrates are attached to the grain surfaces of the rock matrix and are not floating in pore space. By applying the empirical relationships to the AI distribution derived from model-based AI inversion of the three-dimensional (3D) seismic data, we mapped the spatial distribution of hydrate saturation within the Kumano Basin and characterised locally concentrated gas hydrates. Based on the results, we propose two different mechanisms of free gas supply to explain the process of gas hydrate formation in the basin: (1) migration along inclined strata that dip landwards, and (2) migration through the faults or cracks generated by intensive tectonic movements of the accretionary prism. The dipping strata with relatively low AI in the forearc basin could indicate the presence of hydrate formation due to gas migration along the dipping strata. However, high hydrate concentration is observed at fault zones with high pore pressures, thus the second mechanism likely plays an important role in the genesis of gas hydrates in the Kumano Basin. Therefore, the tectonic activities in the accretionary wedge significantly influence the hydrate saturation and distribution in the Kumano Forearc Basin.

Geochemistry of a naturally occurring massive marine gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.; Threlkeld, C.N.; Dendy, Sloan E.

1984-01-01

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4??C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ???0.2% ethane, and ???0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 permil(( 0 00), relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift. ?? 1984.

X-ray Computed Tomography Observation of Methane Hydrate Dissociation

USGS Publications Warehouse

Tomutsa, L.; Freifeld, B.; Kneafsey, T.J.; Stern, L.A.

2002-01-01

Deposits of naturally occurring methane hydrate have been identified in permafrost and deep oceanic environments with global reserves estimated to be twice the total amount of energy stored in fossil fuels. The fundamental behavior of methane hydrate in natural formations, while poorly understood, is of critical importance if the economic recovery of methane from hydrates is to be accomplished. In this study, computed X-ray tomography (CT) scanning is used to image an advancing dissociation front in a heterogeneous gas hydrate/sand sample at 0.1 MPa. The cylindrical methane hydrate and sand aggregate, 2.54 cm in diameter and 6.3 cm long, was contained in a PVC sample holder that was insulated on all but one end. At the uninsulated end, the dissociated gas was captured and the volume of gas monitored. The sample was initially imaged axially using X-ray CT scanning within the methane hydrate stability zone by keeping the sample temperature at 77??K. Subsequently, as the sample warmed through the methane hydrate dissociation point at 194??K and room pressure, gas was produced and the temperature at the bottom of the sample plug was monitored while CT images were acquired. The experiment showed that CT imaging can resolve the reduction in density (as seen by a reduction in beam attenuation) of the hydrate/sand aggregate due to the dissociation of methane hydrate. In addition, a comparison of CT images with gas flow and temperature measurements reveals that the CT scanner is able to resolve accurately and spatially the advancing dissociation front. Future experiments designed to better understand the thermodynamics of hydrate dissociation are planned to take advantage of the temporal and spatial resolution that the CT scanner provides.

Crustal fingering: solidification on a viscously unstable interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Jimenez-Martinez, Joaquin; Cueto-Felgueroso, Luis; Porter, Mark; Juanes, Ruben

2017-11-01

Motivated by the formation of gas hydrates in seafloor sediments, here we study the volumetric expansion of a less viscous gas pocket into a more viscous liquid when the gas-liquid interfaces readily solidify due to hydrate formation. We first present a high-pressure microfluidic experiment to study the depressurization-controlled expansion of a Xenon gas pocket in a water-filled Hele-Shaw cell. The evolution of the pocket is controlled by three processes: (1) volumetric expansion of the gas; (2) rupturing of existing hydrate films on the gas-liquid interface; and (3) formation of new hydrate films. These result in gas fingering leading to a complex labyrinth pattern. To reproduce these observations, we propose a phase-field model that describes the formation of hydrate shell on viscously unstable interfaces. We design the free energy of the three-phase system to rigorously account for interfacial effects, gas compressibility and phase transitions. We model the hydrate shell as a highly viscous fluid with shear-thinning rheology to reproduce shell-rupturing behavior. We present high-resolution numerical simulations of the model, which illustrate the emergence of complex crustal fingering patterns as a result of gas expansion dynamics modulated by hydrate growth at the interface.

Formation of natural gas hydrates in marine sediments. Gas hydrate growth and stability conditioned by host sediment properties

USGS Publications Warehouse

Clennell, M.B.; Henry, P.; Hovland, M.; Booth, J.S.; Winters, W.J.; Thomas, M.

2000-01-01

The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine-grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.

Molecular dynamics study of structure H clathrate hydrates of methane and large guest molecules.

PubMed

Susilo, Robin; Alavi, Saman; Ripmeester, John A; Englezos, Peter

2008-05-21

Methane storage in structure H (sH) clathrate hydrates is attractive due to the relatively higher stability of sH as compared to structure I methane hydrate. The additional stability is gained without losing a significant amount of gas storage density as happens in the case of structure II (sII) methane clathrate. Our previous work has showed that the selection of a specific large molecule guest substance (LMGS) as the sH hydrate former is critical in obtaining the optimum conditions for crystallization kinetics, hydrate stability, and methane content. In this work, molecular dynamics simulations are employed to provide further insight regarding the dependence of methane occupancy on the type of the LMGS and pressure. Moreover, the preference of methane molecules to occupy the small (5(12)) or medium (4(3)5(6)6(3)) cages and the minimum cage occupancy required to maintain sH clathrate mechanical stability are examined. We found that thermodynamically, methane occupancy depends on pressure but not on the nature of the LMGS. The experimentally observed differences in methane occupancy for different LMGS may be attributed to the differences in crystallization kinetics and/or the nonequilibrium conditions during the formation. It is also predicted that full methane occupancies in both small and medium clathrate cages are preferred at higher pressures but these cages are not fully occupied at lower pressures. It was found that both small and medium cages are equally favored for occupancy by methane guests and at the same methane content, the system suffers a free energy penalty if only one type of cage is occupied. The simulations confirm the instability of the hydrate when the small and medium cages are empty. Hydrate decomposition was observed when less than 40% of the small and medium cages are occupied.

Freshwater lake to salt-water sea causing widespread hydrate dissociation in the Black Sea.

PubMed

Riboulot, Vincent; Ker, Stephan; Sultan, Nabil; Thomas, Yannick; Marsset, Bruno; Scalabrin, Carla; Ruffine, Livio; Boulart, Cédric; Ion, Gabriel

2018-01-09

Gas hydrates, a solid established by water and gas molecules, are widespread along the continental margins of the world. Their dynamics have mainly been regarded through the lens of temperature-pressure conditions. A fluctuation in one of these parameters may cause destabilization of gas hydrate-bearing sediments below the seafloor with implications in ocean acidification and eventually in global warming. Here we show throughout an example of the Black Sea, the world's most isolated sea, evidence that extensive gas hydrate dissociation may occur in the future due to recent salinity changes of the sea water. Recent and forthcoming salt diffusion within the sediment will destabilize gas hydrates by reducing the extension and thickness of their thermodynamic stability zone in a region covering at least 2800 square kilometers which focus seepages at the observed sites. We suspect this process to occur in other world regions (e.g., Caspian Sea, Sea of Marmara).

Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

NASA Astrophysics Data System (ADS)

Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

2013-04-01

Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

Influence of sodium borate on the early age hydration of calcium sulfoaluminate cement

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

Champenois, Jean-Baptiste; Dhoury, Mélanie; Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr

Calcium sulfoaluminate (CSA) cements are potential candidates for the conditioning of radioactive wastes with high sodium borate concentrations. This work thus investigates early age hydration of two CSA cements with different gypsum contents (0 to 20%) as a function of the mixing solution composition (borate and NaOH concentrations). Gypsum plays a key role in controlling the reactivity of cement. When the mixing solution is pure water, increasing the gypsum concentration accelerates cement hydration. However, the reverse is observed when the mixing solution contains sodium borate. Until gypsum exhaustion, the pore solution pH remains constant at ~ 10.8, and a poorlymore » crystallized borate compound (ulexite) precipitates. A correlation is established between this transient precipitation and the hydration delay. Decreasing the gypsum content in the binder, or increasing the sodium content in the mixing solution, are two ways of reducing the stability of ulexite, thus decreasing the hydration delay.« less

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

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

Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca; Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca

Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formationmore » of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.« less

Hydrate kinetics study in the presence of nonaqueous liquid by nuclear magnetic resonance spectroscopy and imaging.

PubMed

Susilo, Robin; Moudrakovski, Igor L; Ripmeester, John A; Englezos, Peter

2006-12-28

The dynamics of methane hydrate growth and decomposition were studied by nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI). Three well-known large molecule guest substances (LMGS) were used as structure H hydrate formers: 2,2-dimethylbutane (NH), methylcyclohexane (MCH), tert-butyl methyl ether (TBME). In addition, the impact of a non-hydrate former (n-heptane/nC7) was studied. The methane diffusion and hydrate growth were monitored by recording the 2H NMR spectra at 253 K and approximately 4.5 MPa for 20 h. The results revealed that methane diffuses faster in TBME and NH, slower in nC7, and slowest in MCH. The TBME system gives the fastest hydrate formation kinetics followed by NH, MCH, and nC7. The conversion of water into hydrate was also observed. The imaging study showed that TBME has a strong affinity toward ice, which is not the case for the NH and MCH systems. The degree of ice packing was also found to affect the LMGS distribution between ice particles. Highly packed ice increases the mass transfer resistance and hence limits the contact between LMGS and ice. It was also found that "temperature ramping" above the ice point improves the conversion significantly. Finally, hydrates were found to dissociate quickly within the first hour at atmospheric pressure and subsequently at a much slower rate. Methane dissolved in LMGS was also seen. The residual methane in hydrate phase and dissolved in LMGS phase explain the faster kinetics during hydrate re-formation.

Hydration status of Air Force military basic trainees after implementation of the back-mounted hydration system.

PubMed

Fogt, Donovan L; Brosch, Lorie C; Dacey, Danny C; Kalns, John E; Ketchum, Norma S; Rohrbeck, Patricia; Venuto, Margaret M; Tchandja, Juste B; Bunning, Mike L

2009-08-01

The Air Force makes an extraordinary effort to prevent heat-related illnesses associated with basic military training (BMT) in south Texas. However, inadequate hydration can still contribute to lost training time and qualified trainees leaving military service without completing BMT. The purpose of the present study was to determine whether equipping BMTs with back-mounted hydration systems (BM) is better than the standard-issue (SI) canteens with respect to hydration status. Male BMTs were randomly assigned to either BM (n = 40) or SI (n = 38) groups. Baseline values were assessed at week 0 before any physical readiness training (PRT). Subsequent data collection took place in the a.m. before PRT and in the p.m. before dinner the first 3 weeks, and during the 5 weeks of training. BMT total body water (TBW) and body composition were assessed by bioelectrical impedance. Saliva osmolality and total protein concentration were also determined. Hydration status increased daily in BM and SI and was well maintained over the duration of BMT. A significant hydration effect (p < 0.05) was observed for average daily increases in TBW and body weight with BM gaining more compared to SI. Average a.m. TBW was 0.3-0.8 L greater in SI versus BM (p < 0.05). Our findings demonstrate that adequate hydration status is maintained during Air Force BMT in a hot environment using either hydration mode and therefore do not support widespread issuance of the BM system on the premise of improved hydration during USAF BMT military training.

Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

USGS Publications Warehouse

Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.; McFarlane, J.; Kirkwood, W.

1997-01-01

We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

Coordinated CRISM and Opportunity Observations to Characterize the Mineralogy and Geologic History of Meridiani Planum Outcrops

NASA Astrophysics Data System (ADS)

Arvidson, R. E.

2011-12-01

The Opportunity Mars Exploration Rover has traversed over 30 km across Meridiani Planum since January 2004, acquiring numerous remote sensing and in-situ measurements of rocks and soils at dozens of locations. Over the past year Mars Reconnaissance Orbiter CRISM (0.362 to 3.92 micrometer imaging spectrometer) observations have been used to directly support planning of Opportunity traverses and locations for detailed remote sensing and in-situ measurements. As part of these coordinated observations CRISM's gimbaled optics have been used to spatially oversample acquisition of image data in the along-track direction (ATO or along track oversampled observations). This new acquisition mode allows sharpening the spatial detail from the normal ~18 m/pixel observations to values as small as ~6 m/pixel, with due formal consideration of the decrease in S/N with decreasing pixel sizes for retrieval of the 544 band spectra for each pixel. CRISM ATO observations show that mono-hydrated sulfates, most likely kieserite, outcrop on the walls of Victoria crater and the southeastern rim of Santa Maria crater. Unfortunately, the Victoria identifications are on the opposite side of the crater relative to where Opportunity made measurements of Victoria wall rocks. On the other hand, Opportunity was directed to Santa Maria's southeastern rim based on CRISM spectral reflectance data, spending the last solar conjunction period acquiring long-duration in-situ measurements of outcrop that likely carries the mono-hydrated sulfate signature. Additional ATO data collected over the relatively fresh, 2.3 km wide Ada crater located in southeastern Meridiani Planum show a similar mono-hydrated sulfate signature, implying that these deposits are widespread. Further, ATO observations allow detailed mapping of extensive hydrated sulfates in Botany Bay immediately to the south of Cape York, a rim segment of the largely buried, Noachian age Endeavour crater. Opportunity will cross these hydrated bedrock exposures on the way to Cape York outcrops. We will report on results from Opportunity's measurements on Victoria, Santa Maria, and Ada craters, together with measurements within Botany Bay, focusing on the synergistic use of Opportunity and CRISM observations to understand the mineralogy and geologic history of Meridiani Planum.

Approaching hydrate and free gas distribution at the SUGAR-Site location in the Danube Delta

NASA Astrophysics Data System (ADS)

Bialas, Joerg; Dannowski, Anke; Zander, Timo; Klaeschen, Dirk; Klaucke, Ingo

2017-04-01

Gas hydrates did receive a lot of attention over the last decades when investigating their potential to serve as a possible source for Methane production. Among other world-wide programs the German SUGAR project sets out to investigate the entire chain from exploitation to production in Europe. Therefore research in the scope of the SUGAR project sets out to investigate a site in European EEZ for the detailed studies of hydrate and gas distribution in a permeable sediment matrix. Among others one aim of the project is to provide in situ samples of natural methane hydrate for further investigations by MEBO drilling. The Danube paleo-delta with its ancient canyon and levee systems was chosen as a possible candidate for hydrate formation within the available drilling range of 200 m below seafloor. In order to decide on the best drilling location cruise MSM34 (Bialas et al., 2014) of the German RV MARIA S MERIAN set out to acquire geophysical, geological and geochemical datasets for assessment of the hydrate content within the Danube paleo-delta, Black Sea. The Black Sea is well known for a significant gas content in the sedimentary column. Reports on observations of bottom simulating reflectors (BSR) by Popescu et al. (2007) and others indicate that free gas and hydrate occurrence can be expected within the ancient passive channel levee systems. A variety of inverted reflection events within the gas hydrate stability zone (GHSZ) were observed within the drilling range of MEBO and chosen for further investigation. Here we report on combined seismic investigations of high-resolution 2D & 3D multichannel seismic (MCS) acquisition accompanied by four component Ocean-Bottom-Seismometer (OBS) observations. P- and converted S-wave arrivals within the OBS datasets were analysed to provide overall velocity depth models. Due to the limited length of profiles the majority of OBS events are caused by near vertical reflections. While P-wave events have a significant lateral coverage, converted S-waves do image a much narrower part of the subsurface only because of their low velocities. Therefore detailed modelling of small-scale structural anomalies imaged with MCS data within the GHSZ were undertaken in order to look for promising targets of MEBO drilling. An estimate of the expected hydrate and gas content is provided by comparison with published laboratory studies. Bialas, J., Klaucke, I. and Haeckel, M., 2014. FS MARIA S. MERIAN Fahrtbericht MSM-34 1&2 SUGAR Site, GEOMAR, Kiel. Popescu, I., Lericolais, G., Panin, N., De Batist, M. and Gillet, H., 2007. Seismic expression of gas and gas hydrates across the western Black Sea. Geo-Marine Letters, 27(2): 173-183.

Watershed regressions for pesticides (warp) models for predicting atrazine concentrations in Corn Belt streams

USGS Publications Warehouse

Stone, Wesley W.; Gilliom, Robert J.

2012-01-01

Watershed Regressions for Pesticides (WARP) models, previously developed for atrazine at the national scale, are improved for application to the United States (U.S.) Corn Belt region by developing region-specific models that include watershed characteristics that are influential in predicting atrazine concentration statistics within the Corn Belt. WARP models for the Corn Belt (WARP-CB) were developed for annual maximum moving-average (14-, 21-, 30-, 60-, and 90-day durations) and annual 95th-percentile atrazine concentrations in streams of the Corn Belt region. The WARP-CB models accounted for 53 to 62% of the variability in the various concentration statistics among the model-development sites. Model predictions were within a factor of 5 of the observed concentration statistic for over 90% of the model-development sites. The WARP-CB residuals and uncertainty are lower than those of the National WARP model for the same sites. Although atrazine-use intensity is the most important explanatory variable in the National WARP models, it is not a significant variable in the WARP-CB models. The WARP-CB models provide improved predictions for Corn Belt streams draining watersheds with atrazine-use intensities of 17 kg/km2 of watershed area or greater.

Beauveria bassiana (Ascomycota: Hypocreales) Introduced as an Endophyte in Corn Plants and Its Effects on Consumption, Reproductive Capacity, and Food Preference of Dichroplus maculipennis (Orthoptera: Acrididae: Melanoplinae)

PubMed Central

Mariottini, Yanina; Russo, Leticia M.; Vianna, M. Florencia; Scorsetti, Ana C.; Lange, Carlos E.

2017-01-01

In this study, the effects of strain Beauveria bassiana (LPSC 1067) as an endophyte in corn plants on consumption, fecundity, and food preference of Dichroplus maculipennis were examined. We observed that the daily consumption by grasshoppers fed with control plants was almost twice that of those that were fed treated plants. Significant differences in fecundity of grasshoppers that were fed with treated plants compared with those that only fed on control plants were also observed. The number of eggs laid per female fed with control plants was 27.2, while the number of eggs laid per female that were fed during 15 d with treated plants was 17.7. Similar results were observed when the number of embryonated eggs was evaluated. The highest number of embryonated eggs were recorded in those females that only fed on control plants (96%) while fewer embryonated eggs were recorded in grasshoppers fed for 15 d with treated plants only (25%). In relation to food preference the average consumption rate for D. maculipennis females on control corn plants was 303.8 ± 24.5 mg while it was only 25 ± 2.1 mg on plants treated with B. bassiana as an endophyte. In summary, we observed that B. bassiana as a corn plant endophyte negatively affected the daily consumption rate, fecundity and food preference of D. maculipennis. PMID:28423416

Comprehensive nitrogen budgets for controlled tile drainage fields in eastern ontario, Canada.

PubMed

Sunohara, M D; Craiovan, E; Topp, E; Gottschall, N; Drury, C F; Lapen, D R

2014-03-01

Excessive N loading from subsurface tile drainage has been linked to water quality degradation. Controlled tile drainage (CTD) has the potential to reduce N losses via tile drainage and boost crop yields. While CTD can reduce N loss from tile drainage, it may increase losses through other pathways. A multiple-year field-scale accounting of major N inputs and outputs during the cropping season was conducted on freely drained and controlled tile drained agricultural fields under corn ( L.)-soybean [ (L.) Merr.] production systems in eastern Ontario, Canada. Greater predicted gaseous N emissions for corn and soybean and greater observed lateral seepage N losses were observed for corn and soybean fields under CTD relative to free-draining fields. However, observed N losses from tile were significantly lower for CTD fields, in relation to freely drained fields. Changes in residual soil N were essentially equivalent between drainage treatments, while mass balance residual terms were systematically negative (slightly more so for CTD). Increases in plant N uptake associated with CTD were observed, probably resulting in higher grain yields for corn and soybean. This study illustrates the benefits of CTD in decreasing subsurface tile drainage N losses and boosting crop yields, while demonstrating the potential for CTD to increase N losses via other pathways related to gaseous emissions and groundwater seepage. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Production response to corn silage produced from normal, brown midrib, or waxy corn hybrids.

PubMed

Barlow, J S; Bernard, J K; Mullis, N A

2012-08-01

The objective was to evaluate the nutrient intake and digestibility and milk production response of lactating dairy cows fed diets based on corn silage produced from 3 different types of corn hybrids. Experimental diets contained 36.4% of the dietary dry matter (DM) from corn silage produced from normal (Agratech 1021, AgraTech Seeds Inc., Atlanta, GA), brown midrib (BMR; Mycogen F2F797, Mycogen Seeds, Indianapolis, IN), or waxy (Master's Choice 590, Master's Choice Hybrids, Ullin, IL) hybrids. Thirty-six multiparous and primiparous Holstein cows (66 ± 22 d in milk, 41 ± 8 kg/d of milk) were used in an 11-wk completely randomized design trial during the fall of 2009. All cows were fed a diet containing normal corn silage during the first 2wk of the trial before being assigned to 1 of 3 treatments for the following 9 wk. Data collected during the first 2 wk were used as a covariate in the statistical analysis. No difference was observed in dry matter intake (DMI) among treatments, which averaged 22.6 kg/d. Milk yield was higher for cows fed BMR (37.6 kg/d) compared with waxy (35.2 kg/d) but was similar to that of cows fed control (36.2 kg/d). Milk fat percentage tended to be lower for cows fed control (3.28%) compared with those fed BMR (3.60%) or waxy (3.55%) corn silage. Milk protein percentage tended to be lower for cows fed control (2.79%) compared with waxy (2.89%) but similar to that of those fed BMR (2.85%). No differences were observed in yield of milk components. Energy-corrected milk (ECM) yield and dairy efficiency (ECM:DMI) did not differ among treatments. Cows fed BMR tended to gain more body weight compared with those fed control and waxy. Results of this trial are consistent with previous reports in which cows fed diets based on corn silage produced from BMR hybrids have higher milk yield compared with those fed other hybrids. Corn silage produced from the waxy hybrid supported a similar yield of ECM because of higher milk components, but milk yield was not improved compared with the control. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Standardized Ileal Amino Acid Digestibility of Corn, Corn Distillers' Dried Grains with Solubles, Wheat Middlings, and Bakery By-Products in Broilers and Laying Hens.

PubMed

Adedokun, S A; Jaynes, P; Payne, R L; Applegate, T J

2015-10-01

Standardized ileal amino acid digestibility (SIAAD) of 5 samples of corn distillers dried grain with solubles (DDGS), 5 samples of bakery by-products (BBP), 3 samples of corn, and 1 sample of wheat middlings (WM) were evaluated in broilers and laying hens. Diets containing each of the 14 feed ingredients were evaluated in 21 day-old broiler chickens. The DDGS and BBP containing diets were fed to 30-week-old laying hens, while corn and wheat middling were evaluated in 50-week-old laying hens. All the diets were semi-purified with each feed ingredient being the only source of amino acid (AA). To obtain SIAAD values, apparent ileal AA digestibility was corrected for basal ileal endogenous AA losses using values generated from broilers and laying hens fed a nitrogen-free diet. Ileal crude protein digestibility for the 5 DDGS samples was higher (P < 0.05) in broilers than in laying hens. Broilers had higher SIAAD for DDGS 2, 3, 4, and 5 while there was no difference for DDGS 1 except for 4 AA where broilers had higher (P < 0.05) SIAAD values. Standardized ileal AA digestibility values for broilers were higher (P < 0.05) for BBP 1 and 4. Ileal CP digestibility for corn 1 was higher (P < 0.05) for broilers compared to laying hens, and SIAAD values for the 16 AA (9 indispensable and 7 dispensable) evaluated in this study were higher (P < 0.05) in broilers. Broilers had higher (P < 0.05) SIAAD values for 4 (histidine, leucine, phenylalanine, and valine) and 6 (histidine, leucine, methionine, phenylalanine, threonine, and valine) indispensable and 3 (cysteine, glutamic acid, and proline) and 4 (cysteine, glutamic acid, proline, and serine) dispensable AA for corn 2 and corn 3, respectively. No difference in SIAAD between broilers and laying hens was observed for WM. Results from this study confirm that high variability in digestibility exists between different samples of DDGS. Differences in SIAAD between broilers and laying hens were observed in some samples of DDGS and BBP. © 2015 Poultry Science Association Inc.

NINETY-DAY TOXICITY STUDY OF CHLORAL HYDRATE IN THE SPRAGUE-DAWLEY RAT

EPA Science Inventory

Male and female Sprague-Dawley rats were administered drinking water containing 300, 600, 1200, or 2400 mg/l chloral hydrate for 90 days. ontrol group recieved distilled water only. o animals died during the study and differences were observed in body weight gain or food and wate...

Phase transitions in biogenic amorphous calcium carbonate

NASA Astrophysics Data System (ADS)

Gong, Yutao

Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

Permeability of sediment cores from methane hydrate deposit in the Eastern Nankai Trough, Japan

NASA Astrophysics Data System (ADS)

Konno, Y.; Yoneda, J.; Egawa, K.; Ito, T.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Nagao, J.

2013-12-01

Effective and absolute permeability are key parameters for gas production from methane-hydrate-bearing sandy sediments. Effective and/or absolute permeability have been measured using methane-hydrate-bearing sandy cores and clayey and silty cores recovered from Daini Atsumi Knoll in the Eastern Nankai Trough during the 2012 JOGMEC/JAPEX Pressure coring operation. Liquid-nitrogen-immersed cores were prepared by rapid depressurization of pressure cores recovered by a pressure coring system referred to as the Hybrid PCS. Cores were shaped cylindrically on a lathe with spraying of liquid nitrogen to prevent hydrate dissociation. Permeability was measured by a flooding test or a pressure relaxation method under near in-situ pressure and temperature conditions. Measured effective permeability of hydrate-bearing sediments is less than tens of md, which are order of magnitude less than absolute permeability. Absolute permeability of clayey cores is approximately tens of μd, which would perform a sealing function as cap rocks. Permeability reduction due to a swelling effect was observed for a silty core during flooding test of pure water mimicking hydrate-dissociation-water. Swelling effect may cause production formation damage especially at a later stage of gas production from methane hydrate deposits. This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI).

Direct observations of gas-hydrate formation in natural porous media on the micro-scale

NASA Astrophysics Data System (ADS)

Chaouachi, M.; Sell, K.; Falenty, A.; Enzmann, F.; Kersten, M.; Pinzer, B.; Saenger, E. H.; Kuhs, W. F.

2013-12-01

Gas hydrates (GH) are crystalline, inclusion compounds consisting of hydrogen-bonded water network encaging small gas molecules such as methane, ethane, CO2, etc (Sloan and Koh 2008). Natural gas hydrates are found worldwide in marine sediments and permafrost regions as a result of a reaction of biogenic or thermogenic gas with water under elevated pressure. Although a large amount of research on GH has been carried out over the years, the micro-structural aspects of GH growth, and in particular the contacts with the sedimentary matrix as well as the details of the distribution remain largely speculative. The present study was undertaken to shed light onto the well-established but not fully understood seismic anomalies, in particular the unusual attenuation of seismic waves in GH-bearing sediments, which may well be linked to micro-structural features. Observations of in-situ GH growth have been performed in a custom-build pressure cell (operating pressures up to several bar) mounted at the TOMCAT beam line of SLS/ PSI. In order to provide sufficient absorption contrast between phases and reduce pressure requirements for the cell we have used Xe instead of CH4. To the best of our knowledge this represents the first direct observation of GH growth in natural porous media with sub-micron spatial resolution and gives insight into the nucleation location and growth process of GH. The progress of the formation of sI Xe-hydrate in natural quartz sand was observed with a time-resolution of several minutes; the runs were conducted with an excess of a free-gas phase and show that the nucleation starts at the gas-water interface. Initially, a GH film is formed at this interface with a typical thickness of several μm; this film may well be permeable to gas as suggested in the past - which would explain the rapid transport of gas molecules for further conversion of water to hydrate, completed in less than 20 min. Clearly, initially the growth is directed mainly into the liquid (and not into the gas phase as sometimes suggested). The observations of the 2D slices after full transformation show for all systems studied that hydrates tend to concentrate in the center of pore spaces and do not adhere in a systematic manner to quartz grains. Whether or not a thin film of water remained at the quartz-GH interface after completion of the reaction is presently under investigation. Sloan, E.D., Koh, C.A., (2008) Clathrate hydrates of natural gases. CRC Press, Boca Raton, FL.

Effects of corn oil administered orally on conspicuity of ultrasonographic small intestinal lesions in dogs with lymphangiectasia.

PubMed

Pollard, Rachel E; Johnson, Eric G; Pesavento, Patricia A; Baker, Tomas W; Cannon, Allison B; Kass, Philip H; Marks, Stanley L

2013-01-01

Lymphangiectasia is one of the causes of protein-losing enteropathy in dogs and characteristic ultrasonographic small intestinal lesions have been previously described. The purpose of this study was to determine whether corn oil administered orally (COAO) would result in increased conspicuity of these characteristic small intestinal ultrasonographic lesions in dogs with lymphangiectasia. Affected dogs were included if they underwent corn oil administered orally and had a surgical full-thickness intestinal biopsy diagnosis of lymphangiectasia. Control dogs had normal clinical examination and standard laboratory test findings. Ultrasound images of duodenum, jejunum, and ileum were obtained prior to and 30, 60, 90, and 120 min after corn oil administered orally for all dogs. Parameters recorded for each ultrasound study were intestinal wall thickness, mucosal echogenicity, and presence or absence of hyperechoic mucosal striations (HMS) and a parallel hyperechoic mucosal line (PHML). Nine affected and five controls dogs were included in the study. Seven of the nine dogs with lymphangiectasia had hyperechoic mucosal striations prior to corn oil administered orally. Jejunal hyperechoic mucosal striations were significantly associated with lymphangiectasia at multiple time points (P < 0.05) and were best identified in dogs with lymphangiectasia 60 or 90 min after corn oil administered orally. Increased mucosal echogenicity was observed in all dogs at multiple time points after corn oil administered orally. A parallel hyperechoic mucosal line was present in the jejunum in 4/5 healthy and 6/9 dogs with lymphangiectasia at one or more time points after corn oil administered orally. Findings indicated that corn oil administered orally improves conspicuity of characteristic ultrasonographic lesions in dogs with lymphangiectasia, however some of these lesions may also be present in healthy dogs that recently received a fatty meal. © 2013 Veterinary Radiology & Ultrasound.

Effect of experimental methodology on fasting heat production and the net energy content of corn and soybean meal fed to growing pigs.

PubMed

Liu, Dewen; Jaworski, Neil William; Zhang, Guifeng; Li, Zhongchao; Li, Defa; Wang, Fenglai

2014-01-01

The aim of the three experiments was to evaluated methods to predict fasting heat production (FHP) and to compare methods to determine the net energy (NE) of corn and soybean meal (SBM) fed to growing pigs. To estimate heat production (HP), pigs were housed in respiratory chambers for all experiments. In Experiment 1, six barrows (43.0 ± 1.4 kg body weight [BW]) were fed a Corn-SBM diet for 20 d. The experimental design consisted of following periods: 7 d adaptation, 5 d ad libitum feeding, 3 d feeding at 2 × metabolisable energy (ME) for maintenance (MEm), 3 d feeding at 1 × MEm and 2 d fasting. The FHP was calculated by extrapolating HP measured at the different feeding levels to zero ME intake. The daily FHP [per kg BW(0)(.6)] determined directly after fasting for 24 h and using the regression method was 774 kJ and 694 kJ, respectively. In Experiment 2, 18 barrows (34.3 ± 1.1 kg BW) were randomly allotted to three diets: Diet 1 contained 97.5% corn (direct NE determination of corn); diets 2 and 3 contained 25 % and 15% SBM at the expense of corn, respectively, and were used to calculate the NE of corn by difference. The NE of corn determined directly (13.21 MJ/kg DM) and by difference (13.69 MJ/kg DM) was not different. In Experiment 3, 24 barrows (36.2 ± 1.4 kg BW) were randomly allotted to four diets to determine the effects of different basal diets on the NE content of SBM. The diets were: Basal diet 1 (97.5% corn), Test diet 1 (15% SBM at the expense of corn), Basal diet 2 (contained 72.5% corn and 25% SBM) and Test diet 2 (58% corn and 39.5% SBM). These diets were used to determine the NE of SBM using the Corn-basal diet or the Corn-SBM-basal diet, respectively. It was shown that the estimated NE of SBM did not depend on the used diet (10.04 MJ/kg and 10.62 MJ/kg DM for Basal diet 1 and 2, respectively). In summary, using the regression method to determine FHP results in lower FHP than the fasting method. There was no difference observed in the NE of corn determined directly or by difference, and different basal diets did not affect the NE of SBM.

Cyclic formation and dissociation of methane hydrate within partially water saturated sand

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Nakagawa, S.

2010-12-01

For partially water-saturated sediments, laboratory experiments have shown that methane hydrate forms heterogeneously within a sample at the core scale. The heterogeneous distribution of hydrate in combination with grain-scale hydrate location (eg. grain cementing, load bearing, and pore filling), determines the overall mechanical properties of hydrate-bearing sediments including shear strength and seismic properties. For this reason, understanding the heterogeneity of hydrate-bearing sample is essential when the bulk properties of the sample are examined in the laboratory. We present a series of laboratory methane hydrate formation and dissociation experiments with concurrent x-ray CT imaging and low-frequency (near 1 kHz) seismic measurements. The seismic measurements were conducted using a new acoustic resonant bar technique called the Split Hopkinson Resonant Bar method, which allows using a small sediment core (3.75 cm diameter, 7.5 cm length). The experiment was conducted using a jacketed, pre-compacted, fine-grain silica sand sample with a 40% distilled water saturation. Under isotropic confining stress of 6.9 MPa and a temperature 4 oC, the hydrate was formed in the sample by injecting pure methane gas at 5.6 MPa. Once the hydrate formed, it was dissociated by reducing the pore pressure to 2.8 MPa. This cycle was repeated by three times (dissociation test for the third cycle was not done) to examine the resulting changes in the hydrate distribution and seismic signatures. The repeated formation of hydrate resulted in significant changes in its distribution, which resulted in differences in the overall elastic properties of the sample, determined from the seismic measurements. Interestingly, the time intervals between the dissociation and subsequent formation of hydrate affected the rate of hydrate formation, shorter intervals resulting in faster formation. This memory effect, possibly caused by the presence of residual “seed crystals” in the pore water providing nucleation points for hydrate formation, did not result in rapid formation at all locations in the sample. In spite of heterogeneity, observed seismic properties were very similar for the two measurements during dissociation.

Origin Of Methane Gas And Migration Through The Gas Hydrate Stability Zone Beneath The Permafrost Zone

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Namikawa, T.

2005-12-01

In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data as well as visible gas hydrates have confirmed pore-space hydrate as intergranular pore filling within sandy layers whose saturations are up to 80% in pore volume, but muddy sediments scarcely contain. Plenty of gas hydrate-bearing sand core samples have been obtained from the Mallik wells. According to grain size distributions pore-space hydrate is dominant in medium- to very fine-grained sandy strata. Methane gas accumulation and original pore space large enough to occur within host sediments may be required for forming highly saturated gas hydrate in pore system. The distribution of a porous and coarser-grained host rock should be one of the important factors to control the occurrence of gas hydrate, as well as physicochemical conditions. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sandy core samples also revealed important geologic and sedimentological controls on the formation and concentration of natural gas hydrate. This appears to be a similar mode for conventional oil and gas accumulations. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. The isotopic data of methane show that hydrocarbon gas contained in gas hydrate is generated by thermogenic decomposition of kerogen in deep mature sediments. Based on geochemical and geological data, methane is inferred to migrate upward closely associated with pore water hundreds of meters into and through the hydrate stability zone partly up to the permafrost zone and the surface along faults and permeable sandy pathways. It should be remarked that there are many similar features in appearance and characteristics between the terrestrial and deep marine areas such as Nankai Trough with observations of well-interconnected and highly saturated pore-space hydrate.

Recent research on fumonisins: a review.

PubMed

Scott, P M

2012-01-01

Fumonisins are well known mycotoxins produced by Fusarium verticillioides, F. proliferatum and other Fusarium species. Many new fumonisins and fumonisin-like compounds have been detected by mass spectrometry in cultures of F. verticillioides. Recently, fumonisins B(2) and B(4) were produced by Aspergillus niger isolated from coffee and fumonisin B(2) in A. niger from grapes. Fumonisin B(2) was itself detected in coffee beans, wine and beer, adding to the list of foodstuffs and feedstuffs other than corn (maize) and sorghum in which fumonisins have been found in recent years. Fumonisin B(1) (FB(1)) can bind to proteins (PB FB(1)) and to other matrix components during food processing involving heat. The occurrence of bound fumonisins in processed corn foods is common. Another type of binding (or association) relates to observed instability of fumonisins in rice flour, corn starch and corn meal at room temperature; this can affect the immunoaffinity column clean-up procedure in analysis of naturally contaminated starch-containing corn foods for fumonisins. The occurrence of N-fatty acylated fumonisin derivatives in retail fried corn foods has also been demonstrated. Bioaccessibility of free FB(1) and total bound FB(1) (TB FB(1)) present in corn flakes has been estimated by in vitro digestion experiments. Intentional binding of fumonisins to cholestyramine has been demonstrated in vivo and is a potential means of detoxification of animal feed.

Self-curing concrete with different self-curing agents

NASA Astrophysics Data System (ADS)

Gopala krishna sastry, K. V. S.; manoj kumar, Putturu

2018-03-01

Concrete is recognised as a versatile construction material globally. Properties of concrete depend upon, to a greater extent, the hydration of cement and microstructure of hydrated cement. Congenial atmosphere would aid the hydration of cement and hence curing of concrete becomes essential, till a major portion of the hydration process is completed. But in areas of water inadequacy and concreting works at considerable heights, curing is problematic. Self-Curing or Internal Curing technique overcomes these problems. It supplies redundant moisture, for more than sufficient hydration of cement and diminish self-desiccation. Self-Curing agents substantially help in the conservation of water in concrete, by bringing down the evaporation during the hydration of Concrete. The present study focuses on the impact of self-curing agents such as Poly Ethylene Glycol (PEG), Poly Vinyl Alcohol (PVA) and Super Absorbent Polymer (SAP) on the concrete mix of M25 grade (reference mix). The effect of these agents on strength properties of Concrete such as compressive strength, split tensile strength and flexural strength was observed on a comparative basis which revealed that PEG 4000 was the most effective among all the agents.

Is the tungsten(IV) complex (NEt4)2[WO(mnt)2] a functional analogue of acetylene hydratase?

PubMed Central

Schreyer, Matthias

2017-01-01

The tungsten(IV) complex (Et4N)2[W(O)(mnt)2] (1; mnt = maleonitriledithiolate) was proposed (Sarkar et al., J. Am. Chem. Soc. 1997, 119, 4315) to be a functional analogue of the active center of the enzyme acetylene hydratase from Pelobacter acetylenicus, which hydrates acetylene (ethyne; 2) to acetaldehyde (ethanal; 3). In the absence of a satisfactory mechanistic proposal for the hydration reaction, we considered the possibility of a metal–vinylidene type activation mode, as it is well established for ruthenium-based alkyne hydration catalysts with anti-Markovnikov regioselectivity. To validate the hypothesis, the regioselectivity of tungsten-catalyzed alkyne hydration of a terminal, higher alkyne had to be determined. However, complex 1 was not a competent catalyst for the hydration of 1-octyne under the conditions tested. Furthermore, we could not observe the earlier reported hydration activity of complex 1 towards acetylene. A critical assessment of, and a possible explanation for the earlier reported results are offered. The title question is answered with "no". PMID:29181113

Effect of Nano-SiO₂ on the Early Hydration of Alite-Sulphoaluminate Cement.

PubMed

Sun, Jinfeng; Xu, Zhiqiang; Li, Weifeng; Shen, Xiaodong

2017-05-03

The impact of nano-SiO₂ on the early hydration properties of alite-sulphoaluminate (AC$A) cement was investigated with a fixed water to solid ratio ( w / s ) of one. Nano-SiO₂ was used in partial substitution of AC$A cement at zero, one and three wt %. Calorimetry, X-ray diffraction (XRD), thermogravimetric/derivative thermogravimetric (TG/DTG), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) analyses were used to characterize the hydration and hydrates of the blended cement. The hydration of the AC$A cement was significantly promoted, resulting in an increase of the heat released with the addition of nano-SiO₂. Phase development composition analysis showed that nano-SiO₂ had no effect on the type of crystalline hydration products of the AC$A cement. Moreover, nano-SiO₂ showed significant positive effects on pore refinement where the total porosity decreased by 54.09% at three days with the inclusion of 3% nano-SiO₂. Finally, from the SEM observations, nano-SiO₂ was conducive to producing a denser microstructure than that of the control sample.

Spectral phasor analysis of LAURDAN fluorescence in live A549 lung cells to study the hydration and time evolution of intracellular lamellar body-like structures.

PubMed

Malacrida, Leonel; Astrada, Soledad; Briva, Arturo; Bollati-Fogolín, Mariela; Gratton, Enrico; Bagatolli, Luis A

2016-11-01

Using LAURDAN spectral imaging and spectral phasor analysis we concurrently studied the growth and hydration state of subcellular organelles (lamellar body-like, LB-like) from live A549 lung cancer cells at different post-confluence days. Our results reveal a time dependent two-step process governing the size and hydration of these intracellular LB-like structures. Specifically, a first step (days 1 to 7) is characterized by an increase in their size, followed by a second one (days 7 to 14) where the organelles display a decrease in their global hydration properties. Interestingly, our results also show that their hydration properties significantly differ from those observed in well-characterized artificial lamellar model membranes, challenging the notion that a pure lamellar membrane organization is present in these organelles at intracellular conditions. Finally, these LB-like structures show a significant increase in their hydration state upon secretion, suggesting a relevant role of entropy during this process. Copyright © 2016 Elsevier B.V. All rights reserved.

Direct Measurements of 3D Structure, Chemistry and Mass Density During the Induction Period of C3S Hydration

PubMed Central

Hu, Qinang; Aboustait, Mohammed; Kim, Taehwan; Ley, M. Tyler; Bullard, Jeffrey W.; Scherer, George; Hanan, Jay C.; Rose, Volker; Winarski, Robert; Gelb, Jeffrey

2017-01-01

The reasons for the start and end of the induction period of cement hydration remain topic of controversy. One long-standing hypothesis is that a thin metastable hydrate forming on the surface of cement grains significantly reduces the particle dissolution rate; the eventual disappearance of this layer re-establishes higher dissolution rates at the beginning of the acceleration period. However, the importance, or even the existence, of this metastable layer has been questioned because it cannot be directly detected in most experiments. In this work, a combined analysis using nano-tomography and nano-X-ray fluorescence makes the direct imaging of early hydration products possible. These novel X-ray imaging techniques provide quantitative measurements of 3D structure, chemical composition, and mass density of the hydration products during the induction period. This work does not observe a low density product on the surface of the particle, but does provide insights into the formation of etch pits and the subsequent hydration products that fill them. PMID:28919638

Direct observation of void evolution during cement hydration

DOE PAGES

Moradian, Masoud; Hu, Qinang; Aboustait, Mohammed; ...

2017-09-28

This study follows the hydration of both portland cement and tricalcium silicate pastes between 30 min and 16 h of hydration. In-situ fast X-ray Computed Tomography (fCT) was used to make direct observations of the air-filled void formation in w/s of 0.40 to 0.70 with a micron resolution. The results show that over the first hour of the acceleration period the volume of air-filled voids reaches a maximum value and then decreases during the acceleration period and stays constant. The void distribution changes from a few coarse voids to a large number of smaller and more uniformly distributed voids. Thismore » behavior is suggested to be controlled by changes in the ionic strength that cause exsolution of dissolved air from the pore solution.« less

Direct observation of void evolution during cement hydration

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

Moradian, Masoud; Hu, Qinang; Aboustait, Mohammed

This study follows the hydration of both portland cement and tricalcium silicate pastes between 30 min and 16 h of hydration. In-situ fast X-ray Computed Tomography (fCT) was used to make direct observations of the air-filled void formation in w/s of 0.40 to 0.70 with a micron resolution. The results show that over the first hour of the acceleration period the volume of air-filled voids reaches a maximum value and then decreases during the acceleration period and stays constant. The void distribution changes from a few coarse voids to a large number of smaller and more uniformly distributed voids. Thismore » behavior is suggested to be controlled by changes in the ionic strength that cause exsolution of dissolved air from the pore solution.« less

Physical and sensory characterization and consumer preference of corn and barley-fed beef.

PubMed

Wismer, W V; Okine, E K; Stein, A; Seibel, M R; Goonewardene, L A

2008-11-01

Steaks from corn-fed and barley-fed beef were characterized by a trained panel, which rated corn-fed beef higher (p<0.05) for tenderness attributes and overall flavor intensity. Canadian consumers preferred (p<0.01) cooked and raw steaks from barley-fed beef, while Mexican consumers showed no preference (p>0.05) for either type of finished beef. Japanese consumers showed a preference (p<0.05) for the appearance of raw barley-fed steaks but a preference for cooked corn-fed steaks (p<0.05). No differences (p>0.05) were observed for Warner-Bratzler shear, marbling scores, cooking losses or Hunter colorimeter values. There was a trend for higher concentrations (p<0.08) of the saturated fatty acids in the barley treatment, but no differences (p>0.10) in mono or polyunsaturated fatty acids.

Natural gas hydrate in sediments imaged by cryogenic SEM: Insights from lab experiments on synthetic hydrates as interpretive guides.

NASA Astrophysics Data System (ADS)

Stern, L. A.; Kirby, S. H.

2006-12-01

In the investigation of natural gas hydrates, distinguishing in situ grain textures and microstructures from artifacts produced during retrieval, storage, and examination can be quite challenging. Using cryogenic scanning electron microscopy, we investigated the physical states of gas hydrates produced in our lab as well as of those in drill core of hydrate-bearing sediment from marine and Arctic permafrost environments. Here, we compare grain and pore structures observed in samples from the Cascadia margin (courtesy IODP Expedition 311), McKenzie River Delta (Mallik Well 5L-38), and Gulf of Mexico (RSV Marion Dufresne 2002), with those present in hydrocarbon hydrates grown in our laboratory and subjected to controlled P-T conditions. The following trends are apparent for the natural gas hydrates imaged to-date: (1) Samples typically contain massive domains of polycrystalline gas hydrate that in turn contain isolated gas-filled pores that are sometimes lined with euhedral hydrate crystals. Pores are typically 5 50 microns in diameter and occupy roughly 10-30 percent of the domain. Grain sizes, where visible, are commonly 20 to 50 microns. (2) Hydrate grain boundaries, particularly near the exposed sample surface, are often replaced by a nanoporous material. Based on its location and behavior, this material is presumed to be gas-charged porous ice produced by hydrate decomposition along grain surfaces. In some samples, grains are instead bounded by a framework of dense, tabular material embedded within the sample, best revealed upon sublimation of the hydrate. Their composition is yet unknown but may be salt or carbonate-bearing minerals. (3) Where hydrate grows into clayey sediments, the clays typically arrange with platelets subparallel around the pods or veins of hydrate. (4) Domains of nano-to-micro- porous water ice are also seen in all recovered natural samples, presumed to be hydrate decomposition product produced during drill-core retrieval and handling. Based on lab experiments, we believe the initial liquid product is frozen as a result of the local temperature reduction accompanying the endothermic dissociation reaction. The porous texture is then preserved by liquid nitrogen quenching. (5) Samples from both marine and permafrost environments also display closely juxtaposed regions of dense and porous hydrate and ice. Although the close association of these regions remains puzzling, lab tests verify that dense hydrate can exhibit such porous appearance along it's surface after even minor decomposition at cold conditions (below 273 K). In turn, companion experiments show that nanoporous hydrate anneals to a densely crystalline habit at conditions within the hydrate stability region above 273 K, suggesting that nanoporous gas hydrate is not stable at most in situ natural conditions.

The Growth and Decay of Hydrate Anomalies in Marine Sediments

NASA Astrophysics Data System (ADS)

Irizarry, J. T.; Rempel, A. W.

2014-12-01

Natural gas hydrates, stored in huge quantities beneath permafrost, and in submarine sediments on the continental shelf, have the potential to become a vital clean-burning energy source. However, clear evidence is recorded in coastal sediments worldwide that past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. Arctic permafrost is thawing, and environmental changes can alter ocean circulation to warm the seafloor, causing hydrates to dissociate or dissolve in the sediments beneath. Decades of focused research provide a firm understanding of laboratory conditions under which hydrates become unstable and dissociate, and how hydrate reserves form when microbes convert organic material into methane, which can also dissolve and be carried by pore waters into the hydrate stability zone. Despite these advances, many key questions that concern both the resource potential of hydrates and their role in causing environmental geohazards, are intimately tied to the more poorly understood behavior of hydrate anomalies, which tend to be concentrated in the large pores of sand layers and form segregated lenses and nodules in muds. We present simple models designed to unravel the importance of the diverse physical interactions (i.e. flow focusing, free-gas infiltration, and pore-scale solubility effects) that help control how hydrate anomalies form. Predicted hydrate distributions are qualitatively different when accumulation in anomalies is supplied primarily by: 1. aqueous flow through sediments with enhanced permeability, 2. free-gas transport high above the three-phase stability boundary, or 3. diffusive transport along solubility gradients associated with pore-scale effects. We discuss examples that illustrate each of these distinct generation modes, in hopes of providing a framework for interpreting field observations of hydrate anomalies and their geomechanical properties in terms of the history of environmental forcing that led to their development.

Invasion of drilling mud into gas-hydrate-bearing sediments. Part I: effect of drilling mud properties

NASA Astrophysics Data System (ADS)

Ning, Fulong; Zhang, Keni; Wu, Nengyou; Zhang, Ling; Li, Gang; Jiang, Guosheng; Yu, Yibing; Liu, Li; Qin, Yinghong

2013-06-01

To our knowledge, this study is the first to perform a numerical simulation and analysis of the dynamic behaviour of drilling mud invasion into oceanic gas-hydrate-bearing sediment (GHBS) and to consider the effects of such an invasion on borehole stability and the reliability of well logging. As a case study, the simulation background sets up the conditions of mud temperature over hydrate equilibrium temperature and overbalanced drilling, considering the first Chinese expedition to drill gas hydrate (GMGS-1). The results show that dissociating gas may form secondary hydrates in the sediment around borehole by the combined effects of increased pore pressure (caused by mud invasion and flow resistance), endothermic cooling that accompanies hydrate dissociation compounded by the Joule-Thompson effect and the lagged effect of heat transfer in sediments. The secondary hydrate ring around the borehole may be more highly saturated than the in situ sediment. Mud invasion in GHBS is a dynamic process of thermal, fluid (mud invasion), chemical (hydrate dissociation and reformation) and mechanical couplings. All of these factors interact and influence the pore pressure, flow ability, saturation of fluid and hydrates, mechanical parameters and electrical properties of sediments around the borehole, thereby having a strong effect on borehole stability and the results of well logging. The effect is particularly clear in the borehole SH7 of GMGS-1 project. The borehole collapse and resistivity distortion were observed during practical drilling and wireline logging operations in borehole SH7 of the GMGS-1.mud density (i.e. the corresponding borehole pressure), temperature and salinity have a marked influence on the dynamics of mud invasion and on hydrate stability. Therefore, perhaps well-logging distortion caused by mud invasion, hydrate dissociation and reformation should be considered for identifying and evaluating gas hydrate reservoirs. And some suitable drilling measurements need to be adopted to reduce the risk of well-logging distortion and borehole instability.

Hydrates of nat­ural gas in continental margins

USGS Publications Warehouse

Kvenvolden, K.A.; Barnard, L.A.

1982-01-01

Natural gas hydrates in continental margin sediment can be inferred from the widespread occurrence of an anomalous seismic reflector which coincides with the predicted transition boundary at the base of the gas hydrate zone. Direct evidence of gas hydrates is provided by visual observations of sediments from the landward wall of the Mid-America Trench off Mexico and Guatemala, from the Blake Outer Ridge off the southeastern United States, and from the Black Sea in the U.S.S.R. Where solid gas hydrates have been sampled, the gas is composed mainly of methane accompanied by CO2 and low concentrations of ethane and hydrocarbons of higher molecular weight. The molecular and isotopic composition of hydrocarbons indicates that most of the methane is of biolog cal origin. The gas was probably produced by the bacterial alteration of organic matter buried in the sediment. Organic carbon contents of the sediment containing sampled gas hydrates are higher than the average organic carbon content of marine sediments. The main economic importance of gas hydrates may reside in their ability to serve as a cap under which free gas can collect. To be producible, however, such trapped gas must occur in porous and permeable reservoirs. Although gas hydrates are common along continental margins, the degree to which they are associated with significant reservoirs remains to be investigated.

Biot-type scattering effects in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Rubino, J. GermáN.; Ravazzoli, Claudia L.; Santos, Juan E.

2008-06-01

This paper studies the energy conversions that take place at discontinuities within gas hydrate-bearing sediments and their influence on the attenuation of waves traveling through these media. The analysis is based on a theory recently developed by some of the authors, to describe wave propagation in multiphasic porous media composed of two solids saturated by a single-phase fluid. Real data from the Mallik 5L-38 Gas Hydrate Research well are used to calibrate the physical model, allowing to obtain information about the characteristics of the cementation between the mineral grains and gas hydrates for this well. Numerical experiments show that, besides energy conversions to reflected and transmitted classical waves, significant fractions of the energy of propagating waves may be converted into slow-waves energy at plane heterogeneities within hydrated sediments. Moreover, numerical simulations of wave propagation show that very high levels of attenuation can take place in the presence of heterogeneous media composed of zones with low and high gas hydrate saturations with sizes smaller or on the order of the wavelengths of the fast waves at sonic frequencies. These attenuation levels are in very good agreement with those measured at the Mallik 5L-38 Gas Hydrate Research Well, suggesting that these scattering-type effects may be a key-parameter to understand the high sonic attenuation observed at gas hydrate-bearing sediments.

KIGAM Seafloor Observation System (KISOS) for the baseline study in monitoring of gas hydrate test production in the Ulleung Basin, Korea

NASA Astrophysics Data System (ADS)

Lee, Sung-rock; Chun, Jong-hwa

2013-04-01

For the baseline study in the monitoring gas hydrate test production in the Ulleung Basin, Korea Institute of Geoscience and Mineral Resources (KIGAM) has developed the KIGAM Seafloor Observation System (KISOS) for seafloor exploration using unmanned remotely operated vehicle connected with a ship by a cable. The KISOS consists of a transponder of an acoustic positioning system (USBL), a bottom finding pinger, still camera, video camera, water sampler, and measuring devices (methane, oxygen, CTD, and turbidity sensors) mounted on the unmanned ROV, and a sediment collecting device collecting sediment on the seafloor. It is very important to monitoring the environmental risks (gas leakage and production water/drilling mud discharge) which may be occurred during the gas hydrate test production drilling. The KISOS will be applied to solely conduct baseline study with the KIGAM seafloor monitoring system (KIMOS) of the Korean gas hydrate program in the future. The large scale of environmental monitoring program includes the environmental impact assessment such as seafloor disturbance and subsidence, detection of methane gas leakage around well and cold seep, methane bubbles and dissolved methane, change of marine environments, chemical factor variation of water column and seabed, diffusion of drilling mud and production water, and biological factors of biodiversity and marine habitats before and after drilling test well and nearby areas. The design of the baseline survey will be determined based on the result of SIMAP simulation in 2013. The baseline survey will be performed to provide the gas leakage and production water/drilling mud discharge before and after gas hydrate test production. The field data of the baseline study will be evaluated by the simulation and verification of SIMAP simulator in 2014. In the presentation, the authors would like introduce the configuration of KISOS and applicability to the seafloor observation for the gas hydrate test production in the Ulleung Basin. This work was financially supported by the the Ministry of Knowledge Economy(MKE) and Gas Hydrate R/D Organization(GHDO)

Measuring and modeling the effects of drainage water management on soil greenhouse gas fluxes from corn and soybean fields.

PubMed

Nangia, V; Sunohara, M D; Topp, E; Gregorich, E G; Drury, C F; Gottschall, N; Lapen, D R

2013-11-15

Controlled tile drainage can boost crop yields and improve water quality, but it also has the potential to increase GHG emissions. This study compared in-situ chamber-based measures of soil CH4, N2O, and CO2 fluxes for silt loam soil under corn and soybean cropping with conventional tile drainage (UTD) and controlled tile drainage (CTD). A semi-empirical model (NEMIS-NOE) was also used to predict soil N2O fluxes from soils using observed soil data. Observed N2O and CH4 fluxes between UTD and CTD fields during the farming season were not significantly different at 0.05 level. Soils were primarily a sink for CH4 but in some cases a source (sources were associated exclusively with CTD). The average N2O fluxes measured ranged between 0.003 and 0.028 kg N ha(-1) day(-1). There were some significantly higher (p ≤ 0.05) CO2 fluxes associated with CTD relative to UTD during some years of study. Correlation analyses indicated that the shallower the water table, the greater the CO2 fluxes. Higher corn plant C for CTD tended to offset estimated higher CTD CO2 C losses via soil respiration by ∼100-300 kg C ha(-1). There were good fits between observed and predicted (NEMIS-NOE) N2O fluxes for corn (R(2) = 0.70) and soybean (R(2) = 0.53). Predicted N2O fluxes were higher for CTD for approximately 70% of the paired-field study periods suggesting that soil physical factors, such as water-filled pore space, imposed by CTD have potentially strong impacts on net N fluxes. Model predictions of daily cumulative N2O fluxes for the agronomically-active study period for corn-CTD and corn-UTD, as a percentage of total N fertilizer applied, were 3.1% and 2.6%, respectively. For predicted N2O fluxes on basis of yield units, indices were 0.0005 and 0.0004 (kg N kg(-1) crop grain yield) for CTD and UTD corn fields, respectively, and 0.0011 and 0.0005 for CTD and UTD soybean fields, respectively. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Bell's palsy before Bell: Cornelis Stalpart van der Wiel's observation of Bell's palsy in 1683.

PubMed

van de Graaf, Robert C; Nicolai, Jean-Philippe A

2005-11-01

Bell's palsy is named after Sir Charles Bell (1774-1842), who has long been considered to be the first to describe idiopathic facial paralysis in the early 19th century. However, it was discovered that Nicolaus Anton Friedreich (1761-1836) and James Douglas (1675-1742) preceded him in the 18th century. Recently, an even earlier account of Bell's palsy was found, as observed by Cornelis Stalpart van der Wiel (1620-1702) from The Hague, The Netherlands in 1683. Because our current knowledge of the history of Bell's palsy before Bell is limited to a few documents, it is interesting to discuss Stalpart van der Wiel's description and determine its additional value for the history of Bell's palsy. It is concluded that Cornelis Stalpart van der Wiel was the first to record Bell's palsy in 1683. His manuscript provides clues for future historical research.

Effects of Repeated Intraperitoneal Injection of Pharmaceutical-grade and Nonpharmaceutical-grade Corn Oil in Female C57BL/6J Mice

PubMed Central

Hubbard, Jennifer S; Chen, Patty H; Boyd, Kelli L

2017-01-01

Due to potential adverse effects on animal wellbeing, the use of nonpharmaceutical-grade substances in animal research must be scientifically justified in cases where a pharmaceutical-grade version of the substance exists. This requirement applies to all substances, including vehicles used to solubilize experimental drugs. To date, no studies have evaluated the direct effect of the pharmaceutical classification of a compound on animal wellbeing. In this study, we evaluated intraperitoneal administration of pharmaceutical-grade corn oil, nonpharmaceutical-grade corn oil, and saline in female C57BL/6J mice. Compounds were administered every 48 h for a total of 4 injections. Mice were evaluated clinically by using body weight, body condition score, visual assessment score, CBC, and serum chemistries. Animals were euthanized at 24 h and 14 d after the final injection. Inflammation of the peritoneal wall and mesenteric fat was assessed microscopically by using a semiquantitative scoring system. Saline-dosed groups had lower pathology scores at both time points. At day 21, pharmaceutical-grade corn oil had a significantly higher pathology score compared with nonpharmaceutical-grade corn oil. No other significant differences between the corn oil groups were observed. The use of nonpharmaceutical grade corn oil did not result in adverse clinical consequences and is presumed safe to use for intraperitoneal injection in mice. Differences in inflammation between the 2 groups suggest that the use of either pharmaceutical-grade or nonpharmaceutical-grade corn oil should be consistent within a study. PMID:29256373

Molecular dynamics simulations reveal that water diffusion between graphene oxide layers is slow

DOE PAGES

Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; ...

2016-07-08

Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of a molecular dynamics simulation study of water intercalated between GO layers that have a C/O ratio of 4. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in spacing from about 0.7 nm to 0.8 nm and an increase in mass ofmore » about 14% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. As a result, slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.« less

Properties of Cement Mortar and Ultra-High Strength Concrete Incorporating Graphene Oxide Nanosheets

PubMed Central

Ouyang, Dong

2017-01-01

In this work, the effect of graphene oxide nanosheet (GONS) additives on the properties of cement mortar and ultra-high strength concrete (UHSC) is reported. The resulting GONS-cement composites were easy to prepare and exhibited excellent mechanical properties. However, their fluidity decreased with increasing GONS content. The UHSC specimens were prepared with various amounts of GONSs (0–0.03% by weight of cement). Results indicated that using 0.01% by weight of cement GONSs caused a 7.82% in compressive strength after 28 days of curing. Moreover, adding GONSs improved the flexural strength and deformation ability, with the increase in flexural strength more than that of compressive strength. Furthermore, field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of the hardened cement paste and UHSC samples. FE-SEM observations showed that the GONSs were well dispersed in the matrix and the bonding of the GONSs and the surrounding cement matrix was strong. Furthermore, FE-SEM observation indicated that the GONSs probably affected the shape of the cement hydration products. However, the growth space for hydrates also had an important effect on the morphology of hydrates. The true hydration mechanism of cement composites with GONSs needs further study. PMID:28726750

The Effect of Compaction Force on the Transition to Hydrate of Anhydrous Aripiprazole.

PubMed

Togo, Taichiro; Taniguchi, Toshiya; Nakata, Yoshitaka

2018-01-01

Aripiprazole (APZ) is used to treat schizophrenia and is administered as a tablet containing the anhydrous form of APZ. In this study, the effect of compaction force on the crystal form transition was investigated. The crystalline state was observed by X-ray diffraction (XRD). APZ Anhydrous Form II was compacted into tablets. The XRD intensity of anhydrous APZ became lower with higher compressive force. The degree of crystallinity decreased with the compaction force. The powder and the compacted tablets of anhydrous APZ were stored for one week under 60°C and 75% relative humidity. The powder showed no crystal form transition after storage. For the tablets, however, XRD peaks of APZ hydrate were observed after storage. The tablets compacted with higher force showed the higher XRD diffraction intensity of hydrate form. We concluded that the crystallinity reduction of APZ Anhydrous Form II by compaction caused and accelerated the transition to hydrate under high temperature and humidity conditions. In order to manufacture crystallographically stable tablets containing anhydrous APZ, it is important to prevent this crystallinity reduction during compaction.

Molecular Orientation in Dry and Hydrated Cellulose Fibers: A Coherent Anti-Stokes Raman Scattering Microscopy Study

PubMed Central

Zimmerley, Maxwell; Younger, Rebecca; Valenton, Tiffany; Oertel, David C.; Ward, Jimmie L.; Potma, Eric O.

2012-01-01

Coherent anti-Stokes Raman scattering (CARS) microscopy is combined with spontaneous Raman scattering microspectroscopy and second harmonic generation (SHG) microscopy to interrogate the molecular alignment in dry and hydrated cellulose fibers. Two types of cellulose were investigated: natural cellulose I in cotton fibers and regenerated cellulose II in rayon fibers. On the basis of the orientation of the methylene symmetric stretching vibration, the molecular alignment of cellulose microfibrils is found to be conserved on the micrometer scale. Whereas the molecular orientation in cotton shows modest variability along the fiber, the alignment of the cellulose units in rayon is highly consistent throughout the fiber. The ordered alignment is retained upon fiber hydration. Upon hydration of the cellulose fibers, an anisotropic electronic contribution is observed, which indicates an ordered incorporation of water molecules into the fiber structure. The third-order and second-order electronic polarizability of cellulose I are directed along the axis of the polyglucan chain. No second-order optical response is observed in cellulose II, supporting the antiparallel arrangement of the polyglucan chains in regenerated cellulose. PMID:20684644

Deep-Water Acoustic Anomalies from Methane Hydrate in the Bering Sea

USGS Publications Warehouse

Wood, Warren T.; Barth, Ginger A.; Scholl, David W.; Lebedeva-Ivanova, Nina

2015-01-01

A recent expedition to the central Bering Sea, one of the most remote locations in the world, has yielded observations confirming gas and gas hydrates in this deep ocean basin. Significant sound speed anomalies found using inversion of pre-stack seismic data are observed in association with variable seismic amplitude anomalies in the thick sediment column. The anomalously low sound speeds below the inferred base of methane hydrate stability indicate the presence of potentially large quantities of gas-phase methane associated with each velocity-amplitude anomaly (VAMP). The data acquired are of such high quality that quantitative estimates of the concentrations of gas hydrates in the upper few hundred meters of sediment are also possible, and analyses are under way to make these estimates. Several VAMPs were specifically targeted in this survey; others were crossed incidentally. Indications of many dozens or hundreds of these features exist throughout the portion of the Bering Sea relevant to the U.S. extended continental shelf (ECS) consistent with the United Nations Convention on the Law of the Sea. 

Differential Scanning Calorimetric Study and Potential Model of the Binding of the Primary Water of Hydration to K-Hyaluronate

NASA Astrophysics Data System (ADS)

Whitson, K. B.; Marlowe, R. L.; Lukan, A. M.; Lee, S. A.; Anthony, L.; Rupprecht, A.

1997-11-01

DSC was performed on samples of K-hyaluronate (KHA) through a temperature range of 25-180^oC. A transition peak was observed which is due to the desorption of the primary water of hydration. The maximum position of the peak was observed to change with different scan rates. The average energy of activation, E_A, and enthalpy for desorption of the primary water of hydration was determined to be 0.62 and 0.17 eV per water molecule, respectively. Analysis of Mossbauer data(G. Albanese et al., Hyperfine Int.,) 95, 97 (1995) allowed us to determine the effective force constant, k_eff, of the water bound to KHA to be approximately 19.4 eV/nm^2. The parameters E_A, ΔH,and k_eff allow us to construct a potential model for the primary water of hydration of KHA. Comparison of these parameters with the same parameters for HA and DNA with different counterions reveal that the energy of activation is similar, as well as the enthalpy change.

Strength, leachability and microstructure characteristics of cement-based solidified plating sludge

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

Asavapisit, Suwimol; Naksrichum, Siripat; Harnwajanawong, Naraporn

2005-06-01

The solidification of the stabilized zinc-cyanide plating sludge was carried out using ordinary Portland cement (OPC) and pulverized fuel ash (PFA) as solidification binders. The plating sludge were used at the level of 0%, 10%, 20% and 30% dry weight, and PFA was used to replace OPC at 0%, 10%, 20% and 30% dry weight, respectively. Experimental results showed that a significant reduction in strength was observed when the plating sludge was added to both the OPC and OPC/PFA binders, but the negative effect was minimized when PFA was used as part substitute for OPC. SEM observation reveals that themore » deposition of the plating sludge on the surface of the clinkers and PFA could be the cause for hydration retardation. In addition, calcium zinc hydroxide hydrate complex and the unreacted di- and tricalcium silicates were the major phases in X-ray diffraction (XRD) patterns of the solidified plating waste hydrated for 28 days, although the retardation effect on hydration reactions but Cr concentration in toxicity characteristic leaching procedure (TCLP) leachates was lower than the U.S. EPA regulatory limit.« less

Insights into Gulf of Mexico Gas Hydrate Study Sites GC955 and WR313 from New Multicomponent and High-Resolution 2D Seismic Data

NASA Astrophysics Data System (ADS)

Haines, S. S.; Hart, P. E.; Collett, T. S.; Shedd, W. W.; Frye, M.

2014-12-01

In 2013, the U.S. Geological Survey led a seismic acquisition expedition in the Gulf of Mexico, acquiring multicomponent data and high-resolution 2D multichannel seismic (MCS) data at Green Canyon 955 (GC955) and Walker Ridge 313 (WR313). Based on previously collected logging-while-drilling (LWD) borehole data, these gas hydrate study sites are known to include high concentrations of gas hydrate within sand layers. At GC955 our new 2D data reveal at least three features that appear to be fluid-flow pathways (chimneys) responsible for gas migration and thus account for some aspects of the gas hydrate distribution observed in the LWD data. Our new data also show that the main gas hydrate target, a Pleistocene channel/levee complex, has an areal extent of approximately 5.5 square kilometers and that a volume of approximately 3 x 107 cubic meters of this body lies within the gas hydrate stability zone. Based on LWD-inferred values and reasonable assumptions for net sand, sand porosity, and gas hydrate saturation, we estimate a total equivalent gas-in-place volume of approximately 8 x 108 cubic meters for the inferred gas hydrate within the channel/levee deposits. At WR313 we are able to map the thin hydrate-bearing sand layers in considerably greater detail than that provided by previous data. We also can map the evolving and migrating channel feature that persists in this area. Together these data and the emerging results provide valuable new insights into the gas hydrate systems at these two sites.

Molecular mechanisms responsible for hydrate anti-agglomerant performance.

PubMed

Phan, Anh; Bui, Tai; Acosta, Erick; Krishnamurthy, Pushkala; Striolo, Alberto

2016-09-28

Steered and equilibrium molecular dynamics simulations were employed to study the coalescence of a sI hydrate particle and a water droplet within a hydrocarbon mixture. The size of both the hydrate particle and the water droplet is comparable to that of the aqueous core in reverse micelles. The simulations were repeated in the presence of various quaternary ammonium chloride surfactants. We investigated the effects due to different groups on the quaternary head group (e.g. methyl vs. butyl groups), as well as different hydrophobic tail lengths (e.g. n-hexadecyl vs. n-dodecyl tails) on the surfactants' ability to prevent coalescence. Visual inspection of sequences of simulation snapshots indicates that when the water droplet is not covered by surfactants it is more likely to approach the hydrate particle, penetrate the protective surfactant film, reach the hydrate surface, and coalesce with the hydrate than when surfactants are present on both surfaces. Force-distance profiles obtained from steered molecular dynamics simulations and free energy profiles obtained from umbrella sampling suggest that surfactants with butyl tripods on the quaternary head group and hydrophobic tails with size similar to the solvent molecules can act as effective anti-agglomerants. These results qualitatively agree with macroscopic experimental observations. The simulation results provide additional insights, which could be useful in flow assurance applications: the butyl tripod provides adhesion between surfactants and hydrates; when the length of the surfactant tail is compatible with that of the hydrocarbon in the liquid phase a protective film can form on the hydrate; however, once a molecularly thin chain of water molecules forms through the anti-agglomerant film, connecting the water droplet and the hydrate, water flows to the hydrate and coalescence is inevitable.

The effect of silica particle sizes and promoters to equilibrium moisture content for CO2 hydrate formation in HPVA

NASA Astrophysics Data System (ADS)

Hassan, Mohd Hafiz Abu; Snape, Colin Edwards; Steven, Lee

2018-06-01

The formation of CO2 hydrate (CO2:6H2O) in this work was experimentally investigated in batch mode inside a high pressure volumetric analyser (HPVA). The investigations in pure CO2 gas systems highlighted the effect of type of silicas used and the concentration of promoters used on the amount of equilibrium moisture content available for formation of hydrate. Standard silica gel was the only silica found to show hydrate formation due to the best distribution of pore size with the amount of equilibrium moisture content of 14.8 wt%. The high amount of bulk water inside zeolites 13X and spherical MCF-17 (21.3 and 50.8 wt% respectively) was the main reason of no hydrate formation observed due to the interstitial spaces between both silica particles were fully occupied by water. In other words, diffusion of gas molecules into the water is required for hydrate nucleation as well as hydrate growth. Additionally, the combined-promoters designated type T1-5 (0.01 mol% sodium dodecyl sulphate (SDS)+5.6 mol% tetrahydrofuran (THF)) was the best obtaining a CO2 uptake of 5.95 mmol of CO2 per g of H2O with the amount of equilibrium moisture content of 13.28 wt%.

Generation of hydrate forms of paroxetine HCl from the amorphous state: an evaluation of thermodynamic and experimental predictive approaches.

PubMed

Pina, M Fátima; Pinto, João F; Sousa, João J; Craig, Duncan Q M; Zhao, Min

2015-03-15

In this study, we evaluate the use of theoretical thermodynamic analysis of amorphous paroxetine hydrochloride (HCl) as well as experimental assessment in order to identify the most promising approach to stability and dissolution behaviour prediction, particularly in relation to stoichiometric and nonstoichiometric hydrate formation. Differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared and X-ray diffraction techniques were used. Parameters including heat capacity, configurational thermodynamic quantities, fragility and relaxation time classified amorphous paroxetine HCl as a moderate fragile glass with a considerable degree of molecular mobility. Solubility studies indicated little advantage of the amorphous form over the crystalline due to conversion to the hydrate Form I during equilibration, while the dissolution rate was higher for the amorphous form under sink conditions. A marked difference in the physical stability of amorphous paroxetine HCl was observed between dry and low humidity storage, with the system recrystallizing to the hydrate form. We conclude that, in this particular case (amorphous conversion to the hydrate), water may be playing a dual role in both plasticizing the amorphous form and driving the equilibrium towards the hydrate form, hence prediction of recrystallization behaviour from amorphous characteristics may be confounded by the additional process of hydrate generation. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydration Characteristics of Low-Heat Cement Substituted by Fly Ash and Limestone Powder.

PubMed

Kim, Si-Jun; Yang, Keun-Hyeok; Moon, Gyu-Don

2015-09-01

This study proposed a new binder as an alternative to conventional cement to reduce the heat of hydration in mass concrete elements. As a main cementitious material, low-heat cement (LHC) was considered, and then fly ash (FA), modified FA (MFA) by vibrator mill, and limestone powder (LP) were used as a partial replacement of LHC. The addition of FA delayed the induction period at the hydration heat curve and the maximum heat flow value ( q max ) increased compared with the LHC based binder. As the proportion and fineness of the FA increased, the induction period of the hydration heat curve was extended, and the q max increased. The hydration production of Ca(OH)₂ was independent of the addition of FA or MFA up to an age of 7 days, beyond which the amount of Ca(OH)₂ gradually decreased owing to their pozzolanic reaction. In the case of LP being used as a supplementary cementitious material, the induction period of the hydration heat curve was reduced by comparison with the case of LHC based binder, and monocarboaluminate was observed as a hydration product. The average pore size measured at an age of 28 days was smaller for LHC with FA or MFA than for 100% LHC.

Changes in hydration of the stratum corneum are the most suitable indicator to evaluate the irritation of surfactants on the skin.

PubMed

Fujimura, T; Shimotoyodome, Y; Nishijima, T; Sugata, K; Taguchi, H; Moriwaki, S

2017-02-01

Irritancy levels of surfactants on human skin have not been clarified completely. The relationships between skin damage and changes of skin properties caused by various surfactants were investigated using non-invasive measurements. Aqueous solutions of seven kinds of anionic, non-ionic, and amphoteric surfactants were exposed to the inside of forearm skin of 20 human subjects in two separate studies using the cup method. Hydration of the stratum corneum (SC), transepidermal water loss (TEWL), pH, skin surface roughness, and contents of the SC were measured before and after one exposure and after five and nine consecutive exposures to various surfactants. The discontinuation ratio of subjects for testing in each surfactant was determined by skin irritation symptoms and was defined as the degree of skin damage. Significant changes were observed only in hydration, TEWL, and natural moisturizing factors (NMF) content in the SC following surfactant exposure. A significant correlation was observed between the discontinuation ratio of each surfactant and the changes of hydration, TEWL, and NMF. Especially, the change of SC hydration showed an excellent correlation with the discontinuation ratio both for single (r = 0.942, P < 0.001) and for chronic exposures (r = 0.934, P < 0.001). Our results indicate that the change of hydration of the SC is equivalent to the skin damage caused by surfactants, and therefore is the most suitable indicator to evaluate the irritation of surfactants on the skin. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Temporal Stability of Surface Roughness Effects on Radar Based Soil Moisture Retrieval During the Corn Growth Cycle

NASA Technical Reports Server (NTRS)

Joseph, A.T.; Lang, R.; O'Neill, P.E.; van der Velde, R.; Gish, T.

2008-01-01

A representative soil surface roughness parameterization needed for the retrieval of soil moisture from active microwave satellite observation is difficult to obtain through either in-situ measurements or remote sensing-based inversion techniques. Typically, for the retrieval of soil moisture, temporal variations in surface roughness are assumed to be negligible. Although previous investigations have suggested that this assumption might be reasonable for natural vegetation covers (Moran et al. 2002, Thoma et al. 2006), insitu measurements over plowed agricultural fields (Callens et al. 2006) have shown that the soil surface roughness can change considerably over time. This paper reports on the temporal stability of surface roughness effects on radar observations and soil moisture retrieved from these radar observations collected once a week during a corn growth cycle (May 10th - October 2002). The data set employed was collected during the Optimizing Production Inputs for Economic and Environmental Enhancement (OPE3) field campaign covering this 2002 corn growth cycle and consists of dual-polarized (HH and VV) L-band (1.6 GHz) acquired at view angles of 15, 35, and 55 degrees. Cross-polarized L baud radar data were also collected as part of this experiment, but are not used in the analysis reported on here. After accounting for vegetation effects on radar observations, time-invariant optimum roughness parameters were determined using the Integral Equation Method (IEM) and radar observations acquired over bare soil and cropped conditions (the complete radar data set includes entire corn growth cycle). The optimum roughness parameters, soil moisture retrieval uncertainty, temporal distribution of retrieval errors and its relationship with the weather conditions (e.g. rainfall and wind speed) have been analyzed. It is shown that over the corn growth cycle, temporal roughness variations due to weathering by rain are responsible for almost 50% of soil moisture retrieval uncertainty depending on the sensing configuration. The effects of surface roughness variations are found to be smallest for observations acquired at a view angle of 55 degrees and HH polarization. A possible explanation for this result is that at 55 degrees and HH polarization the effect of vertical surface height changes on the observed radar response are limited because the microwaves travel parallel to the incident plane and as a result will not interact directly with vertically oriented soil structures.

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1998-01-01

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25-30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140-200 K, Pc = 50-100 MPa, and ?? = 10-4 10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, Sabine; Nöthen, Kerstin; Hensen, Christian; Spieß, Volkhard; Blumenberg, Martin; Schneider, Ralph R.

2012-12-01

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Characterization of a stratigraphically constrained gas hydrate system along the western continental margin of Svalbard from ocean bottom seismometer data

NASA Astrophysics Data System (ADS)

Chabert, Anne; Minshull, Tim A.; Westbrook, Graham K.; Berndt, Christian; Thatcher, Kate E.; Sarkar, Sudipta

2011-12-01

The ongoing warming of bottom water in the Arctic region is anticipated to destabilize some of the gas hydrate present in shallow seafloor sediment, potentially causing the release of methane from dissociating hydrate into the ocean and the atmosphere. Ocean-bottom seismometer (OBS) experiments were conducted along the continental margin of western Svalbard to quantify the amount of methane present as hydrate or gas beneath the seabed. P- and S-wave velocities were modeled for five sites along the continental margin, using ray-trace forward modeling. Two southern sites were located in the vicinity of a 30 km long zone where methane gas bubbles escaping from the seafloor were observed during the cruise. The three remaining sites were located along an E-W orientated line in the north of the margin. At the deepest northern site, Vp anomalies indicate the presence of hydrate in the sediment immediately overlying a zone containing free gas up to 100-m thick. The acoustic impedance contrast between the two zones forms a bottom-simulating reflector (BSR) at approximately 195 m below the seabed. The two other sites within the gas hydrate stability zone (GHSZ) do not show the clear presence of a BSR or of gas hydrate. However, anomalously low Vp, indicating the presence of free gas, was modeled for both sites. The hydrate content was estimated from Vp and Vs, using effective-medium theory. At the deepest northern site, modeling suggests a pore-space hydrate concentration of 7-12%, if hydrate forms as part of a connected framework, and about 22% if it is pore-filling. At the two other northern sites, located between the deepest site and the landward limit of the GHSZ, we suggest that hydrate is present in the sediment as inclusions. Hydrate may be present in small quantities at these two sites (4-5%) of the pore space. The variation in lithology for the three sites indicated by high-resolution seismic profiles may control the distribution, concentration and formation of hydrate and free gas.

Hydration-Dependent Dynamical Modes in Xyloglucan from Molecular Dynamics Simulation of 13C NMR Relaxation Times and Their Distributions.

PubMed

Chen, Pan; Terenzi, Camilla; Furó, István; Berglund, Lars A; Wohlert, Jakob

2018-05-15

Macromolecular dynamics in biological systems, which play a crucial role for biomolecular function and activity at ambient temperature, depend strongly on moisture content. Yet, a generally accepted quantitative model of hydration-dependent phenomena based on local relaxation and diffusive dynamics of both polymer and its adsorbed water is still missing. In this work, atomistic-scale spatial distributions of motional modes are calculated using molecular dynamics simulations of hydrated xyloglucan (XG). These are shown to reproduce experimental hydration-dependent 13 C NMR longitudinal relaxation times ( T 1 ) at room temperature, and relevant features of their broad distributions, which are indicative of locally heterogeneous polymer reorientational dynamics. At low hydration, the self-diffusion behavior of water shows that water molecules are confined to particular locations in the randomly aggregated XG network while the average polymer segmental mobility remains low. Upon increasing water content, the hydration network becomes mobile and fully accessible for individual water molecules, and the motion of hydrated XG segments becomes faster. Yet, the polymer network retains a heterogeneous gel-like structure even at the highest level of hydration. We show that the observed distribution of relaxations times arises from the spatial heterogeneity of chain mobility that in turn is a result of heterogeneous distribution of water-chain and chain-chain interactions. Our findings contribute to the picture of hydration-dependent dynamics in other macromolecules such as proteins, DNA, and synthetic polymers, and hold important implications for the mechanical properties of polysaccharide matrixes in plants and plant-based materials.

Sulfates on Mars: A systematic Raman spectroscopic study of hydration states of magnesium sulfates

USGS Publications Warehouse

Wang, A.; Freeman, J.J.; Jolliff, B.L.; Chou, I.-Ming

2006-01-01

The martian orbital and landed surface missions, OMEGA on Mar Express and the two Mars Explorations Rovers, respectively, have yielded evidence pointing to the presence of magnesium sulfates on the martian surface. In situ identification of the hydration states of magnesium sulfates, as well as the hydration states of other Ca- and Fe- sulfates, will be crucial in future landed missions on Mars in order to advance our knowledge of the hydrologic history of Mars as well as the potential for hosting life on Mars. Raman spectroscopy is a technique well-suited for landed missions on the martian surface. In this paper, we report a systematic study of the Raman spectra of the hydrates of magnesium sulfate. Characteristic and distinct Raman spectral patterns were observed for each of the 11 distinct hydrates of magnesium sulfates, crystalline and non-crystalline. The unique Raman spectral features along with the general tendency of the shift of the position of the sulfate ??1 band towards higher wavenumbers with a decrease in the degree of hydration allow in situ identification of these hydrated magnesium sulfates from the raw Raman spectra of mixtures. Using these Raman spectral features, we have started the study of the stability field of hydrated magnesium sulfates and the pathways of their transformations at various temperature and relative humidity conditions. In particular we report on the Raman spectrum of an amorphous hydrate of magnesium sulfate (MgSO4??2H2O) that may have specific relevance for the martian surface. ?? 2006 Elsevier Inc. All rights reserved.

Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas, and carbon dioxide

USGS Publications Warehouse

Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.

1998-01-01

We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO2 into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P-T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9??C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO2 the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO2 mass, and an apparent consolidation of the CH4 hydrate, over a period of about 85 days.

A meta-analysis of outcomes of hydration intervention on phonation threshold pressure.

PubMed

Leydon, Ciara; Wroblewski, Marcin; Eichorn, Naomi; Sivasankar, Mahalakshmi

2010-11-01

Vocal fold hydration is purported to promote optimal biomechanical characteristics of vocal fold mucosa, increase efficiency of vocal fold oscillation, and enhance voice quality. The purpose of this work was to determine the magnitude and consistency of the effect of vocal fold hydration on vocal fold function across published clinical studies. We completed a comprehensive meta-analysis of the effects of superficial and systemic vocal fold hydration on phonation threshold pressure (PTP), a measure of efficiency of voice production. We identified 34 studies that examined the effects of hydration on vocal function. Of these studies, 14 examined the effects of hydration on PTP. Nine of these articles met the criteria for inclusion in this analysis. We observed an average effect size of 0.33, indicating that, overall, hydration treatment demonstrated a tendency to reduce PTP. However, this decrease in phonatory effort did not reach significance at the 95% confidence level. The effects of hydration intervention varied considerably across studies (-0.19 to 3.96). We considered that two factors, pitch level of the task and vocal health of participants, may have contributed to this variability in findings. However, our analysis found that these factors could not account for differences in effect size. To understand the variability in outcomes across studies, the role of factors that may impact the effects of hydration, such as the amount, type, and duration of intervention, must be determined. Only then can we obtain data to guide best clinical practice for protecting and rehabilitating vocal function. Copyright © 2010 The Voice Foundation. Published by Mosby, Inc. All rights reserved.

Analysis of mesoscopic attenuation in gas-hydrate bearing sediments

NASA Astrophysics Data System (ADS)

Rubino, J. G.; Ravazzoli, C. L.; Santos, J. E.

2007-05-01

Several authors have shown that seismic wave attenuation combined with seismic velocities constitute a useful geophysical tool to infer the presence and amounts of gas hydrates lying in the pore space of the sediments. However, it is still not fully understood the loss mechanism associated to the presence of the hydrates, and most of the works dealing with this problem focuse on macroscopic fluid flow, friction between hydrates and sediment matrix and squirt flow. It is well known that an important cause of the attenuation levels observed in seismic data from some sedimentary regions is the mesoscopic loss mechanism, caused by heterogeneities in the rock and fluid properties greater than the pore size but much smaller than the wavelengths. In order to analyze this effect in heterogeneous gas-hydrate bearing sediments, we developed a finite-element procedure to obtain the effective complex modulus of an heterogeneous porous material containing gas hydrates in its pore space using compressibility tests at different oscillatory frequencies in the seismic range. The complex modulus were obtained by solving Biot's equations of motion in the space-frequency domain with appropriate boundary conditions representing a gedanken laboratory experiment measuring the complex volume change of a representative sample of heterogeneous bulk material. This complex modulus in turn allowed us to obtain the corresponding effective phase velocity and quality factor for each frequency and spatial gas hydrate distribution. Physical parameters taken from the Mallik 5L-38 Gas Hydrate Research well (Mackenzie Delta, Canada) were used to analyze the mesoscopic effects in realistic hydrated sediments.

Comparing effectiveness of rhamnolipid biosurfactant with a quaternary ammonium salt surfactant for hydrate anti-agglomeration.

PubMed

York, J Dalton; Firoozabadi, Abbas

2008-01-24

Natural gas is projected to be the premium fuel of the 21st century because of availability, as well as economical and environmental considerations. Natural gas is coproduced with water from the subsurface forming gas hydrates. Hydrate formation may result in shutdown of onshore and offshore operations. Industry practice has been usage of alcohols--which have undesirable environmental impacts--to affect bulk-phase properties and inhibit hydrate formation. An alternative to alcohols is changing the surface properties through usage of polymers and surfactants, effective at 0.5-3 wt % of coproduced water. One group of low-dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are anti-agglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, reported work on hydrate anti-agglomeration is very limited. In this paper, our focus is on the use of two vastly different surfactants as anti-agglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. We examine the effectiveness of a quaternary ammonium salt (i.e., quat). Visual observation measurements show that a small concentration of the quat (0.01%) can prevent agglomeration. However, a quat is not a green chemical and therefore may be undesirable. We show that a rhamnolipid biosurfactant can be effective to a concentration of 0.05 wt %. One difference between the two surfactants is the stability of the water-in-oil emulsions created. The biosurfactant forms a less stable emulsion, which makes it very desirable for hydrate application.

The effects of calcium hydroxide-treated whole-plant and fractionated corn silage on intake, digestion, and lactation performance in dairy cows.

PubMed

Cook, D E; Bender, R W; Shinners, K J; Combs, D K

2016-07-01

The objective of this trial was to evaluate, in dairy cattle, the effects of calcium hydroxide treatment of whole-plant corn and a treatment applied to the bottom stalk fraction of the corn plant, achieved by harvesting corn in 2 crop streams. The treatments were calcium hydroxide-treated corn silage (TRTCS), toplage supplemented with calcium hydroxide-treated stalklage (TPL), a positive control of brown midrib corn silage (BMR), and a negative control of conventional whole-plant corn silage (WPCS). The toplage was harvested at a height of 82 cm with 2 of the 6 rows set as ear-snapping to incorporate higher tissues into the stalklage. Stalklage was harvested at 12 cm, and other corn silages were harvested at 27 cm. Sixteen pens, each with 8 Holstein cows averaging 70±25 d in milk and 46±11 kg of milk d(-1), were assigned 4 per treatment in a completely randomized design. The diet was approximately 40% corn silage, 20% alfalfa silage, and 40% concentrate on a dry matter basis. A 2-wk covariate period with conventional corn silage was followed by an 8-wk treatment period in which the 4 corn silage treatments were the only effective difference in diets. Cows fed TPL and TRTCS consumed more (1.9 and 1.4 kg of organic matter d(-1), respectively) than did cows fed WPCS. Milk yield was greater for cows fed BMR, TPL, and TRTCS. Cows fed BMR and TPL produced 2.9 and 2.7 kg d(-1), respectively, more energy-corrected milk (ECM) than cows fed WPCS, and cows fed TRTCS had the greatest ECM production (4.8 kg of ECM d(-1) greater than cows fed WPCS). No differences in body weight or body condition scored were observed. Milk fat concentration was similar among treatments and milk protein concentration was reduced for TRTCS. Starch and neutral detergent fiber digestibility were greater for cows fed TRTCS. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

The influence of ion hydration on nucleation and growth of LiF crystals in aqueous solution.

PubMed

Lanaro, G; Patey, G N

2018-01-14

Molecular dynamics (MD) simulations are employed to investigate crystal nucleation and growth in oversaturated aqueous LiF solutions. Results obtained for a range of temperatures provide evidence that the rate of crystal growth is determined by a substantial energy barrier (∼49 kJ mol -1 ) related to the loss of water from the ion hydration shells. Employing direct MD simulations, we do not observe spontaneous nucleation of LiF crystals at 300 K, but nucleation is easily observable in NVT simulations at 500 K. This contrasts with the NaCl case, where crystal nucleation is directly observed in similar simulations at 300 K. Based on these observations, together with a detailed analysis of ion clustering in metastable LiF solutions, we argue that the ion dehydration barrier also plays a key role in crystal nucleation. The hydration of the relatively small Li + and F - ions strongly influences the probability of forming large, crystal-like ion clusters, which are a necessary precursor to nucleation. This important factor is not accounted for in classical nucleation theory.

The influence of ion hydration on nucleation and growth of LiF crystals in aqueous solution

NASA Astrophysics Data System (ADS)

Lanaro, G.; Patey, G. N.

2018-01-01

Molecular dynamics (MD) simulations are employed to investigate crystal nucleation and growth in oversaturated aqueous LiF solutions. Results obtained for a range of temperatures provide evidence that the rate of crystal growth is determined by a substantial energy barrier (˜49 kJ mol-1) related to the loss of water from the ion hydration shells. Employing direct MD simulations, we do not observe spontaneous nucleation of LiF crystals at 300 K, but nucleation is easily observable in NVT simulations at 500 K. This contrasts with the NaCl case, where crystal nucleation is directly observed in similar simulations at 300 K. Based on these observations, together with a detailed analysis of ion clustering in metastable LiF solutions, we argue that the ion dehydration barrier also plays a key role in crystal nucleation. The hydration of the relatively small Li+ and F- ions strongly influences the probability of forming large, crystal-like ion clusters, which are a necessary precursor to nucleation. This important factor is not accounted for in classical nucleation theory.

Hydration Dynamics of Hyaluronan and Dextran

PubMed Central

Hunger, Johannes; Bernecker, Anja; Bakker, Huib J.; Bonn, Mischa; Richter, Ralf P.

2012-01-01

Hyaluronan is a polysaccharide, which is ubiquitous in vertebrates and has been reported to be strongly hydrated in a biological environment. We study the hydration of hyaluronan in solution using the rotational dynamics of water as a probe. We measure these dynamics with polarization-resolved femtosecond-infrared and terahertz time-domain spectroscopies. Both experiments reveal that a subensemble of water molecules is slowed down in aqueous solutions of hyaluronan amounting to ∼15 water molecules per disaccharide unit. This quantity is consistent with what would be expected for the first hydration shell. Comparison of these results to the water dynamics in aqueous dextran solution, a structurally similar polysaccharide, yields remarkably similar results. This suggests that the observed interaction with water is a common feature for hydrophilic polysaccharides and is not specific to hyaluronan. PMID:22828349

Beauveria bassiana (Ascomycota: Hypocreales) Introduced as an Endophyte in Corn Plants and Its Effects on Consumption, Reproductive Capacity, and Food Preference of Dichroplus maculipennis (Orthoptera: Acrididae: Melanoplinae).

PubMed

Pelizza, Sebastian A; Mariottini, Yanina; Russo, Leticia M; Vianna, M Florencia; Scorsetti, Ana C; Lange, Carlos E

2017-01-01

In this study, the effects of strain Beauveria bassiana (LPSC 1067) as an endophyte in corn plants on consumption, fecundity, and food preference of Dichroplus maculipennis were examined. We observed that the daily consumption by grasshoppers fed with control plants was almost twice that of those that were fed treated plants. Significant differences in fecundity of grasshoppers that were fed with treated plants compared with those that only fed on control plants were also observed. The number of eggs laid per female fed with control plants was 27.2, while the number of eggs laid per female that were fed during 15 d with treated plants was 17.7. Similar results were observed when the number of embryonated eggs was evaluated. The highest number of embryonated eggs were recorded in those females that only fed on control plants (96%) while fewer embryonated eggs were recorded in grasshoppers fed for 15 d with treated plants only (25%). In relation to food preference the average consumption rate for D. maculipennis females on control corn plants was 303.8 ± 24.5 mg while it was only 25 ± 2.1 mg on plants treated with B. bassiana as an endophyte. In summary, we observed that B. bassiana as a corn plant endophyte negatively affected the daily consumption rate, fecundity and food preference of D. maculipennis. © The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America.

Prediction of pest pressure on corn root nodes: the POPP-Corn model.

PubMed

Agatz, Annika; Ashauer, Roman; Sweeney, Paul; Brown, Colin D

2017-01-01

A model for the corn rootworm Diabrotica spp. combined with a temporally explicit model for development of corn roots across the soil profile was developed to link pest ecology, root damage and yield loss. Development of the model focused on simulating root damage from rootworm feeding in accordance with observations in the field to allow the virtual testing of efficacy from management interventions in the future. We present the model and demonstrate its applicability for simulating root damage by comparison between observed and simulated pest development and root damage (assessed according to the node injury scale from 0 to 3) for field studies from the literature conducted in Urbana, Illinois (US), between 1991 and 2014. The model simulated the first appearance of larvae and adults to within a week of that observed in 88 and 71 % of all years, respectively, and in all cases to within 2 weeks of the first sightings recorded for central Illinois. Furthermore, in 73 % of all years simulated root damage differed by <0.5 node injury scale points compared to the observations made in the field between 2005 and 2014 even though accurate information for initial pest pressure (i.e. number of eggs in the soil) was not measured at the sites or available from nearby locations. This is, to our knowledge, the first time that pest ecology, root damage and yield loss have been successfully interlinked to produce a virtual field. There are potential applications in investigating efficacy of different pest control measures and strategies.

Subchronic toxicity study of corn silk with rats.

PubMed

Wang, Cuina; Zhang, Tiehua; Liu, Jun; Lu, Shuang; Zhang, Cheng; Wang, Erlei; Wang, Zuozhao; Zhang, Yan; Liu, Jingbo

2011-09-01

Corn silk is a traditional herbal medicine in China, which has been used in many parts of the world for the treatment of edema as well as for cystitis, gout, kidney stones, nephritis, prostatitis and similar ailments. However, there is little scientific evidence about its safety. As a part of its safety assessment, a subchronic toxicity was performed in this paper. The subchronic toxicity was investigated in male and female Wistar rats by dietary administration at concentrations of 0.5%, 2.0% and 8.0% (w/w) for 90 days. Overall health, body weight, food consumption, hematology, blood chemistry, organ weights, gross and microscopic appearance of tissues were compared between test and control groups. A number of significant differences were seen between groups, but none of them was considered to be adverse. Based on the present study, the no-observed-adverse-effect level (NOAEL) of corn silk is at least 8.0% which corresponds to a mean daily corn silk intake of approximately 9.354 and 10.308 g/day/kg body weight for males and females, respectively. The results obtained in the present study suggest that consumption of corn silk has no adverse effects and support the safety of corn silk for humans. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Effects of different sources of physically effective fiber on rumen microbial populations.

PubMed

Shaw, C N; Kim, M; Eastridge, M L; Yu, Z

2016-03-01

Physically effective fiber is needed by dairy cattle to prevent ruminal acidosis. This study aimed to examine the effects of different sources of physically effective fiber on the populations of fibrolytic bacteria and methanogens. Five ruminally cannulated Holstein cows were each fed five diets differing in physically effective fiber sources over 15 weeks (21 days/period) in a Latin Square design: (1) 44.1% corn silage, (2) 34.0% corn silage plus 11.5% alfalfa hay, (3) 34.0% corn silage plus 5.1% wheat straw, (4) 36.1% corn silage plus 10.1% wheat straw, and (5) 34.0% corn silage plus 5.5% corn stover. The impact of the physically effective fiber sources on total bacteria and archaea were examined using denaturing gradient gel electrophoresis. Specific real-time PCR assays were used to quantify total bacteria, total archaea, the genus Butyrivibrio, Fibrobacter succinogenes, Ruminococcus albus, Ruminococcus flavefaciens and three uncultured rumen bacteria that were identified from adhering ruminal fractions in a previous study. No significant differences were observed among the different sources of physical effective fiber with respect to the microbial populations quantified. Any of the physically effective fiber sources may be fed to dairy cattle without negative impact on the ruminal microbial community.

The corn smut-made cholera oral vaccine is thermostable and induces long-lasting immunity in mouse.

PubMed

Monreal-Escalante, Elizabeth; Navarro-Tovar, Gabriela; León-Gallo, Amalia; Juárez-Montiel, Margarita; Becerra-Flora, Alicia; Jiménez-Bremont, Juan Francisco; Rosales-Mendoza, Sergio

2016-09-20

The use of corn smut for the production of recombinant vaccines has been recently implemented by our group. In this study, the stability and immunogenic properties of the corn smut-based cholera vaccine, based on the cholera toxin B subunit (CTB), were determined in mouse. The immunogenic potential of distinct corn smut CTB doses ranging from 1 to 30μg were assessed, with maximum humoral responses at both the systemic (IgG) and intestinal (IgA) levels at a dose of 15μg. The humoral response last for up to 70days after the third boost. Mice were fully protected against a challenge with cholera toxin after receiving three 15μg-doses. Remarkably, the corn smut-made vaccine retained its immunogenic activity after storage at room temperature for a period of 1year and no reduction on CTB was observed following exposure at 50°C for 2h. These data support the use of the corn smut-made CTB vaccine as a highly stable and effective immunogen and justify its evaluation in target animal models, such as piglet and sheep, as well as clinical evaluations in humans. Copyright © 2016 Elsevier B.V. All rights reserved.

High performance supercapacitor using porous carbon nanomaterial from corn cob

NASA Astrophysics Data System (ADS)

Sharma, Nallin; Mishra, Neeraj; Sharon, Madhuri; Sharon, Maheshwar

2013-06-01

Carbon synthesized from corn-cob has been used as an electrode in Electrochemical Double Layer Capacitor (EDLC). Dried Corn Cobs, soaked in 1N KOH, 1N HCl or 5% ZnCl2 at 10 0°C for 24 hr, were pyrolyzed in presence of Ar using Co as catalyst at 700-900 °C having dwell time of 60-180 min. The morphology of thus obtained carbon was studied under SEM that showed it to be porous carbon. All the carbon samples synthesized using different parameters were used as electrode for EDLC. Cyclic Voltammetry was used to measure the capacitance. Carbon synthesized from corn cobs pre-treated with 5% ZnCl2 using Co as catalyst pyrolyzed at 700°C for a dwell time of 120 min gave higher Specific capacitance of 270 F/g at scan rate of 5 mV/s. Moreover, this carbon, as observed under SEM, exhibited larger pore size.

Stabilization of Neem Oil Biodiesel with Corn Silk Extract during Long-term Storage.

PubMed

Ali, Rehab Farouk M; El-Anany, Ayman M

2017-02-01

The current study aimed to evaluate the antioxidant efficiency of different extracts of corn silk. In addition, the impact of corn silk extract on oxidative stability of neem biodiesel during storage was studied. The highest phenolics, DPPH radical scavenging and reducing power activities were recorded for methanol-water extract. The longest oxidation stability (10 h) was observed for biodiesel samples blended with 1000 ppm of corn silk extract (CSE). At the end of storage period the induction time of biodiesel samples mixed with 1000 ppm of CSE or butylated hydroxytoluene (BHT) were about 6.72 and 5.63 times as high as in biodiesel samples without antioxidants. Biodiesel samples blended with 1000 ppm of CSE had the lowest acidity at the end of storage period. Peroxide value of biodiesel samples containing 1000 ppm of CSE was about 4.28 times as low as in control sample without antioxidants.

The Pasting and Gel Textural Properties of Corn Starch in Glucose, Fructose and Maltose Syrup

PubMed Central

Sun, Qingjie; Xing, Yan; Qiu, Chao; Xiong, Liu

2014-01-01

The pasting and gel textural properties of corn starch in syrup at different concentrations were investigated by Rapid Visco Analyzer (RVA) and Texture profile analysis (TPA) tests. The results showed that the pasting temperatures of corn starch greatly increased, especially at higher sugar concentration. Increasing concentration of syrup caused an increase in peak, trough and final viscosity of corn starch. Peak viscosity and the disintegration rate of starch increased in the following order: fructose syrup> maltose syrup> glucose syrup. Increasing syrup concentration to 13%, 25% and 50% resulted in a lower retrogradation rate than the control. When the maltose syrup concentration increased to 50%, the retrogradation rate decreased to 14.30% from 33.38%. The highest hardness was observed when the syrup concentration was 25%. There was a particular low hardness when the concentration of syrup was 50%. The springiness of starch gels in syrup was similar at different concentrations. PMID:24755772

The pasting and gel textural properties of corn starch in glucose, fructose and maltose syrup.

PubMed

Sun, Qingjie; Xing, Yan; Qiu, Chao; Xiong, Liu

2014-01-01

The pasting and gel textural properties of corn starch in syrup at different concentrations were investigated by Rapid Visco Analyzer (RVA) and Texture profile analysis (TPA) tests. The results showed that the pasting temperatures of corn starch greatly increased, especially at higher sugar concentration. Increasing concentration of syrup caused an increase in peak, trough and final viscosity of corn starch. Peak viscosity and the disintegration rate of starch increased in the following order: fructose syrup> maltose syrup> glucose syrup. Increasing syrup concentration to 13%, 25% and 50% resulted in a lower retrogradation rate than the control. When the maltose syrup concentration increased to 50%, the retrogradation rate decreased to 14.30% from 33.38%. The highest hardness was observed when the syrup concentration was 25%. There was a particular low hardness when the concentration of syrup was 50%. The springiness of starch gels in syrup was similar at different concentrations.

SEAFLOOR MANIFESTATIONS OF GAS VENTING AND NEAR SEAFLOOR GAS HYDRATE OCCURRENCES

NASA Astrophysics Data System (ADS)

Paull, C. K.; Ussler, W.; Caress, D. W.; Thomas, H.; Lundsten, E.; Riedel, M.; Lapham, L.

2009-12-01

High-resolution multibeam bathymetry and chirp seismic profiles collected with an AUV complimented by ROV observations and sampling reveal the fine scale geomorphology and seafloor structures associated with gas venting and/or near subsurface gas hydrate accumulations along the Pacific North American continental margin. Sites from Santa Monica Basin, northern and southern Hydrate Ridge, Barkley Canyon, Bullseye Vent and three previously unexplored vent sites near Bullseye Vent have been recently investigated. The new AUV data allow the identification of features and seafloor textures that were previously undetected and reveal the impact of gas venting, gas hydrate development and related phenomena on the seafloor morphology. Distinct geomorphic characteristics are interpreted to represent different stages in the development and evolution of the seafloor in these areas. The more mature features include distinct (>10 m high) elevated features (e.g., Santa Monica Mounds and the Hydrate Ridge Pinnacle), widespread areas where methane-derived carbonates are exposed on the surrounding seafloor (e.g., both Hydrate Ridge sites, and an unnamed ridge north of Bullseye Vent), circular seafloor craters with diameters of 3 to 50 m that appear to be associated with missing sections of the original seafloor (e.g., Bullseye Vent, northern Hydrate Ridge, and an unnamed ridge north of Bullseye Vent). Smaller mound-like features (<10 m in diameter and 1-3 m higher than the surrounding seafloor occur at Barkley Canyon and a newly explored vent system called Spinnaker Vent 6 km NW of Bullseye vent. Solid lens of gas hydrate are occasionally exposed along fractures on the sides of these mounds and suggest that these are push-up features associated with gas hydrate growth within the near seafloor sediments. The existence of both extensive methane-derived carbonates and chemosynthetic biological communities characterized by Vesicomya clams and Lamellibrachia tubeworms (which are slow growing) indicate that methane venting has occurred for protracted periods of time at these sites. However, the youngest appearing features occur in a gulch ~1 km NE of Bullseye Vent. They are associated with more-subtle (2-3 m in diameter and ~0.5 m high) seafloor mounds, with their crests crossed with small cracks lined with white bacterial mats, lack exposed methane-derived carbonates, Vesicomya clams or Lamellibrachia tubeworms. ROV-collected vibracores (<1.5 cm long) obtained from these subtle mounds characteristically encountered a hard layer at 30-60 cm sub-bottom. Where this layer was penetrated, methane bubbles would spontaneously gush out the hole and continue to flow out for more than an hour. These observations suggest that these small mounds are young features which have considerable volumes of over-pressured gas trapped near the seafloor. Together these observations reveal the integrated effect that gas and/or gas hydrate occurrences can have on the seafloor. The existence of apparently over-pressured gas within ~1 m of the seafloor has intriguing implications as to the geo-hazard potential of such sites.

Observation of interstitial molecular hydrogen in clathrate hydrates.

PubMed

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular insights into the heterogeneous crystal growth of si methane hydrate.

PubMed

Vatamanu, Jenel; Kusalik, Peter G

2006-08-17

In this paper we report a successful molecular simulation study exploring the heterogeneous crystal growth of sI methane hydrate along its [001] crystallographic face. The molecular modeling of the crystal growth of methane hydrate has proven in the past to be very challenging, and a reasonable framework to overcome the difficulties related to the simulation of such systems is presented. Both the microscopic mechanisms of heterogeneous crystal growth as well as interfacial properties of methane hydrate are probed. In the presence of the appropriate crystal template, a strong tendency for water molecules to organize into cages around methane at the growing interface is observed; the interface also demonstrates a strong affinity for methane molecules. The maximum growth rate measured for a hydrate crystal is about 4 times higher than the value previously determined for ice I in a similar framework (Gulam Razul, M. S.; Hendry, J. G.; Kusalik, P. G. J. Chem. Phys. 2005, 123, 204722).

Cellulose Nanofibers as a Modifier for Rheology, Curing and Mechanical Performance of Oil Well Cement.

PubMed

Sun, Xiuxuan; Wu, Qinglin; Lee, Sunyoung; Qing, Yan; Wu, Yiqiang

2016-08-16

The influence of nanocellulose on oil well cement (OWC) properties is not known in detail, despite recent advances in nanocellulose technology and its related composite materials. The effect of cellulose nanofibers (CNFs) on flow, hydration, morphology, and strength of OWC was investigated using a range of spectroscopic methods coupled with rheological modelling and strength analysis. The Vom-Berg model showed the best fitting result of the rheology data. The addition of CNFs increased the yield stress of OWC slurry and degree of hydration value of hydrated CNF-OWC composites. The flexural strength of hydrated OWC samples was increased by 20.7% at the CNF/OWC ratio of 0.04 wt%. Excessive addition of CNFs into OWC matrix had a detrimental effect on the mechanical properties of hydrated CNF-OWC composites. This phenomenon was attributed to the aggregation of CNFs as observed through coupled morphological and elemental analysis. This study demonstrates a sustainable reinforcing nano-material for use in cement-based formulations.

Cellulose Nanofibers as a Modifier for Rheology, Curing and Mechanical Performance of Oil Well Cement

NASA Astrophysics Data System (ADS)

Sun, Xiuxuan; Wu, Qinglin; Lee, Sunyoung; Qing, Yan; Wu, Yiqiang

2016-08-01

The influence of nanocellulose on oil well cement (OWC) properties is not known in detail, despite recent advances in nanocellulose technology and its related composite materials. The effect of cellulose nanofibers (CNFs) on flow, hydration, morphology, and strength of OWC was investigated using a range of spectroscopic methods coupled with rheological modelling and strength analysis. The Vom-Berg model showed the best fitting result of the rheology data. The addition of CNFs increased the yield stress of OWC slurry and degree of hydration value of hydrated CNF-OWC composites. The flexural strength of hydrated OWC samples was increased by 20.7% at the CNF/OWC ratio of 0.04 wt%. Excessive addition of CNFs into OWC matrix had a detrimental effect on the mechanical properties of hydrated CNF-OWC composites. This phenomenon was attributed to the aggregation of CNFs as observed through coupled morphological and elemental analysis. This study demonstrates a sustainable reinforcing nano-material for use in cement-based formulations.

In vivo skin imaging for hydration and micro relief-measurement.

PubMed

Kardosova, Z; Hegyi, V

2013-01-01

We present the results of our work with device used for measurement of skin capacitance before and after application of moisturizing creams and results of experiment performed on cellulose filter papers soaked with different solvents. The measurements were performed by a device built on capacitance sensor, which provides an investigator with a capacitance image of the skin. The capacitance values are coded in a range of 256 gray levels then the skin hydration can be characterized using parameters derived from gray level histogram by specific software. The images obtained by device allow a highly precise observation of skin topography. Measuring of skin capacitance brings new, objective, reliable information about topographical, physical and chemical parameters of the skin. The study shows that there is a good correlation between the average grayscale values and skin hydration. In future works we need to complete more comparison studies, interpret the average grayscale values to skin hydration levels and use it for follow-up of dynamics of skin micro-relief and hydration changes (Fig. 6, Ref. 15).

Combined effects of lithium and borate ions on the hydration of calcium sulfoaluminate cement

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

Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr; Dhoury, Mélanie; Champenois, Jean-Baptiste

This work investigates the combined influence of borate and lithium ions on the hydration of two calcium sulfoaluminate (CSA) cements containing 0 or 10 wt% gypsum. On the one hand, borates are known to retard CSA cement hydration due to the rapid precipitation of ulexite. On the other hand, lithium ions accelerate CSA cement hydration thanks to the fast precipitation of Li-containing aluminum hydroxide. When borates and lithium are present simultaneously, these two mechanisms are superimposed. With a gypsum-free cement, a third process is additionally observed: lithium promotes the initial precipitation of a borated AFm phase which is later convertedmore » into a borated AFt phase when hydration accelerates. Lithium salts can counteract the retardation by sodium borate. However, their influence is limited once a sufficient amount of Li-containing Al(OH){sub 3} seeds is formed. For the CSA cements under investigation, the threshold lithium concentration is close to 0.03 mmol/g of cement and similar with or without borate.« less

Gel phase in hydrated calcium dipicolinate

NASA Astrophysics Data System (ADS)

Rajak, Pankaj; Mishra, Ankit; Sheng, Chunyang; Tiwari, Subodh; Krishnamoorthy, Aravind; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

2017-11-01

The mineralization of dipicolinic acid (DPA) molecules in bacterial spore cores with Ca2+ ions to form Ca-DPA is critical to the wet-heat resistance of spores. This resistance to "wet-heat" also depends on the physical properties of water and DPA in the hydrated Ca-DPA-rich protoplasm. Using reactive molecular dynamics simulations, we have determined the phase diagram of hydrated Ca-DPA as a function of temperature and water concentration, which shows the existence of a gel phase along with distinct solid-gel and gel-liquid phase transitions. Simulations reveal monotonically decreasing solid-gel-liquid transition temperatures with increasing hydration, which explains the experimental trend of wet-heat resistance of bacterial spores. Our observation of different phases of water also reconciles previous conflicting experimental findings on the state of water in bacterial spores. Further comparison with an unmineralized hydrated DPA system allows us to quantify the importance of Ca mineralization in decreasing diffusivity and increasing the heat resistance of the spore.

Multiscale understanding of tricalcium silicate hydration reactions.

PubMed

Cuesta, Ana; Zea-Garcia, Jesus D; Londono-Zuluaga, Diana; De la Torre, Angeles G; Santacruz, Isabel; Vallcorba, Oriol; Dapiaggi, Monica; Sanfélix, Susana G; Aranda, Miguel A G

2018-06-04

Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates (C-S-H) nanocrystalline gel. This hydration reaction is poorly understood at the nanoscale. The understanding of atomic arrangement in nanocrystalline phases is intrinsically complicated and this challenge is exacerbated by the presence of additional crystalline phase(s). Here, we use calorimetry and synchrotron X-ray powder diffraction to quantitatively follow tricalcium silicate hydration process: i) its dissolution, ii) portlandite crystallization and iii) C-S-H gel precipitation. Chiefly, synchrotron pair distribution function (PDF) allows to identify a defective clinotobermorite, Ca 11 Si 9 O 28 (OH) 2 . 8.5H 2 O, as the nanocrystalline component of C-S-H. Furthermore, PDF analysis also indicates that C-S-H gel contains monolayer calcium hydroxide which is stretched as recently predicted by first principles calculations. These outcomes, plus additional laboratory characterization, yielded a multiscale picture for C-S-H nanocomposite gel which explains the observed densities and Ca/Si atomic ratios at the nano- and meso- scales.

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

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

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

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

Cellulose Nanofibers as a Modifier for Rheology, Curing and Mechanical Performance of Oil Well Cement

PubMed Central

Sun, Xiuxuan; Wu, Qinglin; Lee, Sunyoung; Qing, Yan; Wu, Yiqiang

2016-01-01

The influence of nanocellulose on oil well cement (OWC) properties is not known in detail, despite recent advances in nanocellulose technology and its related composite materials. The effect of cellulose nanofibers (CNFs) on flow, hydration, morphology, and strength of OWC was investigated using a range of spectroscopic methods coupled with rheological modelling and strength analysis. The Vom-Berg model showed the best fitting result of the rheology data. The addition of CNFs increased the yield stress of OWC slurry and degree of hydration value of hydrated CNF-OWC composites. The flexural strength of hydrated OWC samples was increased by 20.7% at the CNF/OWC ratio of 0.04 wt%. Excessive addition of CNFs into OWC matrix had a detrimental effect on the mechanical properties of hydrated CNF-OWC composites. This phenomenon was attributed to the aggregation of CNFs as observed through coupled morphological and elemental analysis. This study demonstrates a sustainable reinforcing nano-material for use in cement-based formulations. PMID:27526784

Gas hydrate reservoirs and gas migration mechanisms in the Terrebonne Basin, Gulf of Mexico

DOE PAGES

Hillman, Jess I. T.; Cook, Ann E.; Daigle, Hugh; ...

2017-07-27

Here, the interactions of microbial methane generation in fine-grained clay-rich sediments, methane migration, and gas hydrate accumulation in coarse-grained, sand-rich sediments are not yet fully understood. The Terrebonne Basin in the northern Gulf of Mexico provides an ideal setting to investigate the migration of methane resulting in the formation of hydrate in thin sand units interbedded with fractured muds. Using 3D seismic and well log data, we have identified several previously unidentified hydrate bearing units in the Terrebonne Basin. Two units are >100 m- thick fine-grained clay-rich units where gas hydrate occurs in near-vertical fractures. In some locations, these fine-grainedmore » units lack fracture features, and they contain 1-4-m thick hydrate bearing-sands. In addition, several other thin sand units were identified that contain gas hydrate, including one sand that was intersected by a well at the location of a discontinuous bottom-simulating reflector. Using correlation of well log data to seismic data, we have mapped and described these new units in detail across the extent of the available data, allowing us to determine the variation of seismic amplitudes and investigate the distribution of free gas and/or hydrate. We present several potential source-reservoir scenarios between the thick fractured mud units and thin hydrate bearing sands. We observe that hydrate preferentially forms within thin sand layers rather than fractures when sands are present in larger marine mud units. Based on regional mapping showing the patchy lateral extent of the thin sand layers, we propose that diffusive methane migration or short-migration of microbially generated methane from the marine mud units led to the formation of hydrate in these thin sands, as discontinuous sands would not be conducive to long-range migration of methane from deeper reservoirs.« less

Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

USGS Publications Warehouse

Clennell, M.B.; Hovland, M.; Booth, J.S.; Henry, P.; Winters, W.J.

1999-01-01

The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability. 

Gas hydrate reservoirs and gas migration mechanisms in the Terrebonne Basin, Gulf of Mexico

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

Hillman, Jess I. T.; Cook, Ann E.; Daigle, Hugh

Here, the interactions of microbial methane generation in fine-grained clay-rich sediments, methane migration, and gas hydrate accumulation in coarse-grained, sand-rich sediments are not yet fully understood. The Terrebonne Basin in the northern Gulf of Mexico provides an ideal setting to investigate the migration of methane resulting in the formation of hydrate in thin sand units interbedded with fractured muds. Using 3D seismic and well log data, we have identified several previously unidentified hydrate bearing units in the Terrebonne Basin. Two units are >100 m- thick fine-grained clay-rich units where gas hydrate occurs in near-vertical fractures. In some locations, these fine-grainedmore » units lack fracture features, and they contain 1-4-m thick hydrate bearing-sands. In addition, several other thin sand units were identified that contain gas hydrate, including one sand that was intersected by a well at the location of a discontinuous bottom-simulating reflector. Using correlation of well log data to seismic data, we have mapped and described these new units in detail across the extent of the available data, allowing us to determine the variation of seismic amplitudes and investigate the distribution of free gas and/or hydrate. We present several potential source-reservoir scenarios between the thick fractured mud units and thin hydrate bearing sands. We observe that hydrate preferentially forms within thin sand layers rather than fractures when sands are present in larger marine mud units. Based on regional mapping showing the patchy lateral extent of the thin sand layers, we propose that diffusive methane migration or short-migration of microbially generated methane from the marine mud units led to the formation of hydrate in these thin sands, as discontinuous sands would not be conducive to long-range migration of methane from deeper reservoirs.« less

Evaluation of the Community Land Model (CLM-Crop) in the United States Corn Belt

NASA Astrophysics Data System (ADS)

Chen, M.; Griffis, T.

2013-12-01

An accurate representation of crop phenology in land surface models is crucial for predicting the carbon, water and energy budgets of managed ecosystems. Soybean and corn are cultivated in approximately 600,000 km2 in the Corn Belt- an area greater than the entire State of California. Accurate prediction of the radiation, energy, and carbon budgets of this region is especially important for understanding its influence on radiative forcing, the thermodynamic properties of the atmospheric boundary layer, and changes in climate. Recently, key algorithms describing crop biophysics and interactive crop management (planting, fertilization, irrigation, harvesting) have been implemented in the Community Land Model (CLM-Crop). CLM-Crop provides a framework for prognostic simulation of crop phenology and evaluation of human management decisions under future climate scenarios. However, there is an important need to evaluate CLM-Crop against a broad range of agricultural site observations in order to understand its limitations and to help optimize the crop biophysical parameterization. Here we evaluated CLM-Crop version 4.5 at 9 AmeriFlux corn/soybean sites that are located within the United States Corn Belt. The following questions were addressed: 1) How well does CLM perform for the 9 crop sites with different management techniques (e.g., tillage vs. no-till, rainfed vs. irrigated)? 2) What are the model's strengths and weaknesses of simulating crop phenology, energy fluxes and carbon fluxes? 3) What steps are needed in order to improve the reliability of the CLM-Crop simulations? Our preliminary results indicate that CLM-Crop can simulate the radiation, energy, and carbon fluxes with reasonable accuracy during the mid growing season. The model performance degrades substantially during the early and late growing seasons, which we attribute to a bias in crop phenology. For instance, we observed that the simulated corn and soybean phenology (LAI) has an earlier phase than the observations by about 15 days at many sites. Here, we show how the optimization of carbon allocation and crop phenology influences the modeled radiation, energy, and carbon fluxes and discuss other model deficiencies associated with the crop biophysics scheme.

Effects of corn replacement by sorghum in broiler diets on performance and intestinal mucosa integrity.

PubMed

Torres, K A A; Pizauro, J M; Soares, C P; Silva, T G A; Nogueira, W C L; Campos, D M B; Furlan, R L; Macari, M

2013-06-01

The effect of replacing corn with low-tannin sorghum on broiler performance, carcass yield, integrity of mucosa of small intestine segments, and activity of membrane enzymes of the jejunum is investigated. A total of 594 male Cobb-500 broiler chicks were randomly assigned to 3 dietary treatments: 100% corn (control), 50% corn replacement with low-tannin sorghum (low sorghum), and 100% corn replacement with low-tannin sorghum (high sorghum). Body weight gain, feed consumption, feed conversion, and carcass yield were determined at 7, 21, and 42 d, and segments of the small intestine were collected. Feed conversion and weight gain were impaired at d 42 in broilers fed the high-sorghum diet, but no differences were observed for carcass yield among the treatments (P > 0.05). Crypt cell mitotic index of the jejunum and ileum at d 21 and 42 was lower in broilers fed the control diet than in those fed low- and high-sorghum diets (P < 0.05). Aminopeptidase activity was higher in broilers fed the control diet than in those fed low- and high-sorghum diets irrespective of age (P < 0.05). Conversely, intestinal alkaline phosphatase activity in the small intestine did not differ among the dietary treatments (P > 0.05). Our results indicate that 50% corn replacement with low-tannin sorghum is suitable for broiler diets, whereas 100% corn replacement with low-tannin sorghum had negative effects on the intestinal mucosa and performance of broilers at 42 d.

Adjacent Habitat Influence on Stink Bug (Hemiptera: Pentatomidae) Densities and the Associated Damage at Field Corn and Soybean Edges

PubMed Central

Venugopal, P. Dilip; Coffey, Peter L.; Dively, Galen P.; Lamp, William O.

2014-01-01

The local dispersal of polyphagous, mobile insects within agricultural systems impacts pest management. In the mid-Atlantic region of the United States, stink bugs, especially the invasive Halyomorpha halys (Stål 1855), contribute to economic losses across a range of cropping systems. Here, we characterized the density of stink bugs along the field edges of field corn and soybean at different study sites. Specifically, we examined the influence of adjacent managed and natural habitats on the density of stink bugs in corn and soybean fields at different distances along transects from the field edge. We also quantified damage to corn grain, and to soybean pods and seeds, and measured yield in relation to the observed stink bug densities at different distances from field edge. Highest density of stink bugs was limited to the edge of both corn and soybean fields. Fields adjacent to wooded, crop and building habitats harbored higher densities of stink bugs than those adjacent to open habitats. Damage to corn kernels and to soybean pods and seeds increased with stink bug density in plots and was highest at the field edges. Stink bug density was also negatively associated with yield per plant in soybean. The spatial pattern of stink bugs in both corn and soybeans, with significant edge effects, suggests the use of pest management strategies for crop placement in the landscape, as well as spatially targeted pest suppression within fields. PMID:25295593

Adjacent habitat influence on stink bug (Hemiptera: Pentatomidae) densities and the associated damage at field corn and soybean edges.

PubMed

Venugopal, P Dilip; Coffey, Peter L; Dively, Galen P; Lamp, William O

2014-01-01

The local dispersal of polyphagous, mobile insects within agricultural systems impacts pest management. In the mid-Atlantic region of the United States, stink bugs, especially the invasive Halyomorpha halys (Stål 1855), contribute to economic losses across a range of cropping systems. Here, we characterized the density of stink bugs along the field edges of field corn and soybean at different study sites. Specifically, we examined the influence of adjacent managed and natural habitats on the density of stink bugs in corn and soybean fields at different distances along transects from the field edge. We also quantified damage to corn grain, and to soybean pods and seeds, and measured yield in relation to the observed stink bug densities at different distances from field edge. Highest density of stink bugs was limited to the edge of both corn and soybean fields. Fields adjacent to wooded, crop and building habitats harbored higher densities of stink bugs than those adjacent to open habitats. Damage to corn kernels and to soybean pods and seeds increased with stink bug density in plots and was highest at the field edges. Stink bug density was also negatively associated with yield per plant in soybean. The spatial pattern of stink bugs in both corn and soybeans, with significant edge effects, suggests the use of pest management strategies for crop placement in the landscape, as well as spatially targeted pest suppression within fields.

Growth of a Hydrate Mound in the Sea of Japan over 300 ka as Revealed by U-Th Ages of MDAC and by H2S Concentrations of Massive Hydrates

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Snyder, G. T.; Hiruta, A.; Kakizaki, Y.; Huang, C. Y.; Shen, C. C.

2017-12-01

The geological and geophysical exploration of gas hydrate in the Sea of Japan has revealed that hydrates occur as thick massive deposits within gas chimneys which often give rise to pingo-like hydrate mounds on the seafloor. We examine one case in which LWD has demonstrated anomalous profiles including both very low natural gamma ray (<10 API) and high acoustic velocities (2.5 to 3.5 km/s) extending down to 120mbsf, the base of gas hydrate stability (BGHS)[1]. Both conventional and pressure coring have confirmed thick, massive deposits of pure-gas hydrates. Hydrates in the shallow subsurface (< 20mbsf) are characterized by high H2S concentrations corresponding to AOM-induced production of HS-. The deeper hydrates generally have negligible amounts of H2S, with occasional exceptions in which H2S is moderately high. These observations lead us to conclude that both the re-equilibration and growth of hydrates in high CH4 and low to zero H2S conditions has continued during burial, and that this ongoing growth is an essential processes involved in the development of massive hydrates in the Sea of Japan.Regardless of depth, the Japan Sea gas hydrates are closely associated with 13-C depleted, methane-derived authigenic carbonates (MDACs). These MDACs are considered to have been formed at near-SMT depths as a response to increased alkalinity caused by AOM and, as such, MDACs are assumed to represent approximate paleo-seafloor at times of enhanced methane flux and intensive accumulation of gas hydrate in shallow subsurface. U-Th ages of MDACs collected from various depths in a mound-chimney system in central Joetsu Spur have revealed that the paleo-seafloor of 300 ka is presently situated at 30 to 55 mbsf within the gas chimney, in contrast to off-mound sites where it is situated at 100 mbsf. This suggests that at 300 ka the mound stood as a "hydrate-pingo" of 70 m high relative to the surrounding sea floor. At this time, the BGHS shoaled upwards 10m due to eustatic sea level fall, resulting in the dissociation of gas hydrates right above the BGHS and an enhancement of methane flux through the gas chimney. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI. Reference [1] Matsumoto et al. (2017), Fire in the Ice, 17, 1-6.

A Circuit Model of Real Time Human Body Hydration.

PubMed

Asogwa, Clement Ogugua; Teshome, Assefa K; Collins, Stephen F; Lai, Daniel T H

2016-06-01

Changes in human body hydration leading to excess fluid losses or overload affects the body fluid's ability to provide the necessary support for healthy living. We propose a time-dependent circuit model of real-time human body hydration, which models the human body tissue as a signal transmission medium. The circuit model predicts the attenuation of a propagating electrical signal. Hydration rates are modeled by a time constant τ, which characterizes the individual specific metabolic function of the body part measured. We define a surrogate human body anthropometric parameter θ by the muscle-fat ratio and comparing it with the body mass index (BMI), we find theoretically, the rate of hydration varying from 1.73 dB/min, for high θ and low τ to 0.05 dB/min for low θ and high τ. We compare these theoretical values with empirical measurements and show that real-time changes in human body hydration can be observed by measuring signal attenuation. We took empirical measurements using a vector network analyzer and obtained different hydration rates for various BMI, ranging from 0.6 dB/min for 22.7 [Formula: see text] down to 0.04 dB/min for 41.2 [Formula: see text]. We conclude that the galvanic coupling circuit model can predict changes in the volume of the body fluid, which are essential in diagnosing and monitoring treatment of body fluid disorder. Individuals with high BMI would have higher time-dependent biological characteristic, lower metabolic rate, and lower rate of hydration.

Carbohydrate composition and in vitro digestibility of dry matter and nonstarch polysaccharides in corn, sorghum, and wheat and coproducts from these grains.

PubMed

Jaworski, N W; Lærke, H N; Bach Knudsen, K E; Stein, H H

2015-03-01

The objectives of this work were to determine carbohydrate composition and in vitro digestibility of DM and nonstarch polysaccharides (NSP) in corn, wheat, and sorghum and coproducts from these grains. In the initial part of this work, the carbohydrate composition of 12 feed ingredients was determined. The 12 ingredients included 3 grains (corn, sorghum, and wheat), 3 coproducts from the dry grind industry (corn distillers dried grains with solubles [DDGS] and 2 sources of sorghum DDGS), 4 coproducts from the wet milling industry (corn gluten meal, corn gluten feed, corn germ meal, and corn bran), and 2 coproducts from the flour milling industry (wheat middlings and wheat bran). Results indicated that grains contained more starch and less NSP compared with grain coproducts. The concentration of soluble NSP was low in all ingredients. Cellulose, arabinoxylans, and other hemicelluloses made up approximately 22, 49, and 29% (DM basis), respectively, of the NSP in corn and corn coproducts and approximately 25, 43, and 32% (DM basis), respectively, of the NSP in sorghum and sorghum DDGS. Cellulose, arabinoxylans, and other hemicelluloses made up approximately 16, 64, and 20% (DM basis), respectively, of the NSP in wheat and wheat coproducts. The concentration of lignin in grains was between 0.8 and 1.8% (DM basis), whereas coproducts contained between 2.2 and 11.5% lignin (DM basis). The in vitro ileal digestibility of NSP was close to zero or negative for all feed ingredients, indicating that pepsin and pancreas enzymes have no effect on in vitro degradation of NSP. A strong negative correlation ( = 0.97) between in vitro ileal digestibility of DM and the concentration of NSP in feed ingredients was observed. In vitro total tract digestibility of NSP ranged from 6.5% in corn bran to 57.3% in corn gluten meal. In conclusion, grains and grain coproducts contain mostly insoluble NSP and arabinoxylans make up the majority of the total NSP fraction. The in vitro digestibility of NSP depends on the amount and type of NSP and degree of lignification in the feed ingredient. The NSP composition of grains and grain coproducts plays an important role in determining the extent of fermentation of NSP; therefore, NSP composition influences the energy value of grains and grain coproducts.

Iodine and Bromine Distributions in Pore Waters: A Comparison Between Permafrost and Marine Gas Hydrate Fields

NASA Astrophysics Data System (ADS)

Tomaru, H.; Fehn, U.; Lu, Z.

2005-12-01

Iodine and, to a lesser degree, bromine are commonly enriched in waters associated with hydrocarbons. The concentrations of these halogens and their ratios can thus be used to identify potential source formations for hydrocarbons such as gas hydrates. While the largest reservoir of gas hydrates is found in marine sediments, permafrost locations are also an important source of gas hydrates. We measured iodine and bromine concentrations in pore waters associated with gas hydrates in the Mallik exploration well, a permafrost location in the Mackenzie delta, Northwest Territory, Canada and compared them to results from gas hydrates in marine sediments. Gas hydrates are found in the Mallik site in two horizons below the permafrost layer which reaches a depth of about 600 m in this location. We measured concentrations in samples collected from depths between 850 and 1150 m. Large sections of the test well have iodine concentrations around 1 μM, but the concentrations increase to values between 10 and 20 μM at the gas hydrate horizons. Bromine concentrations show a similar pattern, with maxima reaching values between 700 and 800 μM. Although iodine concentrations are considerably higher than in seawater (0.4 μM), they are much lower than in marine gas hydrate locations such as Nankai (200 μM); Blake Ridge (2 mM) or Hydrate Ridge (2.5 mM). Bromine concentrations at Mallik do not reach the seawater value (840 μM) in contrast to marine hydrate locations where Br is enriched by factors of four or more compared to seawater. Chlorine concentrations at Mallik are close to that of seawater, in this case similar to the marine hydrate locations. The comparison between marine hydrate locations and Mallik suggests that the organic sources responsible for the methane at Mallik are considerably different from those in marine situations. Since iodine concentrations are generally higher in marine organisms than in terrestrial organisms, the relatively low concentrations of iodine and bromine at Mallik suggest that the source material there is of more terrestrial character than in the marine locations, a observation supported by the presence of several coal seams at Mallik. The large volume of methane in this region suggests that terrestrial sources may play an important role in the accumulation of gas hydrates.

Early Diagenesis of Subseafloor Sandy Sediments Closely Related to Gas Hydrate Occurrences and Their Provenances in the Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Uchida, T.; Sakai, H.; Horiuchi, S.; Matsumoto, R.

2015-12-01

A lot of effort have been put into recovering gas hydrate, methane induced carbonate, and associated sediments in order to develop the geologic model of gas hydrate accumulation and evaluate its possible environmental impact for the last glacial-interglacial cycles. Having investigated gas hydrate occurrences in the eastern margin of Japan Sea revealed wide distributions of chimney-shape gas hydrate concentrations beneath the seafloor, confirmed off Shimane and off Akita/Yamagata as well as off Joetsu (Niigata), which are quite different from the occurrences of pore space hydrate filling intergranular pore systems of sands recognized in Nankai Trough, Mallik and other sites. Many sediment samples have been obtained below from the Umitaka Spur, Joetsu Channel, Toyama Trough, Mogami Trough and Okushiri Ridge areas. Small amounts of sandy sediment have been retrieved as thin intercalations in Holocene and Pleistocene silty/muddy layers, where trace fossils and strong bioturbations are commonly observed. Sandy sediments consist of very fine- to fine-grained sand grains, and are sometimes tuffaceous. Pore-size distribution measurements and thin-section observations of these sands were carried out, which indicate that porosities of silty sediments are around 50 % but those of arenites range from 42 to 52 %, of which mean pore sizes and permeabilities are larger than those of silty sediments. These coarser sediments might have been transported approximately around 3 to 30 ka due to the tephra ages, where supplying sediments might be abundant due to sea level fluctuation during the Pleistocene ice age. Sandy sediments contain not only detrital quartz and feldspar but mafic minerals (pyroxene, amphibole and mica), contents of which may indicate their provenances. Silty/muddy sediments usually contain diatom tests, foraminifers and framboidal pyrites, and, in particular, the shapes of diatom are usually various, dominantly fragmental and infrequently preserved. It is remarked that physical diagenesis proceeds first due to mechanical compaction, whereas chemical diagenesis advances very slowly in early diagenesis. This study was performed as a part of the MH21 Research Consortium on methane hydrate in Japan and the METI project entitled "FY2014 promoting research and development on methane hydrate."

Numerical modeling of the simulated gas hydrate production test at Mallik 2L-38 in the pilot scale pressure reservoir LARS - Applying the "foamy oil" model

NASA Astrophysics Data System (ADS)

Abendroth, Sven; Thaler, Jan; Klump, Jens; Schicks, Judith; Uddin, Mafiz

2014-05-01

In the context of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) we conducted a series of experiments in the LArge Reservoir Simulator (LARS) at the German Research Centre of Geosciences Potsdam. These experiments allow us to investigate the formation and dissociation of hydrates at large scale laboratory conditions. We performed an experiment similar to the field-test conditions of the production test in the Mallik gas hydrate field (Mallik 2L-38) in the Beaufort Mackenzie Delta of the Canadian Arctic. The aim of this experiment was to study the transport behavior of fluids in gas hydrate reservoirs during depressurization (see also Heeschen et al. and Priegnitz et al., this volume). The experimental results from LARS are used to provide details about processes inside the pressure vessel, to validate the models through history matching, and to feed back into the design of future experiments. In experiments in LARS the amount of methane produced from gas hydrates was much lower than expected. Previously published models predict a methane production rate higher than the one observed in experiments and field studies (Uddin et al. 2010; Wright et al. 2011). The authors of the aforementioned studies point out that the current modeling approach overestimates the gas production rate when modeling gas production by depressurization. They suggest that trapping of gas bubbles inside the porous medium is responsible for the reduced gas production rate. They point out that this behavior of multi-phase flow is not well explained by a "residual oil" model, but rather resembles a "foamy oil" model. Our study applies Uddin's (2010) "foamy oil" model and combines it with history matches of our experiments in LARS. Our results indicate a better agreement between experimental and model results when using the "foamy oil" model instead of conventional models of gas flow in water. References Uddin M., Wright J.F. and Coombe D. (2010) - Numerical Study of gas evolution and transport behaviors in natural gas hydrate reservoirs; CSUG/SPE 137439. Wright J.F., Uddin M., Dallimore S.R. and Coombe D. (2011) - Mechanisms of gas evolution and transport in a producing gas hydrate reservoir: an unconventional basis for successful history matching of observed production flow data; International Conference on Gas Hydrates (ICGH 2011).

Effect of Nano-SiO2 on the Early Hydration of Alite-Sulphoaluminate Cement

PubMed Central

Sun, Jinfeng; Xu, Zhiqiang; Li, Weifeng; Shen, Xiaodong

2017-01-01

The impact of nano-SiO2 on the early hydration properties of alite-sulphoaluminate (AC$A) cement was investigated with a fixed water to solid ratio (w/s) of one. Nano-SiO2 was used in partial substitution of AC$A cement at zero, one and three wt %. Calorimetry, X-ray diffraction (XRD), thermogravimetric/derivative thermogravimetric (TG/DTG), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) analyses were used to characterize the hydration and hydrates of the blended cement. The hydration of the AC$A cement was significantly promoted, resulting in an increase of the heat released with the addition of nano-SiO2. Phase development composition analysis showed that nano-SiO2 had no effect on the type of crystalline hydration products of the AC$A cement. Moreover, nano-SiO2 showed significant positive effects on pore refinement where the total porosity decreased by 54.09% at three days with the inclusion of 3% nano-SiO2. Finally, from the SEM observations, nano-SiO2 was conducive to producing a denser microstructure than that of the control sample. PMID:28467348

Design, characterization, and clinical evaluation of argan oil nanostructured lipid carriers to improve skin hydration

PubMed Central

Tichota, Deise Michele; Silva, Ana Catarina; Sousa Lobo, José Manuel; Amaral, Maria Helena

2014-01-01

Given its advantages in skin application (eg, hydration, antiaging, and protection), argan oil could be used in both dermatological and cosmetic formulations. Therefore, the preparation of nanostructured lipid carriers (NLCs) using argan oil as a liquid lipid is a promising technique, since the former constitute well-established systems for dermal delivery. The aim of this work was to develop a topical formulation of argan oil NLCs to improve skin hydration. Firstly an NLC dispersion was developed and characterized, and afterward an NLC-based hydrogel was prepared. The in vivo evaluation of the suitability of the prepared formulation for the proposed application was assessed in volunteers, by measuring different skin-surface parameters for 1 month. An argan oil NLC-based hydrogel formulation was successfully prepared and characterized. Moreover, the entrapment of the NLCs in the hydrogel net did not affect their colloidal sizes. Additionally, it was observed that this formulation precipitated an increase in skin hydration of healthy volunteers. Therefore, we concluded that the preparation of NLC systems using argan oil as the liquid lipid is a promising strategy, since a synergistic effect on the skin hydration was obtained (ie, NLC occlusion plus argan oil hydration). PMID:25143733

Systemic Hydration: Relating Science to Clinical Practice in Vocal Health

PubMed Central

Hartley, Naomi A.; Thibeault, Susan L.

2014-01-01

Objectives To examine the current state of the science regarding the role of systemic hydration in vocal function and health. Study Design Literature Review Methods Literature search spanning multiple disciplines, including speech-language pathology, nutrition and dietetics, medicine, sports and exercise science, physiology and biomechanics. Results The relationship between hydration and physical function is an area of common interest amongst multiple professions. Each discipline provides valuable insight into the connection between performance and water balance, as well as complimentary methods of investigation. Existing voice literature suggests a relationship between hydration and voice production, however the underlying mechanisms are not yet defined and a treatment effect for systemic hydration remains to be demonstrated. Literature from other disciplines sheds light on methodological shortcomings and in some cases offers an alternative explanation for observed phenomena. Conclusions A growing body of literature in the field of voice science is documenting a relationship between hydration and vocal function, however greater understanding is required to guide best practice in the maintenance of vocal health and management of voice disorders. Integration of knowledge and technical expertise from multiple disciplines facilitates analysis of existing literature and provides guidance as to future research. PMID:24880674

Design, characterization, and clinical evaluation of argan oil nanostructured lipid carriers to improve skin hydration.

PubMed

Tichota, Deise Michele; Silva, Ana Catarina; Sousa Lobo, José Manuel; Amaral, Maria Helena

2014-01-01

Given its advantages in skin application (eg, hydration, antiaging, and protection), argan oil could be used in both dermatological and cosmetic formulations. Therefore, the preparation of nanostructured lipid carriers (NLCs) using argan oil as a liquid lipid is a promising technique, since the former constitute well-established systems for dermal delivery. The aim of this work was to develop a topical formulation of argan oil NLCs to improve skin hydration. Firstly an NLC dispersion was developed and characterized, and afterward an NLC-based hydrogel was prepared. The in vivo evaluation of the suitability of the prepared formulation for the proposed application was assessed in volunteers, by measuring different skin-surface parameters for 1 month. An argan oil NLC-based hydrogel formulation was successfully prepared and characterized. Moreover, the entrapment of the NLCs in the hydrogel net did not affect their colloidal sizes. Additionally, it was observed that this formulation precipitated an increase in skin hydration of healthy volunteers. Therefore, we concluded that the preparation of NLC systems using argan oil as the liquid lipid is a promising strategy, since a synergistic effect on the skin hydration was obtained (ie, NLC occlusion plus argan oil hydration).

Effects of physiological environments on the hydration behavior of mineral trioxide aggregate.

PubMed

Lee, Yuan-Ling; Lee, Bor-Shiunn; Lin, Feng-Huei; Yun Lin, Ava; Lan, Wan-Hong; Lin, Chun-Pin

2004-02-01

Utilizing scanning electron microscope, X-ray diffraction (XRD) and microhardness tests, we evaluated how various physiological environments affect the hydration behavior and physical properties of mineral trioxide aggregate (MTA). We found that the microstructure of hydrated MTA consists of cubic and needle-like crystals. The former comprised the principal structure of MTA, whereas the later were less prominent and formed in the inter-grain spaces between the cubic crystals. MTA samples were hydrated in distilled water, normal saline, pH 7, and pH 5. However, no needle-like crystals were observed in the pH 5 specimens, and erosion of the cubic crystal surfaces was noted. XRD indicated a peak corresponding to Portlandite, a hydration product of MTA, and the peak decreased noticeably in the pH 5 group. The pH 5 specimens' microhardness was also significantly weaker compared to the other three groups (p<0.0001). These findings suggest that physiological environmental effects on MTA formation are determined, in part, by environmental pH and the presence of ions. In particular, an acidic environment of pH 5 adversely affects both the physical properties and the hydration behavior of MTA.

Corn silk aqueous extracts and intraocular pressure of systemic and non-systemic hypertensive subjects.

PubMed

George, Gladys O; Idu, Faustina K

2015-03-01

Hypotensive properties have been attributed to the stigma/style of Zea mays L (corn silk). Although the effect of corn silk extract on blood pressure has been documented in animal studies, we are not aware of any study on its effect on human blood pressure and intraocular pressure. A randomised study was carried out on the effect of water only, masked doses of corn silk aqueous extract (60, 130, 192.5 and 260 mg/kg body weight) on intraocular pressure and blood pressure of 20 systemic and 20 non-systemic hypertensive subjects. Intraocular pressure and blood pressure were measured at baseline and every hour for eight hours after administering water or a masked dose of corn silk aqueous extract. Each dose was administered at two-week intervals to each subject in the two study groups. The results showed that the last three doses of corn silk aqueous extract gave a statistically significant reduction (p < 0.001) in mean intraocular pressure and blood pressure within eight hours of administration. The peak effect on intraocular pressure was observed after four hours and this was preceded by the peak effect on blood pressure, which occurred after three hours of administration. The hypotensive effect was dose-dependent in the two groups. Corn silk aqueous extract has a lowering effect on intraocular pressure in systemic and non-systemic hypertensive subjects. This may have resulted from the fall in blood pressure that is due to potassium-induced natriuresis and diuresis caused by the high potassium content in the high doses of the corn silk extract. © 2015 The Authors. Clinical and Experimental Optometry © 2015 Optometry Australia.

Odorous Volatile Organic Compounds, Escherichia coli, and Nutrient Concentrations when Kiln-Dried Pine Chips and Corn Stover Bedding Are Used in Beef Bedded Manure Packs.

PubMed

Spiehs, Mindy J; Berry, Elaine D; Wells, James E; Parker, David B; Brown-Brandl, Tami M

2017-07-01

Pine ( spp.) bedding has been shown to lower the concentration of odorous volatile organic compounds (VOCs) and pathogenic bacteria compared with corn ( L.) stover bedding, but availability and cost limit the use of pine bedding in cattle confinement facilities. The objectives of this study were to determine if the addition of pine wood chips to laboratory-scaled bedded packs containing corn stover (i) reduced odorous VOC emissions; (ii) reduced total ; and (iii) changed the nutrient composition of the resulting manure-bedded packs. Bedding treatments included 0, 10, 20, 30, 40, 60, 80, and 100% pine chips, with the balance being corn stover. Four bedded packs for each mixture were maintained for 42 d ( = 4 observations per bedding material). The production of total sulfur compounds increased significantly when 100% pine chips were used (44.72 ng L) compared with bedding mixture containing corn stover (18.0-24.56 ng L). The carbon-to-nitrogen ratio exceeded the ideal ratio of 24:1 for the optimum activity of soil microorganisms when ≥60% pine chips (25.3-27.5 ng L) were included in the mixture. The use of 100% pine chips as bedding increased sulfide concentration in the facility 1.8 to 2.4 times over the use of corn stover bedding. was not influenced by the addition of pine chips to the corn stover bedding material but did decrease as the bedded pack aged. Bedding material mixtures containing 30 to 60% pine and 40 to 70% corn stover may be the ideal combination to mitigate odors from livestock facilities using deep bedded systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

The presence of Bacillus thuringiensis (Bt) protein in earthworms Eisenia fetida has no deleterious effects on their growth and reproduction.

PubMed

Shu, Yinghua; Ma, Honghui; Du, Yan; Li, Zhixian; Feng, Yuanjiao; Wang, Jianwu

2011-11-01

Earthworms Eisenia fetida, bred in substances with stover of two genetically-engineered Bacillus thuringiensis (Bt) corns (5422Bt1 (Event Bt11) and 5422CBCL (MON810)) expressing Cry1Ab and their near-isogenic non-Bt corn (5422), were used to investigate the non-target effects of Bt corn on soil-dwelling organisms. Cry1Ab concentrations in substances, casts and guts of E. fetida were also investigated by Enzyme-linked immunosorbent assay (ELISA). More than 90% individuals of E. fetida survived over a period of 30 d, irrespective of whether they received Bt corn or non-Bt corn. Compared to 5422 treatments, significantly higher relative growth rate and more number of new offspring and cocoons of E. fetida were found in 5422Bt1 and 5422CBCL treatments. These results were unlikely to be directly caused by Cry1Ab released from Bt corns but rather by differences in other factors of plants such as plant components (soluble sugar, total organic carbon, total protein and available phosphorus of Bt corns were more than 5422). ELISA results indicated immunoreactive Cry1Ab was detectable in substances, and the casts, guts of E. fetida from Bt corns treatments, of which the highest levels were detected in substances under the corresponding experimental conditions. With the increase of treated time, a strong decline was observed in Cry1Ab from substances and casts of E. fetida, whereas Cry1Ab in guts of E. fetida from 5422Bt1 treatments gradually increased and that from 5422CBCL treatments increased between 14 and 30 d. Therefore, the presence of Cry1Ab in E. fetida had no deleterious effects on their growth and reproduction. Copyright © 2011 Elsevier Ltd. All rights reserved.

Seismic evidence for mass-transport deposits and BSR occurrence on the forearc region along the central Ryukyu Islands, Japan

NASA Astrophysics Data System (ADS)

Komatsu, Y.; Kobayashi, T.; Fujii, T.

2017-12-01

Mass-transport deposits (MTDs) are widely observed from many continental margins and are a significant component of both slope and basin-floor settings. Although MTDs are typically mud-prone, some MTDs above certain porosity thresholds can act as important hydrocarbon reservoirs. MTDs associated with gas hydrate occurrence in the Ulleung basin were documented. The recovery of gas hydrate by drilling and piston coring has confirmed the gas hydrate accumulations in the basin. Gas hydrate dissociation may have played a role in the slide-initiation at the Storegga Slide offshore Norway. In this study, to identify the gas hydrate reservoir potential of MTDs, we focus on seismic characteristics (seismic facies, attributes, and velocity) of MTDs associated with bottom simulating reflectors (BSR). Our study area is in the forearc region along the central Ryukyu Islands (southeast Japan). In this area, BSR have been widely observed. However, the studies were insufficient for the evaluation of gas hydrate due to poor-quality 2-D seismic data. We use high-quality 3-D seismic volumes in water depths ranging from approximately 150 to 2000 m between Okinawa Island and Miyako Island. BSR in the eastern region of the study area was interpreted within Neogene to Quaternary MTDs. Strata in MTDs are correlated with the upper Shimajiri group based on the characteristics of well data outside of the seismic exploration area and stratigraphy of land areas. The Shimajiri group is composed of homogeneous siltstone intercalated with lenticular, thin-bedded, fine sandstone. Their group is water-dissolved gas reservoir in Okinawa Island and Miyako Island. On our seismic data, MTDs are shown as chaotic, poorly discontinuous strata of low amplitude, partially continuous moderate- to high-amplitude reflections. The seismic velocity profile shows a relative increase in MTD intervals above the BSR, similar to gas hydrate-bearing sediments. It is also indicative of over-consolidation that was result of compression caused by slumping.

Relict gas hydrates as possible reason of gas emission from shallow permafrost at the northern part of West Siberia

NASA Astrophysics Data System (ADS)

Chuvilin, Evgeny; Bukhanov, Boris; Tumskoy, Vladimir; Istomin, Vladimir; Tipenko, Gennady

2017-04-01

Intra-permafrost gas (mostly methane) is represent a serious geological hazards during exploration and development of oil and gas fields. Special danger is posed by large methane accumulations which usually confined to sandy and silty sand horizons and overlying in the frozen strata on the depth up to 200 meters. Such methane accumulations are widely spread in a number of gas fields in the northern part of Western Siberia. According to indirect indicators this accumulations can be relic gas hydrates, that formed earlier during favorable conditions for hydrate accumulation (1, 2). Until now, they could be preserved in the frozen sediments due to geological manifestation of the self-preservation effect of gas hydrates at temperatures below zero. These gas hydrate formations, which are lying above the gas hydrate stability zone today, are in a metastable state and are very sensitive to various anthropogenic impacts. During drilling and operation of production wells in the areas where the relic of gas hydrates can occur, there are active gas emission and gas explosion, that can lead to various technical complications up to the accident. Mathematical and experimental simulations were were conducted to evaluate the possibility of existence of relic gas hydrates in the northern part of West Siberia. The results of math simulations revealed stages of geological history when the gas hydrate stability zone began virtually from the ground surface and saturated in shallow permafrost horizons. Later permafrost is not completely thaw. Experimental simulations of porous gas hydrate dissociation in frozen soils and evaluation of self-preservation manifestation of gas hydrates at negative temperatures were carried out for identification conditions for relic gas hydrates existence in permafrost of northern part of West Siberia. Sandy and silty sand sediments were used in experimental investigations. These sediments are typical of most gas-seeping (above the gas hydrate stability zone) permafrost horizons. The results show that all investigated frozen hydrate-bearing sandy and silty sand samples in the temperature range from -16 °C to -2 °C are characterized by not complete decomposition of pore hydrate at relieving pressure below the equilibrium. It was observed that at typical north Western Siberian permafrost temperature of -6 ° C the safety of pore hydrate in frozen samples can reach 60% at the pressure reducing below the equilibrium. In was found that with increasing temperature and particle size (dispersity) the efficiency of pore hydrate self-preservation is decreased, but even at the temperature of -2 °C there is residual pore methane hydrate content in non-saline sandy samples. All this suggests about high preservation of methane hydrates in frozen sediments at non-equilibrium thermobaric conditions, close to reservoir conditions. Based on the results of mathematical and experimental simulations about the possibility of relic gas hydrates existence on permafrost depth up to 200 m in the northern part of Western Siberia on the less than 200 m due to geological manifestation of the self-preservation effect of gas hydrates. References. 1.Chuvilin EM, Yakushev VS, Perlova EV. Gas and gas hydrates in the permafrost of Bovanenkovo gas field, Yamal Peninsula, West Siberia. // Polarforschung 68: 215-219, 1998. (erschienen 2000). 2.Yakushev V.S., Chuvilin E.M. 2000. Natural gas and hydrate accumulation within permafrost in Russia. Cold Regions Science and Technology. 31: 189-197. These researches are supported by grant RSF №16-17-00051.

Corn rootworm-active RNA DvSnf7: Repeat dose oral toxicology assessment in support of human and mammalian safety.

PubMed

Petrick, Jay S; Frierdich, Gregory E; Carleton, Stephanie M; Kessenich, Colton R; Silvanovich, Andre; Zhang, Yuanji; Koch, Michael S

2016-11-01

Genetically modified (GM) crops have been developed and commercialized that utilize double stranded RNAs (dsRNA) to suppress a target gene(s), producing virus resistance, nutritional and quality traits. MON 87411 is a GM maize variety that leverages dsRNAs to selectively control corn rootworm through production of a 240 base pair (bp) dsRNA fragment targeting for suppression the western corn rootworm (Diabrotica virgifera virgifera) Snf7 gene (DvSnf7). A bioinformatics assessment found that endogenous corn small RNAs matched ∼450 to 2300 unique RNA transcripts that likely code for proteins in rat, mouse, and human, demonstrating safe dsRNA consumption by mammals. Mice were administered DvSnf7 RNA (968 nucleotides, including the 240 bp DvSnf7 dsRNA) at 1, 10, or 100 mg/kg by oral gavage in a 28-day repeat dose toxicity study. No treatment-related effects were observed in body weights, food consumption, clinical observations, clinical chemistry, hematology, gross pathology, or histopathology endpoints. Therefore, the No Observed Adverse Effect Level (NOAEL) for DvSnf7 RNA was 100 mg/kg, the highest dose tested. These results demonstrate that dsRNA for insect control does not produce adverse health effects in mammals at oral doses millions to billions of times higher than anticipated human exposures and therefore poses negligible risk to mammals. Copyright © 2016 Monsanto Company. Published by Elsevier Inc. All rights reserved.

Geologic controls on gas hydrate occurrence in the Mount Elbert prospect, Alaska North Slope

USGS Publications Warehouse

Boswell, R.; Rose, K.; Collett, T.S.; Lee, M.; Winters, W.; Lewis, K.A.; Agena, W.

2011-01-01

Data acquired at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled in the Milne Point area of the Alaska North Slope in February, 2007, indicates two zones of high gas hydrate saturation within the Eocene Sagavanirktok Formation. Gas hydrate is observed in two separate sand reservoirs (the D and C units), in the stratigraphically highest portions of those sands, and is not detected in non-sand lithologies. In the younger D unit, gas hydrate appears to fill much of the available reservoir space at the top of the unit. The degree of vertical fill with the D unit is closely related to the unit reservoir quality. A thick, low-permeability clay-dominated unit serves as an upper seal, whereas a subtle transition to more clay-rich, and interbedded sand, silt, and clay units is associated with the base of gas hydrate occurrence. In the underlying C unit, the reservoir is similarly capped by a clay-dominated section, with gas hydrate filling the relatively lower-quality sands at the top of the unit leaving an underlying thick section of high-reservoir quality sands devoid of gas hydrate. Evaluation of well log, core, and seismic data indicate that the gas hydrate occurs within complex combination stratigraphic/structural traps. Structural trapping is provided by a four-way fold closure augmented by a large western bounding fault. Lithologic variation is also a likely strong control on lateral extent of the reservoirs, particularly in the D unit accumulation, where gas hydrate appears to extend beyond the limits of the structural closure. Porous and permeable zones within the C unit sand are only partially charged due most likely to limited structural trapping in the reservoir lithofacies during the period of primary charging. The occurrence of the gas hydrate within the sands in the upper portions of both the C and D units and along the crest of the fold is consistent with an interpretation that these deposits are converted free gas accumulations formed prior to the imposition of gas hydrate stability conditions. ?? 2009.

Natural Gas Evolution in a Gas Hydrate Melt: Effect of Thermodynamic Hydrate Inhibitors.

PubMed

Sujith, K S; Ramachandran, C N

2017-01-12

Natural gas extraction from gas hydrate sediments by injection of hydrate inhibitors involves the decomposition of hydrates. The evolution of dissolved gas from the hydrate melt is an important step in the extraction process. Using classical molecular dynamics simulations, we study the evolution of dissolved methane from its hydrate melt in the presence of two thermodynamic hydrate inhibitors, NaCl and CH 3 OH. An increase in the concentration of hydrate inhibitors is found to promote the nucleation of methane nanobubbles in the hydrate melt. Whereas NaCl promotes bubble formation by enhancing the hydrophobic interaction between aqueous CH 4 molecules, CH 3 OH molecules assist bubble formation by stabilizing CH 4 bubble nuclei formed in the solution. The CH 3 OH molecules accumulate around the nuclei leading to a decrease in the surface tension at their interface with water. The nanobubbles formed are found to be highly dynamic with frequent exchange of CH 4 molecules between the bubble and the surrounding liquid. A quantitative analysis of the dynamic behavior of the bubble is performed by introducing a unit step function whose value depends on the location of CH 4 molecules with respect to the bubble. It is observed that an increase in the concentration of thermodynamic hydrate inhibitors reduces the exchange process, making the bubble less dynamic. It is also found that for a given concentration of the inhibitor, larger bubbles are less dynamic compared to smaller ones. The dependence of the dynamic nature of nanobubbles on bubble size and inhibitor concentration is correlated with the solubility of CH 4 and the Laplace pressure within the bubble. The effect of CO 2 on the formation of nanobubble in the CH 4 -CO 2 mixed gas hydrate melt in the presence of inhibitors is also examined. The simulations show that the presence of CO 2 molecules significantly reduces the induction time for methane nanobubble nucleation. The role of CO 2 in the early nucleation of bubble is explained based on the interaction between the bubble and the dissolved CO 2 molecules.

The occurrence of macro- and mesoscopic methane hydrate in the eastern margin of Japan Sea

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Kakuwa, Y.; Tanahashi, M.; Hiruta, A.

2016-12-01

Shallow methane hydrate is known to occur in muddy sediments that were deposited in the eastern margin of Japan Sea. In such settings, the hydrate occurs just below the seabed or is exposed directly on the seabed. Its presence is quite different from the pore-filling type of hydrate typically found in sandstone of the Pacific Ocean side of the Japanese islands. This presentation focuses on categorizing the distribution of gas hydrate in Japan Sea which, until recently, has been poorly understood. Macroscopic occurrence: Numerous gas chimney structures, which are characterized by an acoustic blanking on sub-bottom profiler images, have been discovered in the eastern margin of Japan Sea. We carried out seafloor drilling at several topographic highs that showed gas chimney structures. The results confirm that, while methane hydrate does not occur in the well-stratified part of SBP images, it does occur uniquely in the gas chimney structure-bearing mounds and pockmarks. Several horizons of methane hydrate-concentrated layers are identified by our LWD data and are traceable over lateral distances of as much as a kilometer.. In another case, the methane hydrate-concentrated layers occur stratigraphically in a regular manner with methane-derived carbonate nodules. We interpret the second case as one in which methane gas was supplied by regularly repeated movements of active fault(s). Mesoscopic occurrence: Methane hydrate is classified into 5 types that are readily observable in drilled cores: granular, nodular, platy, veiny and massive. The granular type is common over shallower intervals, while platy and veiny types are more common in the deeper intervals. Nevertheless, a significant fraction of the granular type may have possibly originated from the destruction and dissociation of other types during drilling and recovery. The massive type hydrate that characterizes highly-concentrated layers transitions to other types laterally as methane hydrate becomes poorly concentrated. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

Calibration and validation of a numerical model against experimental data of methane hydrate formation and dissociation in a sandy porous medium

NASA Astrophysics Data System (ADS)

Yin, Z.; Moridis, G. J.; Chong, Z. R.; Linga, P.

2017-12-01

Methane hydrates (MH) are known to trap enormous amounts of CH4 in oceanic and permafrost-associated deposits, and are being considered as a potential future energy source. Several powerful numerical simulators were developed to describe the behavior of natural hydrate-bearing sediments (HBS). The complexity and strong nonlinearities in HBS do not allow analytical solutions for code validation. The only reliable method to develop confidence in these models is through comparisons to laboratory and/or field experiments. The objective of this study is to reproduce numerically the results from earlier experiments of MH formation and depressurization (and the corresponding fluid production) in 1.0L reactor involving unconsolidated sand, thus validating and calibrating the TOUGH+Hydrate v1.5 simulator. We faithfully describe the reactor geometry and the experimental process that involves both hydrate formation and dissociation. We demonstrate that the laboratory experiments can only be captured by a kinetic hydration model. There is an excellent agreement between observations and predictions (a) of the cumulative gas depletion (during formation) and production (during dissociation) and (b) of pressure over time. The temperature agreement is less satisfactory, and the deviations are attributed to the fixed locations of the limited number of sensors that cannot fully capture the hydrate heterogeneity. We also predict the spatial distributions over time of the various phase (gas, aqueous and hydrate) saturations. Thus, hydrates form preferentially along the outer boundary of the sand core, and the hydrate front moves inward leaving a significant portion of the sand at the center hydrate-free. During depressurization, dissociation advances again inward from the reactor boundary to the center of the reactor. As expected, methane gas accumulates initially at the locations of most intense dissociation, and then gradually migrates to the upper section of the reactor because of buoyancy and of the pressure gradient caused by the pressure outlet. Sensitivity analysis indicates that the composite thermal conductivity of the HBS and the kinetic parameters of the hydration reaction are the dominant factors. The absolute permeability of the sand does not play a significant role in this small reactor.

Microbial Life in Soil - Linking Biophysical Models with Observations

NASA Astrophysics Data System (ADS)

Or, Dani; Tecon, Robin; Ebrahimi, Ali; Kleyer, Hannah; Ilie, Olga; Wang, Gang

2015-04-01

Microbial life in soil occurs within fragmented aquatic habitats formed in complex pore spaces where motility is restricted to short hydration windows (e.g., following rainfall). The limited range of self-dispersion and physical confinement promote spatial association among trophically interdepended microbial species. Competition and preferences for different nutrient resources and byproducts and their diffusion require high level of spatial organization to sustain the functioning of multispecies communities. We report mechanistic modeling studies of competing multispecies microbial communities grown on hydrated surfaces and within artificial soil aggregates (represented by 3-D pore network). Results show how trophic dependencies and cell-level interactions within patchy diffusion fields promote spatial self-organization of motile microbial cells. The spontaneously forming patterns of segregated, yet coexisting species were robust to spatial heterogeneities and to temporal perturbations (hydration dynamics), and respond primarily to the type of trophic dependencies. Such spatially self-organized consortia may reflect ecological templates that optimize substrate utilization and could form the basic architecture for more permanent surface-attached microbial colonies. Hydration dynamics affect structure and spatial arrangement of aerobic and anaerobic microbial communities and their biogeochemical functions. Experiments with well-characterized artificial soil microbial assemblies grown on porous surfaces provide access to community dynamics during wetting and drying cycles detected through genetic fingerprinting. Experiments for visual observations of spatial associations of tagged bacterial species with known trophic dependencies on model porous surfaces are underway. Biophysical modeling provide a means for predicting hydration-mediated critical separation distances for activation of spatial self-organization. The study provides new modeling and observational tools that enable new mechanistic insights into how differences in substrate affinities among microbial species and soil micro-hydrological conditions may give rise to a remarkable spatial and functional order in an extremely heterogeneous soil microbial world

Microbial Life in Soil - Linking Biophysical Models with Observations

NASA Astrophysics Data System (ADS)

Or, D.; Tecon, R.; Ebrahimi, A.; Kleyer, H.; Ilie, O.; Wang, G.

2014-12-01

Microbial life in soil occurs within fragmented aquatic habitats in complex pore spaces where motility is restricted to short hydration windows (e.g., following rainfall). The limited range of self-dispersion and physical confinement promote spatial association among trophically interdepended microbial species. Competition and preferences for different nutrient resources and byproducts and their diffusion require high level of spatial organization to sustain the functioning of multispecies communities. We report mechanistic modeling studies of competing multispecies microbial communities grown on hydrated surfaces and within artificial soil aggregates (represented by 3-D pore network). Results show how trophic dependencies and cell-level interactions within patchy diffusion fields promote spatial self-organization of motile microbial cells. The spontaneously forming patterns of segregated, yet coexisting species were robust to spatial heterogeneities and to temporal perturbations (hydration dynamics), and respond primarily to the type of trophic dependencies. Such spatially self-organized consortia may reflect ecological templates that optimize substrate utilization and could form the basic architecture for more permanent surface-attached microbial colonies. Hydration dynamics affect structure and spatial arrangement of aerobic and anaerobic microbial communities and their biogeochemical functions. Experiments with well-characterized artificial soil microbial assemblies grown on porous surfaces provide access to community dynamics during wetting and drying cycles detected through genetic fingerprinting. Experiments for visual observations of spatial associations of tagged bacterial species with known trophic dependencies on model porous surfaces are underway. Biophysical modeling provide a means for predicting hydration-mediated critical separation distances for activation of spatial self-organization. The study provides new modeling and observational tools that enable new mechanistic insights into how differences in substrate affinities among microbial species and soil micro-hydrological conditions may give rise to a remarkable spatial and functional order in an extremely heterogeneous soil microbial world.

Offshore gas hydrate sample database with an overview and preliminary analysis

USGS Publications Warehouse

Booth, James S.; Rowe, Mary M.; Fisher, Kathleen M.

1996-01-01

Synopsis -- A database of offshore gas hydrate samples was constructed from published observations and measurements. More than 90 samples from 15 distinct regions are represented in 13 data categories. This database has permitted preliminary description of gas hydrate (chiefly methane hydrate) tendencies and associations with respect to their geological environment. Gas hydrates have been recovered from offshore sediment worldwide and from total depths (water depth plus subseabed depth) ranging from 500 m to nearly 6,000 m. Samples have come from subbottom depths ranging from 0 to 400 m. Various physiographic provinces are represented in the data set including second order landforms such as continental margins and deep-sea trenches, and third order forms such as submarine canyons, continental slopes, continental margin ridges and intraslope basins. There is a clear association between fault zones and other manifestations of local, tectonic-related processes, and hydrate-bearing sediment. Samples of gas hydrate frequently consist of individual grains or particles. These types of hydrates are often further described as inclusions or disseminated in the sediment. Moreover, hydrates occur as a cement, as nodules, or as layers (mostly laminae) or in veins. The preponderance of hydrates that could be characterized as 2- dimensional (planar) were associated with fine sediment, either as intercalated layers or in fractures. Hydrate cements were commonly associated with coarser sediment. Hydrates have been found in association with grain sizes ranging from clay through gravel. More hydrates are associated with the more abundant finer-grained sediment than with coarser sediment, and many were discovered in the presence of both fine (silt and clay) and coarse sediment. The thickness of hydrate zones (i. e., sections of hydrate-bearing sediment) varies from a few centimeters to as much as 30 m. In contrast, the thickness of layers of pure hydrate or the dimensions of individual hydrate grains were most often characterized in terms of millimeters or centimeters, although a pure hydrate layer discovered in the Middle America Trench off Guatemala was as much as 3-4-m-thick. The data suggest that grains, or thin veins or laminae of pure gas hydrate may be ubiquitous in many hydrate zones but that typically they may only comprise a minor component of the thicker zones. In more than 80 percent of the hydrate samples the methane was of biogenic origin. The methane in the remainder was either classified as (or may be at least part) thermogenic. Each site where thermogenic gas was identified is characterized by faults or other manifestions of a dynamic geological environment (e.g., diapirs, mud volcanoes, gas seeps). Every sample in the database came from within the zone of theoretical methane hydrate stability, as determined on the basis of assumed regional pressure and temperature gradients. Most show that they were situated --- expressed in terms of depth --- well above the phase boundary and about 70% of the samples were located more than 100 m above the assumed regional position of that boundary. The calculated subseabed positions of the phase boundaries and the BSRs (bottom simulating reflector) are essentially identical. This may be taken as general corroboration of the regional phase boundary calculations and the concept of the BSR. Three provocative aspects of marine gas hydrates have been disclosed by the database: gas hydrates are frequently situated at much shallower subseabed depths than the assumed contemporary position of the regional phase boundary hydrates are often found in areas typified by faults or other indicators of a dynamic geological environment zones of gas hydrate-bearing sediment tend to be tens of centimeters to tens of meters thick but the hydrate within the thicker zones tends to be only a minor constituent. Whether existing as dispersed particles, cements, or pure layers or vein

Peculiarities of CO2 sequestration in the Permafrost area

NASA Astrophysics Data System (ADS)

Guryeva, Olga; Chuvilin, Evgeny; Moudrakovski, Igor; Lu, Hailong; Ripmeester, John; Istomin, Vladimir

2010-05-01

Natural gas and gas-condensate accumulations in North of Western Siberia contain an admixture of CO2 (about 0.5-1.0 mol.%). Recently, the development and transportation of natural gas in the Yamal peninsula has become of interest to Russian scientists. They suggest liquifaction of natural gas followed by delivery to consumers using icebreaking tankers. The technique of gas liquefaction requires CO2 to be absent from natural gas, and therefore the liquefaction technology includes the amine treatment of gas. This then leads to a problem with utilization of recovered CO2. It is important to note, that gas reservoirs in the northern part of Russia are situated within the Permafrost zone. The thickness of frozen sediment reaches 500 meters. That is why one of the promising places for CO2 storage can be gas-permeable collectors in under-permafrost horizons. The favorable factors for preserving CO2 in these places are as follows: low permeability of overlying frozen sediments, low temperatures, the existence of a CO2 hydrate stability zone, and the possibility of sequestration at shallow depths (less then 800-1000 meters). When CO2 (in liquid or gas phase) is pumped into the under-permafrost collectors it is possible that some CO2 migrates towards the hydrate stability zone and hydrate-saturated horizons can be formed. This can result on the one hand in the increase of effective capacity of the collector, and on the other hand, in the increase of isolating properties of cap rock. Therefore, CO2 injection sometimes can be performed without a good cap rock. In connection with the abovementioned, to elaborate an effective technology for CO2 injection it is necessary to perform a comprehensive experimental investigation with computer simulation of different utilization schemes, including the process of CO2 hydrate formation in porous media. There are two possible schemes of hydrate formation in pore medium of sediments: from liquid CO2 or the gas. The pore water in the sediment may be either in frozen or liquid states. To study these processes, an experimental investigation of hydrate formation kinetics from liquid and gaseous CO2 has been performed using the method of NMR imaging*. Experiments were made with samples of quartz sand (particles' diameter 0,21-0,297mm) with different water saturation in the range of temperatures between -3 and +8oC and pressures between 3 and 6 MPa. The experiments performed revealed the main regularities of hydrate accumulation from liquid CO2 in sediment. The influence of temperature on the rate of pore hydrate growth was analyzed. For example, the rate of hydrate growth at +7.2oC was 6 times smaller then at -3 оС. Fast hydrate formation from liquid CO2 was observed in sand samples with water saturation below 20-30%. With an increase in water saturation to 50%, the rate of hydrate formation decreased significantly, and when water saturation was 60% or more, nucleation was not observed during the time of the experiment (1-3 days). Experimental results revealed that pressure variation in the range between 4 and 6 MPa does not have any influence on the kinetics of hydrate formation from liquid CO2. Comparison of kinetics of hydrate formation from liquid and gas CO2 showed that hydrate accumulation is faster from gas CO2 then from liquid CO2. Thus, 50% of pore water that reacted with liquid CO2 transformed into hydrate in 0.8 hours after nucleation, and when reacted with CO2-gas, it transformed in 0.3 hours. The completed experiments allowed us to consider the peculiarities of hydrate formation and filtration of liquid and gaseous CO2 towards the hydrate stability zone, which is important to take into account during the elaboration of industrial techniques of CO2 injection in under-permafrost collectors. * Experiments have been made in the laboratory of NRC of Canada.

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Reliability of a Skin Diagnostic Device in Assessing Hydration and Erythema.

PubMed

Huimin, Koh; Rowledge, Alexandra M; Borzdynski, Caroline J; Miller, Charne; Frescos, Nicoletta; McKenzie, Gayle; Perry, Elizabeth; McGuiness, William

2017-10-01

To examine the reliability of a skin diagnostic device, the SD202 (Courage+Khazaka GmBH, Cologne, Germany), in assessing hydration and erythema of periwound skin and pressure injury-prone areas. Intrarater reliabilities from 3 cross-sectional and prospective studies are reported. Patients attending an outpatient, nurse-led wound dressing clinic (n = 16), a podiatrist-led high-risk foot clinic (n = 17), and residents (n = 38) at a single residential aged-care facility. Skin hydration and erythema levels assessed using the SD202. High internal consistency was maintained for consecutive skin hydration and erythema measures at a single point on the venous leg ulcer periwound (α > .996 and α > .970 for hydration and erythema, respectively) and for the pressure-prone areas of the sacrum (α > .916), right (α > .994) and left (α > .967) ischium, right (α > .989) and left (α > .916) trochanter, right (α > .985) and left (α > .992) calcaneus, and right (α > .991) and left (α > .990) lateral malleolus. High consistency was also found for the measures obtained at 4 different locations around the periwound for the venous leg ulcer (α > .935 and α > .870 for hydration and erythema, respectively). In diabetic foot ulcer assessment, acceptable internal consistency of hydration measures around the periwound was observed (α > .634). Internal consistency of erythema measures was variable, ranging from low to high reliability, particularly among predebridement measures. Using the protocols outlined in this study, the SD202 demonstrates high reliability for assessing skin hydration and erythema levels. It is possible that the SD202 can be used in clinical practice as an appropriate tool for skin hydration and erythema assessment.

Rethinking the global carbon cycle with a large, dynamic and microbially mediated gas hydrate capacitor

NASA Astrophysics Data System (ADS)

Dickens, Gerald R.

2003-08-01

Prominent negative δ13C excursions characterize several past intervals of abrupt (<100 kyr) environmental change. These anomalies, best exemplified by the >2.5‰ drop across the Paleocene/Eocene thermal maximum (PETM) ca. 55.5 Ma, command our attention because they lack explanation with conventional models for global carbon cycling. Increasingly, Earth scientists have argued that they signify massive release of CH4 from marine gas hydrates, although typically without considering the underlying process or the ensuing ramifications of such an interpretation. At the most basic level, a large, dynamic 'gas hydrate capacitor' stores and releases 13C-depleted carbon at rates linked to external conditions such as deep ocean temperature. The capacitor contains three internal reservoirs: dissolved gas, gas hydrate, and free gas. Carbon enters and leaves these reservoirs through microbial decomposition of organic matter, anaerobic oxidation of CH4 in shallow sediment, and seafloor gas venting; carbon cycles between these reservoirs through several processes, including fluid flow, precipitation and dissolution of gas hydrate, and burial. Numerical simulations show that simple gas hydrate capacitors driven by inferred changes in bottom water warming during the PETM can generate a global δ13C excursion that mimics observations. The same modeling extended over longer time demonstrates that variable CH4 fluxes to and from gas hydrates can partly explain other δ13C excursions, rapid and slow, large and small, negative and positive. Although such modeling is rudimentary (because processes and variables in modern and ancient gas hydrate systems remain poorly constrained), acceptance of a vast, externally regulated gas hydrate capacitor forces us to rethink δ13C records and the operation of the global carbon cycle throughout time.

Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

DOE PAGES

Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk; ...

2015-01-06

Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP)more » methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.« less

Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

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

Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk

Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP)more » methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.« less

Application of enzyme-treated corn starches in breakfast cereal coating.

PubMed

Luckett, Curtis R; Wang, Ya-Jane

2012-08-01

Presently ready-to-eat cereals are coated with high levels of sugar coating to extend the bowl life. Because of health concerns of added sugar, there is a need to identify alternative coating materials. This study was designed to test the efficacy of debranched corn starches with varying amylose contents as a cereal coating. Hylon VII (70% amylose), common, and waxy corn starches were gelatinized and debranched, and then sprayed onto ready-to-eat breakfast cereal flakes. The surface morphology, milk absorption, texture, and digestibility of coated cereals were determined. A starch film with a thickness of 50 to 130 μm was observed with scanning electron microscopy on the surface of the cereals coated with Hylon VII. All starch-coated cereals had a lower milk absorption value than the uncoated and glucose-coated controls. Among starch coatings, common corn starch and Hylon VII resulted in lower milk absorption than did waxy corn starch. After soaking in milk for 3 min, the peak force and work to peak of the cereals coated with corn starches were higher than those of the glucose control and uncoated reference. The cereals coated with Hylon VII were found to have an increase in dietary fiber content. The results suggest that debranched amylose-containing corn starches could extend the bowl-life of ready-to-eat cereals. Currently, many cereals are coated with sugar to keep them from becoming soggy in milk. However, added sugar has been linked to obesity, hyperactivity, and dental caries. This has led to the investigation of alternative coating materials. This study employed the film-forming properties of enzyme-treated corn starch to function as a coating material in breakfast cereal flakes. In addition, the enzyme-treated high amylose corn starch also increased the dietary fiber content of the cereal flakes. © 2012 Institute of Food Technologists®

Experimental and Numerical Investigation of Guest Molecule Exchange Kinetics based on the 2012 Ignik Sikumi Gas Hydrate Field Trial

NASA Astrophysics Data System (ADS)

Ruprecht Yonkofski, C. M.; Horner, J.; White, M. D.

2015-12-01

In 2012 the U.S. DOE/NETL, ConocoPhillips Company, and Japan Oil, Gas and Metals National Corporation jointly sponsored the first field trial of injecting a mixture of N2-CO2 into a CH4-hydrate bearing formation beneath the permafrost on the Alaska North Slope. Known as the Ignik Sikumi #1 Gas Hydrate Field Trial, this experiment involved three stages: 1) the injection of a N2-CO2 mixture into a targeted hydrate-bearing layer, 2) a 4-day pressurized soaking period, and 3) a sustained depressurization and fluid production period. Data collected during the three stages of the field trial were made available after a thorough quality check. The Ignik Sikumi #1 data set is extensive, but contains no direct evidence of the guest-molecule exchange process. This study uses numerical simulation to provide an interpretation of the CH4/CO2/N2 guest molecule exchange process that occurred at Ignik Sikumi #1. Simulations were further informed by experimental observations. The goal of the scoping experiments was to understand kinetic exchange rates and develop parameters for use in Iġnik Sikumi history match simulations. The experimental procedure involves two main stages: 1) the formation of CH4 hydrate in a consolidated sand column at 750 psi and 2°C and 2) flow-through of a 77.5/22.5 N2/CO2 molar ratio gas mixture across the column. Experiments were run both above and below the hydrate stability zone in order to observe exchange behavior across varying conditions. The numerical simulator, STOMP-HYDT-KE, was then used to match experimental results, specifically fitting kinetic behavior. Once this behavior is understood, it can be applied to field scale models based on Ignik Sikumi #1.

Comparing acoustic measurement data in eastern margin of Sea of Japan and Umitaka Spur

NASA Astrophysics Data System (ADS)

Kondo, M., IV; Aoyama, C.

2017-12-01

Recently, methane hydrate is gaining remarkable attention for the abundant amount in the sea area around Japan, and also for its carbon dioxide emission amount being as little as that of natural resources when being combusted. Two types of methane hydrates are known to exist, depending on the settings. Sand layer type methane hydrate contains sand particles and is extracted mainly in the Pacific Ocean, around 100 to 400m below seafloor. On the other hand, shallow type is found around 100m below seafloor in the Sea of Japan, in clumps, veins, and particles. One of the extraction methods of shallow type methane hydrate observed in the Sea of Japan is the seabed exploration system using acoustic equipment, which Chiharu Aoyama owns patent. Methane plumes often exist in the vicinity of shallow type methane hydrate and these seeping plumes are visualized as images on acoustic instruments such as quantitative echo sounder and multi-beam echo sounder (hereinafter referred to as MBES). These images look like rising beams on monitors and are called gas plumes. Methane hydrate can be explored effectively in the area using this method and it is understood that even when the same plume is examined, backscattering strength data (hereinafter referred as SV) observed using acoustic equipment will not be the same on quantitative echo sounder and MBES. In June 2017, measurement of acoustic data using multi-beam sonar (EM122) and quantitative echo sounder (EA600) were performed onboard DAIICHI KAIYOMARU (KAIYO ENGINEERING CO., LTD) at eastern margin of Sea of Japn and at Umitaka Spur. In this study, author will make comparisons of the acoustic data.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

PubMed Central

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

In Situ Raman Spectroscopic Observations of Gas-Saturated Rising Oil droplets: Simulation with Decane as an Oil-Equivalent Substitute

NASA Astrophysics Data System (ADS)

Peltzer, E. T.; Walz, P. M.; Brewer, P. G.

2016-02-01

Oil droplets rising from the sea floor, whether from seeps or well leakage, contain very large quantities of dissolved gas that profoundly affects their density and critical oil-water interfacial characteristics. The primary dissolved gas is methane which may be up to 30% of the molar volume. This can create a hydrate skin as the methane gas is shed from the oil as it rises through the water column, thus decreasing in pressure and increasing in temperature, and steadily changing the rising droplet buoyancy. We have explored this phenomenon by executing controlled ROV based experiments with a "bubble cup" technique in which a small volume of gas saturated decane (saturated with pure methane, a mix of methane and nitrogen , or a mix of methane and CO2) is interrogated by laser Raman spectroscopy. The use of decane as an oil "substitute" is required since natural oil samples are highly fluorescent due to the presence of polycyclic aromatic hydrocarbons. We have devised Matlab techniques for extracting the spectroscopic dissolved methane signal from the thicket of decane peaks that surround it. We have directly observed the rate at which gases are lost from the "oil" per unit area at depths in the water column that are both within and outside the hydrate forming phase boundary. We have compared the behavior of both a non-hydrate forming dissolved gas (nitrogen) with CO2 where the hydrate phase boundary is at significantly shallower depth. The results indicate complex interfacial behavior and physical chemistry. We did not observe direct gas bubble formation on the decane outer surface but did observe gas bubble formation within the oil droplets as they rose through the water column. Because there are significant energy barriers for homogeneous bubble formation within the decane phase, we took this as evidence of significant gas super-saturation within the oil droplet. The gas loss rates increased significantly in all cases when the hydrate phase boundary was crossed.

Effects of hydrated lime on radionuclides stabilization of Hanford tank residual waste.

PubMed

Wang, Guohui; Um, Wooyong; Cantrell, Kirk J; Snyder, Michelle M V; Bowden, Mark E; Triplett, Mark B; Buck, Edgar C

2017-10-01

Chemical stabilization of tank residual waste is part of a Hanford Site tank closure strategy to reduce overall risk levels to human health and the environment. In this study, a set of column leaching experiments using tank C-104 residual waste were conducted to evaluate the leachability of uranium (U) and technetium (Tc) where grout and hydrated lime were applied as chemical stabilizing agents. The experiments were designed to simulate future scenarios where meteoric water infiltrates through the vadose zones into the interior of the tank filled with layers of grout or hydrated lime, and then contacts the residual waste. Effluent concentrations of U and Tc were monitored and compared among three different packing columns (waste only, waste + grout, and waste + grout + hydrated lime). Geochemical modeling of the effluent compositions was conducted to determine saturation indices of uranium solid phases that could control the solubility of uranium. The results indicate that addition of hydrated lime strongly stabilized the uranium through transforming uranium to a highly insoluble calcium uranate (CaUO 4 ) or similar phase, whereas no significant stabilization effect of grout or hydrated lime was observed on Tc leachability. The result implies that hydrated lime could be a great candidate for stabilizing Hanford tank residual wastes where uranium is one of the main concerns. Published by Elsevier Ltd.

Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A.

2016-12-01

The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and AL/AS value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in AL/AS values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point.

Global minimum-energy structure and spectroscopic properties of I2(*-) x n H2O clusters: a Monte Carlo simulated annealing study.

PubMed

Pathak, Arup Kumar; Mukherjee, Tulsi; Maity, Dilip Kumar

2010-01-18

The vibrational (IR and Raman) and photoelectron spectral properties of hydrated iodine-dimer radical-anion clusters, I(2)(*-) x n H(2)O (n=1-10), are presented. Several initial guess structures are considered for each size of cluster to locate the global minimum-energy structure by applying a Monte Carlo simulated annealing procedure including spin-orbit interaction. In the Raman spectrum, hydration reduces the intensity of the I-I stretching band but enhances the intensity of the O-H stretching band of water. Raman spectra of more highly hydrated clusters appear to be simpler than the corresponding IR spectra. Vibrational bands due to simultaneous stretching vibrations of O-H bonds in a cyclic water network are observed for I(2)(*-) x n H(2)O clusters with n > or = 3. The vertical detachment energy (VDE) profile shows stepwise saturation that indicates closing of the geometrical shell in the hydrated clusters on addition of every four water molecules. The calculated VDE of finite-size small hydrated clusters is extrapolated to evaluate the bulk VDE value of I(2)(*-) in aqueous solution as 7.6 eV at the CCSD(T) level of theory. Structure and spectroscopic properties of these hydrated clusters are compared with those of hydrated clusters of Cl(2)(*-) and Br(2)(*-).

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

DOE PAGES

Alam, Todd M.; Pearce, Charles Joseph

2015-06-28

The infrared (IR) spectra of micro-hydrated Sarin•(H 2O) n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (~1270 to 1290 cm –1) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (~810 to 815 cm –1) and the C-O-P vibrational modes (~995 to 1004 cm –1) showed that the water interactions with these functional groups were minor, and that themore » structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. As a result, the H 2O•H 2O vibrational modes (~3450 to 3660 cm –1) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters.« less

Magnetic hysteresis parameters and Day plot analysis to characterize diagenetic alteration in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Enkin, Randolph J.; Baker, Judith; Nourgaliev, Danis; Iassonov, Pavel; Hamilton, Tark S.

2007-06-01

The J meter coercivity spectrometer is a machine capable of rapid and simple measurement of magnetic hysteresis, isothermal remanence acquisition and magnetic viscosity of rocks and sediments. The J meter was used to study a suite of samples collected from strata in the gas hydrate-bearing JAPEX/JNOC/GSC Mallik 5L-38 well (69.5°N, 134.6°W) in the Mackenzie Delta of the northwestern Canadian Arctic. The Day plot of magnetic hysteresis ratios for these samples is exotic in that the points do not plot along a hyperbola as is usually observed. Rather, they plot as a scatter which is shown to contour into vertical slices using coercivity field (HC) or saturation magnetization (JS), and horizontal slices using the relative quantity of superparamagnetism (JSPM/JS). Optical microscopy reveals that the magnetic minerals are detrital magnetite and authigenic greigite. Greigite is dominant in sands which in situ had >70% gas hydrate saturation and in silts in which gas hydrate growth was blocked by insufficient porosity. We infer that the silts were the accumulation sites for solutes which had been excluded from the pore waters in neighboring coarser-grained sediments during the course of gas hydrate formation. Consequently, we conclude that magnetic properties are related to gas hydrate-related processes, and as such, may have potential as a method of remote sensing for gas hydrate deposits.

The role of water in gas hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

Postglacial response of Arctic Ocean gas hydrates to climatic amelioration

PubMed Central

Serov, Pavel; Mienert, Jürgen; Patton, Henry; Portnov, Alexey; Silyakova, Anna; Panieri, Giuliana; Carroll, Michael L.; Carroll, JoLynn; Andreassen, Karin; Hubbard, Alun

2017-01-01

Seafloor methane release due to the thermal dissociation of gas hydrates is pervasive across the continental margins of the Arctic Ocean. Furthermore, there is increasing awareness that shallow hydrate-related methane seeps have appeared due to enhanced warming of Arctic Ocean bottom water during the last century. Although it has been argued that a gas hydrate gun could trigger abrupt climate change, the processes and rates of subsurface/atmospheric natural gas exchange remain uncertain. Here we investigate the dynamics between gas hydrate stability and environmental changes from the height of the last glaciation through to the present day. Using geophysical observations from offshore Svalbard to constrain a coupled ice sheet/gas hydrate model, we identify distinct phases of subglacial methane sequestration and subsequent release on ice sheet retreat that led to the formation of a suite of seafloor domes. Reconstructing the evolution of this dome field, we find that incursions of warm Atlantic bottom water forced rapid gas hydrate dissociation and enhanced methane emissions during the penultimate Heinrich event, the Bølling and Allerød interstadials, and the Holocene optimum. Our results highlight the complex interplay between the cryosphere, geosphere, and atmosphere over the last 30,000 y that led to extensive changes in subseafloor carbon storage that forced distinct episodes of methane release due to natural climate variability well before recent anthropogenic warming. PMID:28584081

Hydrogen storage in double clathrates with tert-butylamine.

PubMed

Prasad, Pinnelli S R; Sugahara, Takeshi; Sum, Amadeu K; Sloan, E Dendy; Koh, Carolyn A

2009-06-18

The first proof-of-concept of the formation of a double tert-butylamine (t-BuNH(2)) + hydrogen (H(2)) clathrate hydrate has been demonstrated. Binary clathrate hydrates with different molar concentrations of the large guest t-BuNH(2) (0.98-9.31 mol %) were synthesized at 13.8 MPa and 250 K, and characterized by powder X-ray diffraction and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed under hydrogen pressures. Raman spectroscopic data suggested that the hydrogen molecules occupied the small cages and had similar occupancy to hydrogen in the double tetrahydrofuran (THF) + H(2) clathrate hydrate. The hydrogen storage capacity in this system was approximately 0.7 H(2) wt % at the molar concentration of t-BuNH(2) close to the sII stoichiometry.

Borehole Tool for the Comprehensive Characterization of Hydrate-bearing Sediments

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

Dai, Sheng; Santamarina, J. Carlos

Reservoir characterization and simulation require reliable parameters to anticipate hydrate deposits responses and production rates. The acquisition of the required fundamental properties currently relies on wireline logging, pressure core testing, and/or laboratory observations of synthesized specimens, which are challenged by testing capabilities and innate sampling disturbances. The project reviews hydrate-bearing sediments, properties, and inherent sampling effects, albeit lessen with the developments in pressure core technology, in order to develop robust correlations with index parameters. The resulting information is incorporated into a tool for optimal field characterization and parameter selection with uncertainty analyses. Ultimately, the project develops a borehole tool formore » the comprehensive characterization of hydrate-bearing sediments at in situ, with the design recognizing past developments and characterization experience and benefited from the inspiration of nature and sensor miniaturization.« less

Influence of overconsolidated condition on permeability evolution in silica sand

NASA Astrophysics Data System (ADS)

Kimura, S.; Kaneko, H.; Ito, T.; Nishimura, O.; Minagawa, H.

2013-12-01

Permeability of sediments is important factors for production of natural gas from natural gas hydrate bearing layers. Methane-hydrate is regarded as one of the potential resources of natural gas. As results of coring and logging, the existence of a large amount of methane-hydrate is estimated in the Nankai Trough, offshore central Japan, where many folds and faults have been observed. In the present study, we investigate the permeability of silica sand specimen forming the artificial fault zone after large displacement shear in the ring-shear test under two different normal consolidated and overconsolidated conditions. The significant influence of overconsolidation ratio (OCR) on permeability evolution is not found. The permeability reduction is influenced a great deal by the magnitude of normal stress during large displacement shearing. The grain size distribution and structure observation in the shear zone of specimen after shearing at each normal stress level are analyzed by laser scattering type particle analyzer and scanning electron microscope, respectively. It is indicated that the grain size and porosity reduction due to the particle crushing are the factor of the permeability reduction. This study is financially supported by METI and Research Consortium for Methane Hydrate Resources in Japan (the MH21 Research Consortium).

A fermented barley and soybean formula enhances skin hydration.

PubMed

Lee, Sein; Kim, Jong-Eun; Suk, Sujin; Kwon, Oh Wook; Park, Gaeun; Lim, Tae-Gyu; Seo, Sang Gwon; Kim, Jong Rhan; Kim, Dae Eung; Lee, Miyeong; Chung, Dae Kyun; Jeon, Jong Eun; Cho, Dong Woon; Hurh, Byung Serk; Kim, Sun Yeou; Lee, Ki Won

2015-09-01

Skin hydration is one of the primary aims of beauty and anti-aging treatments. Barley (Hordeum vulgare) and soybean (Glycine max) are major food crops, but can also be used as ingredients for the maintenance of skin health. We developed a natural product-based skin treatment using a barley and soybean formula (BS) incorporating yeast fermentation, and evaluated its skin hydration effects as a dietary supplement in a clinical study. Participants ingested a placebo- (n = 33) or BS- (3 g/day) containing drink (n = 32) for 8 weeks. A significant increase in hydration in the BS group as compared to the placebo group was observed on the faces of subjects after 4 and 8 weeks, and on the forearm after 4 weeks. Decreases in stratum corneum (SC) thickness were also observed on the face and forearm. BS enhanced hyaluronan (HA) and skin barrier function in vitro and reduced Hyal2 expression in human dermal fibroblasts (HDF). BS also recovered ultraviolet (UV) B-induced downregulation of HA in HaCaT cells. These results suggest that BS has promising potential for development as a health functional food to enhance skin health.

A fermented barley and soybean formula enhances skin hydration

PubMed Central

Lee, Sein; Kim, Jong-Eun; Suk, Sujin; Kwon, Oh Wook; Park, Gaeun; Lim, Tae-gyu; Seo, Sang Gwon; Kim, Jong Rhan; Kim, Dae Eung; Lee, Miyeong; Chung, Dae Kyun; Jeon, Jong Eun; Cho, Dong Woon; Hurh, Byung Serk; Kim, Sun Yeou; Lee, Ki Won

2015-01-01

Skin hydration is one of the primary aims of beauty and anti-aging treatments. Barley (Hordeum vulgare) and soybean (Glycine max) are major food crops, but can also be used as ingredients for the maintenance of skin health. We developed a natural product-based skin treatment using a barley and soybean formula (BS) incorporating yeast fermentation, and evaluated its skin hydration effects as a dietary supplement in a clinical study. Participants ingested a placebo- (n = 33) or BS- (3 g/day) containing drink (n = 32) for 8 weeks. A significant increase in hydration in the BS group as compared to the placebo group was observed on the faces of subjects after 4 and 8 weeks, and on the forearm after 4 weeks. Decreases in stratum corneum (SC) thickness were also observed on the face and forearm. BS enhanced hyaluronan (HA) and skin barrier function in vitro and reduced Hyal2 expression in human dermal fibroblasts (HDF). BS also recovered ultraviolet (UV) B-induced downregulation of HA in HaCaT cells. These results suggest that BS has promising potential for development as a health functional food to enhance skin health. PMID:26388675

Repulsive hydration forces between calcite surfaces and their effect on the brittle strength of calcite-bearing rocks

NASA Astrophysics Data System (ADS)

Røyne, Anja; Dalby, Kim N.; Hassenkam, Tue

2015-06-01

The long-term mechanical strength of calcite-bearing rocks is highly dependent on the presence and nature of pore fluids, and it has been suggested that the observed effects are due to changes in nanometer-scale surface forces near fracture tips and grain contacts. In this letter, we present measurements of forces between two calcite surfaces in air and water-glycol mixtures using the atomic force microscope. We show a time- and load-dependent adhesion at low water concentrations and a strong repulsion in the presence of water, which is most likely due to hydration of the strongly hydrophilic calcite surfaces. We argue that this hydration repulsion can explain the commonly observed water-induced decrease in strength in calcitic rocks and single calcite crystals. Furthermore, this relatively simple experimental setup may serve as a useful tool for analyzing surface forces in other mineral-fluid combinations.

Can xenon in water inhibit ice growth? Molecular dynamics of phase transitions in water-Xe system.

PubMed

Artyukhov, Vasilii I; Pulver, Alexander Yu; Peregudov, Alex; Artyuhov, Igor

2014-07-21

Motivated by recent experiments showing the promise of noble gases as cryoprotectants, we perform molecular dynamics modeling of phase transitions in water with xenon under cooling. We follow the structure and dynamics of xenon water solution as a function of temperature. Homogeneous nucleation of clathrate hydrate phase is observed and characterized. As the temperature is further reduced we observe hints of dissociation of clathrate due to stronger hydrophobic hydration, pointing towards a possible instability of clathrate at cryogenic temperatures and conversion to an amorphous phase comprised of "xenon + hydration shell" Xe·(H2O)21.5 clusters. Simulations of ice-xenon solution interface in equilibrium and during ice growth reveal the effects of xenon on the ice-liquid interface, where adsorbed xenon causes roughening of ice surface but does not preferentially form clathrate. These results provide evidence against the ice-blocker mechanism of xenon cryoprotection.

Distinctive Geomorphology of Gas Venting and Near Seafloor Gas Hydrate-Bearing sites

NASA Astrophysics Data System (ADS)

Paull, C. K.; Caress, D. W.; Lundsten, E.; Anderson, K.; Gwiazda, R.; McGann, M. L.; Edwards, B. D.; Riedel, M.; Herguera, J.

2012-12-01

High-resolution multibeam bathymetry and chirp seismic-reflection profiles collected with an Autonomous Underwater Vehicle (AUV) complimented by Remotely Operated Vehicle (ROV) observations and sampling reveal the fine scale geomorphology associated with gas venting and/or near subsurface gas hydrate accumulations along the Pacific North American continental margin (Santa Monica Basin, Hydrate Ridge, Eel River, Barkley Canyon, and Bullseye Vent) and along the transform faults in the Gulf of California. At the 1 m multibeam grid resolution of the new data, distinctive features and textures that are undetectable at lower resolution, show the impact of gas venting, gas hydrate development, and related phenomena on the seafloor morphology. Together a suite of geomorphic characteristics illustrates different stages in the development of seafloor gas venting systems. The more mature and/or impacted areas are associated with widespread exposures of methane-derived carbonates, which form broken and irregular seafloor pavements with karst-like voids in between the cemented blocks. These mature areas also contain elevated features >10 m high and circular seafloor craters with diameters of 3-50 m that appear to be associated with missing sections of the original seafloor. Smaller mound-like features (<10 m in diameter and 1-3 m higher than the surrounding seafloor) occur at multiple sites. Solid lenses of gas hydrate are occasionally exposed along fractures on the sides of these mounds and suggest that these are push-up features associated with gas hydrate growth within the near seafloor sediments. The youngest appearing features are associated with more-subtle (<3 m in diameter and ~0.5 m high) seafloor mounds, the crests of which are crossed with small cracks lined with white bacterial mats. ROV-collected (<1.5 m long) cores obtained from these subtle mounds encountered a hard layer at 30-60 cm sub-bottom. When this layer was penetrated, methane bubbles gushed out and continued to flow out for over an hour. These observations indicate that these small mounds are young features that trap considerable volumes of gas near the seafloor. Together these observations reveal the integrated effect that gas and/or gas hydrate occurrences can have on the seafloor. The existence of gaseous methane within ~1 m of the seafloor has intriguing implications as to the geo-hazard potential of such sites.

The phase transition of methane caused by pressure change during its seeping up from seepage, revealed by video observation and acoustic reflection data

NASA Astrophysics Data System (ADS)

Aoyama, C.

2017-12-01

Methane plumes often exist in the vicinity sea area where shallow type methane hydrates are extracted and they are observed as images displayed on monitors of multi-beam sonar and echo sounder onboard, where methane hydrates are expected at sea bottom on ROV observation data. The hydrates are generally considered to be generated in shallow depths below the sea floor. In this study, author examined annual amount of methane dissolving into seawater by measuring the amount of plume in order to make a quantification of dissolving methane from seafloor. Measurement procedure is plume exploration using multi-beam and quantitative echo sounder , submerge ROV to gushing point at seafloor , calculate the rising speed of methane plumes and examine the phases by monitoring seeping plumes from seafloor with high-definition camera. Components of seeping plumes were defined as methane hydrate particles based on the result by measuring water temperature. From this procedure, it can be concluded that the minimum rising speed of methane hydrate particles from gushing point is 1.6×10-1(m/s) and the maximum of 2.0×10-1(m/s) indicating a difference of more than ten times the gaseous theoretical value of 2.74(m/s). This speed is theoretically closer to the solid speed of the material with physical property similar to hydrates, which is 3.05×10-1 (m/s). Therefore, it can be determined that those particles are in the solid state, immediately above seafloor. To measure the amount of plumes seeping from gushing points funnel-shaped instruments with 20cm diameter opening were used to collect methane plumes in this sea area. This was performed in three different gushing points. As a result, 300ml of methane plume was collected in 643 seconds. Assuming that gushing points exist evenly in the sea area, the annual amount of methane gas seeping from these points will be 7.7×105m3 /per m2. Result shows a large quantity of methane seeping from seafloor into the water. This data is an important factor when considering carbon cycle and future development the shallow methane hydrate resources.

Acetylene reduction (nitrogen fixation) associated with corn inoculated with Spirillum.

PubMed

Barber, L E; Tjepkema, J D; Russell, S A; Evans, H J

1976-07-01

Sorghum and corn breeding lines were grown in soil in field and greenhouse experiments with and without an inoculum of N2-fixing in Spirillum strains from Brazil. Estimated rates of N2 fixation associated with field-grown corn and sorghum plants were less than 4 g of N2/ha per day. The mean estimated N2-fixation rates determined on segments of roots from corn inoculated with Spirillum and grown in the greenhouse at 24 to 27 degrees C were 15 g of N2/ha per day (16 inbreds), 25 g of N2/ha per day (six hybrids), and 165 g of N2/ha per day for one hybird which was heavily inoculated. The corresponding mean rates determined from measurements of in situ cultures of the same series of corn plants (i.e., 16 inbreds, six hybrids, and one heavily inoculated hybrid) were 0.4, 2.3, and 1.1 g of N2/ha per day, respectively. Lower rates of C2H2 reduction were associated with control corn cultures which had been treated with autoclaved Spirillum than with cultures inoculated with live Spirillum. No C2H2 reduction was detected in plant cultures treated with ammonium nitrate. Numbers of nitrogen-fixing bacteria on excised roots of corn plants increased an average of about 30-fold during an overnight preincubation period, and as a result acetylene reduction assays of root samples after preincubation failed to serve as a valid basis for estimating N2 fixation by corn in pot cultures. Plants grown without added nitrogen either with or without inoculum exhibited severe symptoms of nitrogen deficiency and in most cases produced significantly less dry weight than those supplied with fixed nitrogen. Although substantial rates of C2H2 reduction by excised corn roots were observed after preincubation under limited oxygen, the yield and nitrogen content of inoculated plants and the C2H2-reduction rates by inoculated pot cultures of corn, in situ, provided no evidence of appreciable N2 fixation.

Sedimentological Properties of Natural Gas Hydrates-Bearing Sands in the Nankai Trough and Mallik Areas

NASA Astrophysics Data System (ADS)

Uchida, T.; Tsuji, T.; Waseda, A.

2009-12-01

The Nankai Trough parallels the Japanese Island, where extensive BSRs have been interpreted from seismic reflection records. High resolution seismic surveys have definitely indicated gas hydrate distributions, and drilling the MITI Nankai Trough wells in 2000 and the METI Tokai-oki to Kumano-nada wells in 2004 have revealed subsurface gas hydrate in the eastern part of Nankai Trough. In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that also clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. During the field operations, the LWD and wire-line well log data were continuously obtained and plenty of gas hydrate-bearing sand cores were recovered. Subsequence sedimentological and geochemical analyses performed on those core samples revealed the crucial geologic controls on the formation and preservation of natural gas hydrate in sediments. Pore-space gas hydrates reside in sandy sediments mostly filling intergranular porosity. Pore waters chloride anomalies, core temperature depression and core observations on visible gas hydrates confirm the presence of pore-space gas hydrates within moderate to thick sandy layers, typically 10 cm to a meter thick. Sediment porosities and pore-size distributions were obtained by mercury porosimetry, which indicate that porosities of gas hydrate-bearing sandy strata are approximately 45 %. According to grain size distribution curves, gas hydrate is dominant in fine- to very fine-grained sandy strata. Gas hydrate saturations are typically up to 80 % in pore volume throughout most of the hydrate-dominant sandy layers, which are estimated by well log analyses as well as pore water chloride anomalies. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicated that highly saturated sands should have permeability of 1 x 10-15 to 5 x 10-15 m2 (1 to 5 millidarcies). Most of gas hydrates fill the intergranular pore systems of sandy layers, which are derived from the sedimentary facies such as channels and crevasse splay/levee deposits. It is remarked that those sandy strata are usually composed of arenite sands with matrix-free intergranular pore systems. Gas hydrates are less frequently found in fine-grained sediments such as siltstone and mudstone from overbank deposits. Methane gas accumulation and original pore space large enough to occur within host sediments may be required for forming highly saturated gas hydrate in pore system. The distribution of a porous and coarser-grained host rock should be one of the important factors to control the occurrence of gas hydrate, as well as physicochemical conditions. This appears to be a similar mode for conventional oil and gas accumulations, and this knowledge is important to predicting the location of other hydrate deposits and their eventual energy resource. This study was performed as a part of the MH21 Research Consortium on methane hydrate in Japan.

A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2012-12-01

The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, nonaqueous liquid, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulations that predict the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. The phase equilibria for the ternary gas hydrate system within the gas hydrate stability range of composition, temperature and pressure, includes regions where the gas hydrate is in equilibrium with gas, nonaqueous liquid, or mixtures of gas and nonaqeuous liquid near the CO2-CH4-N2 mixture critical point. In these regions, solutions to cubic equations of state can be nonconvergent without accurate initial guesses. A hybrid tabular-cubic equation of state is described which avoids convergence issues, but conserves the characteristics and advantages of the cubic equation of state approaches to phase equilibria calculations. The application of interest will be the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

Comparison of the composting process using ear corn residue and three other conventional bulking agents during cow manure composting under high-moisture conditions.

PubMed

Hanajima, Dai

2014-10-01

To elucidate the characteristics of ear corn residue as a bulking agent, the composting process using this residue was compared with processes using three other conventional materials such as sawdust, wheat straw and rice husk, employing a bench-scale composting reactor. As evaluated via biochemical oxygen demand (BOD), ear corn residue contains 3.3 and 2.0 times more easily digestible materials than sawdust and rice husk, respectively. In addition, mixing ear corn residue with manure resulted in reduced bulk density, which was the same as that of wheat straw and was 0.58 and 0.67 times lower than that of sawdust and a rice husk mixture, respectively. To evaluate temperature generation during the composting process, the maximum temperature and area under the temperature curve (AUCTEMP) were compared among the mixed composts of four bulking agents. Maximum temperature (54.3°C) as well as AUCTEMP (7310°C●h) of ear corn residue were significantly higher than those of sawdust and rice husk (P<0.05), and they are similar to that of wheat straw mixed compost. Along with the value of AUCTEMP, the highest organic matter losses of 31.1% were observed in ear corn residue mixed compost, followed by wheat straw, saw dust and rice husk. © 2014 Japanese Society of Animal Science.

Peripheral nerve metabolism and zinc levels in streptozotocin induced diabetic rats. Effect of diets high in fish and corn oil

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

Burke, J.P.; Fenton, M.R.

1991-03-15

This study was designed to assess the effects of diets high in fish and corn oil on peripheral nerve metabolism in streptozotocin (STZ) induced diabetic rats. A type I diabetic state was induced in female Sprague-Dawley rats by injection of STZ. Animals were divided into three dietary groups; normal rat chow, high corn oil diet and high fish oil diet. After 4 weeks animals were analyzed for nerve conduction velocity, bled and then sacrificed. Sciatic nerves were removed, processed and several biochemical parameters determined. Plasma zinc levels were elevated in the STZ normal chow group compared to non-diabetic controls. Bothmore » corn oil and fish oil diets tended to eliminate the rise in plasma zinc. Differences in subcellular distribution of zinc in sciatic nerves were also observed. Normal chow STZ animals displayed a 20% decrease in nerve conduction velocity compared to control. Dietary supplementation with either fish or corn oil seemed to ameliorate these effects. Biochemical analysis of Na{sup +}-K{sup +}-ATPase and protein kinase C revealed a decrease in activity in normal chow animals compared to control groups. Again, dietary intervention with either fish or corn oil seemed to return these activities back to normal. The results suggest a link between zinc metabolism and peripheral nerve metabolism which can be modified by dietary intervention.« less

Corn silage replacement with barley silage in dairy cows' diet does not change milk quality, cheese quality and yield.

PubMed

Migliorati, Luciano; Boselli, Leonardo; Pirlo, Giacomo; Moschini, Maurizio; Masoero, Francesco

2017-08-01

Considering that water availability for agricultural needs is being restricted, an alternative to corn in animal nutrition should be explored in the Po Valley. The present study aimed to evaluate the effects of either a partial (Trial I) or a total (Trial II) corn silage substitution with barley silage in dairy cows' diet on milk yield and composition, its coagulation properties, cheese yield and the sensorial profile of 16-month-aged Grana Padano cheese. A partial or a total substitution of corn silage with barley silage had no effect on milk yield. Milk fat content in Trial I and milk urea content in both trials were higher with barley silage based diets than in corn silage based diets. No effects were observed concerning the lactodinamographic profile for milk aptitude to cheese-making, cheese yield and its organoleptic traits between feed treatments in Trials I and II. In both trials, hardness, friability and solubility scores were generally lower than reference values, whereas deformability, elasticity and stickiness scores were generally higher than reference values. A partial or a total substitution of corn silage with barley silage in diets for dairy cows did not induce any negative effects on animal performance, nor on milk-quality traits, cheese quality and yield. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Submarine creeping landslide deformation controlled by the presence of gas hydrates: The Tuaheni Landslide Complex, New Zealand

NASA Astrophysics Data System (ADS)

Gross, Felix; Mountjoy, Joshu; Crutchle, Garethy; Koch, Stephanie; Bialas, Jörg; Pecher, Ingo; Woelz, Susi; Dannowski, Anke; Carey, Jon; Micallef, Aaron; Böttner, Christoph; Huhn, Katrin; Krastel, Sebastian

2016-04-01

Methane hydrate occurrence is bound to a finite pressure/temperature window on continental slopes, known as the gas hydrate stability zone (GHSZ). Hydrates within sediment pore spaces and fractures are recognized to act like a cement, increasing shear strength and stabilizing slopes. However, recent studies show that over longer strain periods methane hydrates can undergo ductile deformation. This combination of short term strengthening and longer term ductile behavior is implicated in the development of slow creeping submarine landforms within the GHSZ. In order to study this phenomenon, a new high-resolution seismic 3D volume was acquired at the Tuaheni Landslide Complex (TLC) at the Hikurangi margin offshore the North Island of New Zealand. Parts of TLC have been interpreted as a slow moving landslide controlled by the gas hydrate system. Two hypotheses for its slow deformation related to the presence of methane hydrates have been proposed: i) Hydrofracturing, driven by gas pressure at the base of the GHSZ, allows pressurized fluids to ascend toward the seafloor, thereby weakening the shallow debris and promoting failure. ii) The mixture of methane hydrates and sediment results in a rheology that behaves in a ductile way under sustained loading, resulting in slow deformation comparable to that of terrestrial and extra-terrestrial rock glaciers. The 3D dataset reveals the distribution of gas and the extend of gas hydrate stability within the deformed debris, as well as deformation fabrics like tectonic-style faulting and a prominent basal décollement, known to be a critical element of terrestrial earth-flows and rock glaciers. Observations from 3D data indicate that the TLC represents the type example of a new submarine landform - an active creeping submarine landslide - which is influenced by the presence of gas hydrates. The morphology, internal structure and deformation of the landslide are comparable with terrestrial- and extra-terrestrial earth flows and rock-glaciers.

Seismic imaging of a fractured gas hydrate system in the Krishna-Godavari Basin offshore India

USGS Publications Warehouse

Riedel, M.; Collett, T.S.; Kumar, P.; Sathe, A.V.; Cook, A.

2010-01-01

Gas hydrate was discovered in the Krishna-Godavari (KG) Basin during the India National Gas Hydrate Program (NGHP) Expedition 1 at Site NGHP-01-10 within a fractured clay-dominated sedimentary system. Logging-while-drilling (LWD), coring, and wire-line logging confirmed gas hydrate dominantly in fractures at four borehole sites spanning a 500m transect. Three-dimensional (3D) seismic data were subsequently used to image the fractured system and explain the occurrence of gas hydrate associated with the fractures. A system of two fault-sets was identified, part of a typical passive margin tectonic setting. The LWD-derived fracture network at Hole NGHP-01-10A is to some extent seen in the seismic data and was mapped using seismic coherency attributes. The fractured system around Site NGHP-01-10 extends over a triangular-shaped area of ~2.5 km2 defined using seismic attributes of the seafloor reflection, as well as " seismic sweetness" at the base of the gas hydrate occurrence zone. The triangular shaped area is also showing a polygonal (nearly hexagonal) fault pattern, distinct from other more rectangular fault patterns observed in the study area. The occurrence of gas hydrate at Site NGHP-01-10 is the result of a specific combination of tectonic fault orientations and the abundance of free gas migration from a deeper gas source. The triangular-shaped area of enriched gas hydrate occurrence is bound by two faults acting as migration conduits. Additionally, the fault-associated sediment deformation provides a possible migration pathway for the free gas from the deeper gas source into the gas hydrate stability zone. It is proposed that there are additional locations in the KG Basin with possible gas hydrate accumulation of similar tectonic conditions, and one such location was identified from the 3D seismic data ~6 km NW of Site NGHP-01-10. ?? 2010.