Limitation of biocompatibility of hydrated nanocrystalline hydroxyapatite

NASA Astrophysics Data System (ADS)

Minaychev, V. V.; Teleshev, A. T.; Gorshenev, V. N.; Yakovleva, M. A.; Fomichev, V. A.; Pankratov, A. S.; Menshikh, K. A.; Fadeev, R. S.; Fadeeva, I. S.; Senotov, A. S.; Kobyakova, M. I.; Yurasova, Yu B.; Akatov, V. S.

2018-04-01

Nanostructured hydroxyapatite (HA) in the form of hydrated paste is considered to be a promising material for a minor-invasive surgical curing of bone tissue injure. However questions about adhesion of cells on this material and its biocompatibility still remain. In this study biocompatibility of paste-formed nanosized HA (nano-HA) by in vitro methods is investigated. Nano-HA (particles sized about 20 nm) was synthesized under conditions of mechano-acoustic activation of an aqueous reaction mixture of ammonium hydrophosphate and calcium nitrate. It was ascertained that nanocrystalline paste was not cytotoxic although limitation of adhesion, spreading and growth of the cells on its surface was revealed. The results obtained point on the need of modification of hydrated nano-HA in the aims of increasing its biocompatibility and osteoplastic potential.

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.

The Effect of Moisture on the Hydrolysis of Basic Salts.

PubMed

Shi, Xiaoyang; Xiao, Hang; Chen, Xi; Lackner, Klaus S

2016-12-19

A great deal of information exists concerning the hydration of ions in bulk water. Much less noticeable, but equally ubiquitous is the hydration of ions holding on to several water molecules in nanoscopic pores or in natural air at low relative humidity. Such hydration of ions with a high ratio of ions to water molecules (up to 1:1) are essential in determining the energetics of many physical and chemical systems. Herein, we present a quantitative analysis of the energetics of ion hydration in nanopores based on molecular modeling of a series of basic salts associated with different numbers of water molecules. The results show that the degree of hydrolysis of basic salts in the presence of a few water molecules is significantly different from that in bulk water. The reduced availability of water molecules promotes the hydrolysis of divalent and trivalent basic ions (S 2 - , CO 3 2- , SO 3 2- , HPO 4 2- , SO 4 2- , PO 4 3- ), which produces lower valent ions (HS - , HCO 3 - , HSO 3 - , H 2 PO 4 - , HSO 4 - , HPO 4 2- ) and OH - ions. However, reducing the availability of water inhibits the hydrolysis of monovalent basic ions (CN - , HS - ). This finding sheds some light on a vast number of chemical processes in the atmosphere and on solid porous surfaces. The discovery has wide potential applications including designing efficient absorbents for acidic gases. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and evaluation of liposomal formulation of pilocarpine nitrate.

PubMed

Rathod, S; Deshpande, S G

2010-03-01

Prolonged release drug delivery system of pilocarpine nitrate was made by optimizing thin layer film hydration method. Egg phosphatidylcholine and cholesterol were used to make multilamellar vesicles. Effects of charges over the vesicles were studied by incorporating dicetylphosphate and stearylamine. Various factors, which may affect the size, shape, encapsulation efficiency and release rate, were studied. Liposomes in the size range 0.2 to 1 µm were obtained by optimizing the process. Encapsulation efficiency of neutral, positive and negatively charged liposomes were found to be 32.5, 35.4 and 34.2 percent, respectively. In vitro drug release rate was studied on specially designed model. Biological response in terms of reduction in intraocular pressure was observed on rabbit eyes. Pilocarpine nitrate liposomes were lyophilized and stability studies were conducted.

Nitrate leaching index

USDA-ARS?s Scientific Manuscript database

The Nitrate Leaching Index is a rapid assessment tool that evaluates nitrate (NO3) leaching potential based on basic soil and climate information. It is the basis for many nutrient management planning efforts, but it has considerable limitations because of : 1) an oversimplification of the processes...

Thermodynamics of complexation in an aqueous solution of Tb(III) nitrate at 298 K

NASA Astrophysics Data System (ADS)

Lobacheva, O. L.; Berlinskii, I. V.; Dzhevaga, N. V.

2017-01-01

The pH of the formation of hydroxo complexes and hydrates in an aqueous solution of terbium Tb(III) is determined using combined means of potentiometric and conductometric titration. The stability constants of the hydroxo complexes, the products of hydroxide solubility, and the Gibbs energy of terbium hydroxo complex formation are calculated.

Obsidian hydration profile measurements using a nuclear reaction technique

USGS Publications Warehouse

Lee, R.R.; Leich, D.A.; Tombrello, T.A.; Ericson, J.E.; Friedman, I.

1974-01-01

AMBIENT water diffuses into the exposed surfaces of obsidian, forming a hydration layer which increases in thickness with time to a maximum depth of 20-40 ??m (ref. 1), this layer being the basic foundation of obsidian dating2,3. ?? 1974 Nature Publishing Group.

Research opportunities in salt hydrates for thermal energy storage

NASA Astrophysics Data System (ADS)

Braunstein, J.

1983-11-01

The state of the art of salt hydrates as phase change materials for low temperature thermal energy storage is reviewed. Phase equilibria, nucleation behavior and melting kinetics of the commonly used hydrate are summarized. The development of efficient, reliable inexpensive systems based on phase change materials, especially salt hydrates for the storage (and retrieval) of thermal energy for residential heating is outlined. The use of phase change material thermal energy storage systems is not yet widespread. Additional basic research is needed in the areas of crystallization and melting kinetics, prediction of phase behavior in ternary systems, thermal diffusion in salt hydrate systems, and in the physical properties pertinent to nonequilibrium and equilibrium transformations in these systems.

Development of media for dynamic latent heat storage for the low-temperature range. Part 1: Thermal analyses of selected salt hydrate systems

NASA Technical Reports Server (NTRS)

Kanwischer, H.; Tamme, R.

1985-01-01

Phase change temperatures and phase change enthalpies of seventeen salt hydrates, three double salts, and four eutectics were measured thermodynamically and the results reported herein. Good results were obtained, especially for congruently melting salt hydrates. Incongruently melting salt hydrates appear less suitable for heat storage applications. The influence of the second phase - water, acid and hydroxide - to the latent heat is described. From these results, basic values of the working temperatures and storage capabilities of various storage media compositions may be derived.

DEHYDRATION OF DEUTERIUM OXIDE SLURRIES

DOEpatents

Hiskey, C.F.

1959-03-10

A method is presented for recovering heavy water from uranium oxide-- heavy water slurries. The method consists in saturating such slurries with a potassium nitrate-sodium nitrate salt mixture and then allowing the self-heat of the slurry to raise its temperature to a point slightly in excess of 100 deg C, thus effecting complete evaporation of the free heavy water from the slurry. The temperature of the slurry is then allowed to reach 300 to 900 deg C causing fusion of the salt mixture and expulsion of the water of hydration. The uranium may be recovered from the fused salt mixture by treatment with water to leach the soluble salts away from the uranium-containing residue.

The importance of dehydration in determining ion transport in narrow pores.

PubMed

Richards, Laura A; Schäfer, Andrea I; Richards, Bryce S; Corry, Ben

2012-06-11

The transport of hydrated ions through narrow pores is important for a number of processes such as the desalination and filtration of water and the conductance of ions through biological channels. Here, molecular dynamics simulations are used to systematically examine the transport of anionic drinking water contaminants (fluoride, chloride, nitrate, and nitrite) through pores ranging in effective radius from 2.8 to 6.5 Å to elucidate the role of hydration in excluding these species during nanofiltration. Bulk hydration properties (hydrated size and coordination number) are determined for comparison with the situations inside the pores. Free energy profiles for ion transport through the pores show energy barriers depend on pore size, ion type, and membrane surface charge and that the selectivity sequence can change depending on the pore size. Ion coordination numbers along the trajectory showed that partial dehydration of the transported ion is the main contribution to the energy barriers. Ion transport is greatly hindered when the effective pore radius is smaller than the hydrated radius, as the ion has to lose some associated water molecules to enter the pore. Small energy barriers are still observed when pore sizes are larger than the hydrated radius due to re-orientation of the hydration shell or the loss of more distant water. These results demonstrate the importance of ion dehydration in transport through narrow pores, which increases the current level of mechanistic understanding of membrane-based desalination and transport in biological channels. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prototype Scale Development of an Environmentally Benign Yellow Smoke Hand-Held Signal Formulation Based on Solvent Yellow 33

DTIC Science & Technology

2013-04-15

VAAR) was purchased from McGean. Hydrated basic magnesium carbonate was obtained from Pine Bluff Arsenal (Pine Bluff, AR) and was confirmed to be Mg5( CO3 ...a potential environmental exposure of approximately 29 g of the toxic yellow dyes throughout the life cycle of a single M194 signal! To mitigate this...consists of Solvent Yellow 33 as the smoke sublimating agent, hydrated basic magnesium carbonate (Mg5( CO3 )4(OH)2·4H2O) instead of sodium bicarbonate (NaHCO3

Hydration of nonelectrolytes in binary aqueous solutions

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2010-10-01

Literature data on the thermodynamic properties of binary aqueous solutions of nonelectrolytes that show negative deviations from Raoult's law due largely to the contribution of the hydration of the solute are briefly surveyed. Attention is focused on simulating the thermodynamic properties of solutions using equations of the cluster model. It is shown that the model is based on the assumption that there exists a distribution of stoichiometric hydrates over hydration numbers. In terms of the theory of ideal associated solutions, the equations for activity coefficients, osmotic coefficients, vapor pressure, and excess thermodynamic functions (volume, Gibbs energy, enthalpy, entropy) are obtained in analytical form. Basic parameters in the equations are the hydration numbers of the nonelectrolyte (the mathematical expectation of the distribution of hydrates) and the dispersions of the distribution. It is concluded that the model equations adequately describe the thermodynamic properties of a wide range of nonelectrolytes partly or completely soluble in water.

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.

Thermal Plasma Synthesis of Crystalline Gallium Nitride Nanopowder from Gallium Nitrate Hydrate and Melamine

PubMed Central

Kim, Tae-Hee; Choi, Sooseok; Park, Dong-Wha

2016-01-01

Gallium nitride (GaN) nanopowder used as a blue fluorescent material was synthesized by using a direct current (DC) non-transferred arc plasma. Gallium nitrate hydrate (Ga(NO3)3∙xH2O) was used as a raw material and NH3 gas was used as a nitridation source. Additionally, melamine (C3H6N6) powder was injected into the plasma flame to prevent the oxidation of gallium to gallium oxide (Ga2O3). Argon thermal plasma was applied to synthesize GaN nanopowder. The synthesized GaN nanopowder by thermal plasma has low crystallinity and purity. It was improved to relatively high crystallinity and purity by annealing. The crystallinity is enhanced by the thermal treatment and the purity was increased by the elimination of residual C3H6N6. The combined process of thermal plasma and annealing was appropriate for synthesizing crystalline GaN nanopowder. The annealing process after the plasma synthesis of GaN nanopowder eliminated residual contamination and enhanced the crystallinity of GaN nanopowder. As a result, crystalline GaN nanopowder which has an average particle size of 30 nm was synthesized by the combination of thermal plasma treatment and annealing. PMID:28344295

The effect of gyrolite additive on the hydration properties of Portland cement

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

Eisinas, A., E-mail: anatolijus.eisinas@ktu.lt; Baltakys, K.; Siauciunas, R.

2012-01-15

The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C-S-H, with higher basicity (C/S {approx} 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stagemore » II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C{sub 3}S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.« less

Nitrate Leaching Management

USDA-ARS?s Scientific Manuscript database

Nitrate (NO3) leaching is a significant nitrogen (N) loss process for agriculture that must be managed to minimize NO3 enrichment of groundwater and surface waters. Managing NO3 leaching should involve the application of basic principles of understanding the site’s hydrologic cycle, avoiding excess ...

The efficiency of Amberjet 4200 resin in removing nitrate in the presence of competitive anions from Shiraz drinking water.

PubMed

Dehghani, M; Haghighi, A Binaee; Zamanian, Z

2010-06-01

The aim of this research is to study the feasibility of removing nitrates from water by means of anion exchange. In the purposed work an attempt was made to utilize strong basic anion resin to remove nitrate in the presence of competitive anion. Amberjet Cl- 4200 ion exchange resin was used in a batch scale. The fixation rate of nitrate without the presences of any competitive anion was almost constant (94.60-96.43) when the nitrate concentrations are in the range of 100-150 mg L(-1). The fixation rate of nitrate in the presences of two competitive anions (sulphate and chloride) was reduced to 82% when the concentration of nitrate was 100 mg L(-1).

Using Demonstrations Involving Combustion and Acid-Base Chemistry to Show Hydration of Carbon Dioxide, Sulfur Dioxide, and Magnesium Oxide and Their Relevance for Environmental Climate Science

ERIC Educational Resources Information Center

Shaw, C. Frank, III; Webb, James W.; Rothenberger, Otis

2016-01-01

The nature of acidic and basic (alkaline) oxides can be easily illustrated via a series of three straightforward classroom demonstrations for high school and general chemistry courses. Properties of carbon dioxide, sulfur dioxide, and magnesium oxide are revealed inexpensively and safely. Additionally, the very different kinetics of hydration of…

Identifying the morphologies of gas hydrate distribution using P-wave velocity and density: a test from the GMGS2 expedition in the South China Sea

NASA Astrophysics Data System (ADS)

Liu, Tao; Liu, Xuewei

2018-06-01

Pore-filling and fracture-filling are two basic distribution morphologies of gas hydrates in nature. A clear knowledge of gas hydrate morphology is important for better resource evaluation and exploitation. Improper exploitation may cause seafloor instability and exacerbate the greenhouse effect. To identify the gas hydrate morphologies in sediments, we made a thorough analysis of the characteristics of gas hydrate bearing sediments (GHBS) based on rock physics modeling. With the accumulation of gas hydrate in sediments, both the velocities of two types of GHBS increase, and their densities decrease. Therefore, these two morphologies cannot be differentiated only by velocity or density. After a series of tests, we found the attribute ρ {{V}{{P}}}0.5 as a function of hydrate concentration show opposite trends for these two morphologies due to their different formation mechanisms. The morphology of gas hydrate can thus be identified by comparing the measured ρ {{V}{{P}}}0.5 with its background value, which means the ρ {{V}{{P}}}0.5 of the hydrate-free sediments. In 2013, China’s second gas hydrate expedition was conducted by Guangzhou Marine Geologic Survey to explore gas hydrate resources in the northern South China Sea, and both two hydrate morphologies were recovered. We applied this method to three sites, which include two pore-filling and three fracture-filling hydrate layers. The data points, that agree with the actual situations, account for 72% and 82% of the total for the two pore-filling hydrate layers, respectively, and 86%, 74%, and 69% for the three fracture-filling hydrate layers, respectively.

Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system

NASA Astrophysics Data System (ADS)

Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten

2014-01-01

The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (<10-7 M) and forms a soft surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

[Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

PubMed

Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

2015-11-01

Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

Interactions of the "piano-stool" [ruthenium(II)(η(6) -arene)(quinolone)Cl](+) complexes with water; DFT computational study.

PubMed

Zábojníková, Tereza; Cajzl, Radim; Kljun, Jakob; Chval, Zdeněk; Turel, Iztok; Burda, Jaroslav V

2016-07-15

Full optimizations of stationary points along the reaction coordinate for the hydration of several quinolone Ru(II) half-sandwich complexes were performed in water environment using the B3PW91/6-31+G(d)/PCM/UAKS method. The role of diffuse functions (especially on oxygen) was found crucial for correct geometries along the reaction coordinate. Single-point (SP) calculations were performed at the B3LYP/6-311++G(2df,2pd)/DPCM/saled-UAKS level. In the first part, two possible reaction mechanisms-associative and dissociative were compared. It was found that the dissociative mechanism of the hydration process is kinetically slightly preferred. Another important conclusion concerns the reaction channels. It was found that substitution of chloride ligand (abbreviated in the text as dechlorination reaction) represents energetically and kinetically the most feasible pathway. In the second part the same hydration reaction was explored for reactivity comparison of the Ru(II)-complexes with several derivatives of nalidixic acid: cinoxacin, ofloxacin, and (thio)nalidixic acid. The hydration process is about four orders of magnitude faster in a basic solution compared to neutral/acidic environment with cinoxacin and nalidixic acid as the most reactive complexes in the former and latter environments, respectively. The explored hydration reaction is in all cases endergonic; nevertheless the endergonicity is substantially lower (by ∼6 kcal/mol) in basic environment. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

The inhibition of methane hydrate formation by water alignment underneath surface adsorption of surfactants

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

Nguyen, Ngoc N.; Nguyen, Anh V.; Dang, Liem X.

Sodium dodecyl sulfate (SDS) has been widely shown to strongly promote the formation of methane hydrate. Here we show that SDS displays an extraordinary inhibition effect on methane hydrate formation when the surfactant is used in sub-millimolar concentration (around 0.3 mM). We have also employed Sum Frequency Generation vibrational spectroscopy (SFG) and molecular dynamics simulation (MDS) to elucidate the molecular mechanism of this inhibition. The SFG and MDS results revealed a strong alignment of water molecules underneath surface adsorption of SDS in its sub-millimolar solution. Interestingly, both the alignment of water and the inhibition effect (in 0.3 mM SDS solution)more » went vanishing when an oppositely-charged surfactant (tetra-n-butylammonium bromide, TBAB) was suitably added to produce a mixed solution of 0.3 mM SDS and 3.6 mM TBAB. Combining structural and kinetic results, we pointed out that the alignment of water underneath surface adsorption of dodecyl sulfate (DS-) anions gave rise to the unexpected inhibition of methane hydration formation in sub-millimolar solution of SDS. The adoption of TBAB mitigated the SDS-induced electrostatic field at the solution’s surface and, therefore, weakened the alignment of interfacial water which, in turn, erased the inhibition effect. We discussed this finding using the concept of activation energy of the interfacial formation of gas hydrate. The main finding of this work is to reveal the interplay of interfacial water in governing gas hydrate formation which sheds light on a universal molecular-scale understanding of the influence of surfactants on gas hydrate formation. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Simultaneous Thermal Analysis of WIPP and LANL Waste Drum Samples: A Preliminary Report

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

Wayne, David M.

2015-10-19

On Friday, February 14, 2014, an incident in P7R7 of the WIPP underground repository released radioactive material into the environment. The direct cause of the event was a breached transuranic (TRU) waste container, subsequently identified as Drum 68660. Photographic and other evidence indicates that the breach of 68660 was caused by an exothermic event. Subsequent investigations (Britt, 2015; Clark and Funk, 2015; Wilson et al., 2015; Clark, 2015) indicate that the combination of nitrate salts, pH neutralizing chemicals, and organic-based adsorbent represented a potentially energetic mixture. The materials inside the breached steel drum consisted of remediated, 30- to 40-year old,more » Pu processing wastes from LANL. The contents were processed and repackaged in 2014. Processing activities at LANL included: 1) neutralization of acidic liquid contents, 2) sorption of the neutralized liquid, and 3) mixing of acidic nitrate salts with an absorber to meet waste acceptance criteria. The contents of 68660 and its sibling, 68685, were derived from the same parent drum, S855793. Drum S855793 originally contained ten plastic bags of acidic nitrate salts, and four bags of mixed nitrate and oxalate salts generated in 1985 by Pu recovery operations. These salts were predominantly oxalic acid, hydrated nitrate salts of Mg, Ca, and Fe, anhydrous Na(NO 3), and minor amounts of anhydrous and hydrous nitrate salts of Pb, Al, K, Cr, and Ni. Other major components include sorbed water, nitric acid, dissolved nitrates, an absorbent (Swheat Scoop®) and a neutralizer (KolorSafe®). The contents of 68660 are described in greater detail in Appendix E of Wilson et al. (2015)« less

Tetrafluoroethane (R134a) hydrate formation within variable volume reactor accompanied by evaporation and condensation.

PubMed

Jeong, K; Choo, Y S; Hong, H J; Yoon, Y S; Song, M H

2015-03-01

Vast size hydrate formation reactors with fast conversion rate are required for the economic implementation of seawater desalination utilizing gas hydrate technology. The commercial target production rate is order of thousand tons of potable water per day per train. Various heat and mass transfer enhancement schemes including agitation, spraying, and bubbling have been examined to maximize the production capacities in scaled up design of hydrate formation reactors. The present experimental study focused on acquiring basic knowledge needed to design variable volume reactors to produce tetrafluoroethane hydrate slurry. Test vessel was composed of main cavity with fixed volume of 140 ml and auxiliary cavity with variable volume of 0 ∼ 64 ml. Temperatures at multiple locations within vessel and pressure were monitored while visual access was made through front window. Alternating evaporation and condensation induced by cyclic volume change provided agitation due to density differences among water and vapor, liquid and hydrate R134a as well as extended interface area, which improved hydrate formation kinetics coupled with latent heat release and absorption. Influences of coolant temperature, piston stroke/speed, and volume change period on hydrate formation kinetics were investigated. Suggestions of reactor design improvement for future experimental study are also made.

Acoustic Velocity Log Numerical Simulation and Saturation Estimation of Gas Hydrate Reservoir in Shenhu Area, South China Sea

PubMed Central

Xiao, Kun; Zou, Changchun; Xiang, Biao; Liu, Jieqiong

2013-01-01

Gas hydrate model and free gas model are established, and two-phase theory (TPT) for numerical simulation of elastic wave velocity is adopted to investigate the unconsolidated deep-water sedimentary strata in Shenhu area, South China Sea. The relationships between compression wave (P wave) velocity and gas hydrate saturation, free gas saturation, and sediment porosity at site SH2 are studied, respectively, and gas hydrate saturation of research area is estimated by gas hydrate model. In depth of 50 to 245 m below seafloor (mbsf), as sediment porosity decreases, P wave velocity increases gradually; as gas hydrate saturation increases, P wave velocity increases gradually; as free gas saturation increases, P wave velocity decreases. This rule is almost consistent with the previous research result. In depth of 195 to 220 mbsf, the actual measurement of P wave velocity increases significantly relative to the P wave velocity of saturated water modeling, and this layer is determined to be rich in gas hydrate. The average value of gas hydrate saturation estimated from the TPT model is 23.2%, and the maximum saturation is 31.5%, which is basically in accordance with simplified three-phase equation (STPE), effective medium theory (EMT), resistivity log (Rt), and chloride anomaly method. PMID:23935407

Tetrafluoroethane (R134a) hydrate formation within variable volume reactor accompanied by evaporation and condensation

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

Jeong, K.; Choo, Y. S.; Hong, H. J.

Vast size hydrate formation reactors with fast conversion rate are required for the economic implementation of seawater desalination utilizing gas hydrate technology. The commercial target production rate is order of thousand tons of potable water per day per train. Various heat and mass transfer enhancement schemes including agitation, spraying, and bubbling have been examined to maximize the production capacities in scaled up design of hydrate formation reactors. The present experimental study focused on acquiring basic knowledge needed to design variable volume reactors to produce tetrafluoroethane hydrate slurry. Test vessel was composed of main cavity with fixed volume of 140 mlmore » and auxiliary cavity with variable volume of 0 ∼ 64 ml. Temperatures at multiple locations within vessel and pressure were monitored while visual access was made through front window. Alternating evaporation and condensation induced by cyclic volume change provided agitation due to density differences among water and vapor, liquid and hydrate R134a as well as extended interface area, which improved hydrate formation kinetics coupled with latent heat release and absorption. Influences of coolant temperature, piston stroke/speed, and volume change period on hydrate formation kinetics were investigated. Suggestions of reactor design improvement for future experimental study are also made.« less

Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

PubMed

Park, Taehyung; Kyung, Daeseung; Lee, Woojin

2014-06-17

In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

Hydration: certain basic aspects for developing technical and scientific parameters into the nutrition knowledge

PubMed

Perales-García, Aránzazu; Estévez-Martínez, Isabel; Urrialde, Rafael

2016-07-12

Introduction: Hydration is defined as the water intake coming from food and beverages. Its study has become an area by itself, within the nutrition field. Meaning that in 2010 the European Food Safety Authority (EFSA) approved the water intake recommendations, but the study of this topic implies a rigorous methodology, which represents several issues. Objective: Showing as a glance the main methodological issues in hydration studies. Material and methods: Bibliographic revision of scientific literature. Results: The main methodological issues presented are: sample selection (investigation field and sample design), selection of the method to evaluate hydration status (dilution techniques, bioelectrical impedance, plasmatic and urinary indicators, changes in body composition, water losses and clinic symptoms) selection of the method to evaluate water intake (biomarker, questionnaires, informatics programs, smartphone use, 24-h register, dietary history and food frequency questionnaire), and the main sources of hydration. Conclusions: Hydration status should be understood as a routine model, with daily frequency, according to gender, age, physical activity and environmental conditions. Furthermore, the correct design of the methodology has a special importance in order to take into account all the aspects

Seismic reflections identify finite differences in gas hydrate resources

USGS Publications Warehouse

Dillon, William P.; Max, M.

1999-01-01

Gas hydrate is a gas-bearing, ice-like crystalline solid. The substance's build ing blocks consist of a gas molecule (generally methane) sur-rounded by a cage of water molecules. The total amount of methane in hydrate in the world is immense - the most recent speculative estimate centers on values of 21x1015 cu meters. Thus, it may represent a future energy resource. This estimate was presented by Keith Kvenvolden at the International Symposium on Methane Hydrates, Resources in the Near Future, sponsor ed by Japanese National Oil Company (Tokyo, October, 1998).But, as with any natural resource, there is a need to find naturally occurring concentrations in order to effectively extract gas. We need to answer four basic questions:Do methane hydrate concentrations suitable for methane extraction exist?How can we recognize these concentrations?Where are concentrations located?What processes control methane hydrate concentrations?Gas hydrate occurs naturally at the pressure/ temperature/chemical conditions that are present within ocean floor sediments at water depths greater than about 500 meters. The gas hydrate stability zone (GHSZ) extends from the sea bottom downward to a depth where the natural increase in temperature causes the hydrate to melt (dissociate), even though the downward pressure increase is working to increase gas hydrate stability.Thus, the base of the GHSZ tends to parallel the seafloor at any given water depth (pressure), because the sub-seafloor isotherms (depths of constant temperature) generally parallel the seafloor. The layer at which gas hydrate is stable commonly extends from the sea floor to several hundred meters below it. The gas in most gas hydrates is methane, generated by bacteria in the sediments. In some cases, it can be higher carbon-number, thermogenic hydrocarbon gases that rise from greater depths.

The Dependence of Water Permeability in Quartz Sand on Gas Hydrate Saturation in the Pore Space

NASA Astrophysics Data System (ADS)

Kossel, E.; Deusner, C.; Bigalke, N.; Haeckel, M.

2018-02-01

Transport of fluids in gas hydrate bearing sediments is largely defined by the reduction of the permeability due to gas hydrate crystals in the pore space. Although the exact knowledge of the permeability behavior as a function of gas hydrate saturation is of crucial importance, state-of-the-art simulation codes for gas production scenarios use theoretically derived permeability equations that are hardly backed by experimental data. The reason for the insufficient validation of the model equations is the difficulty to create gas hydrate bearing sediments that have undergone formation mechanisms equivalent to the natural process and that have well-defined gas hydrate saturations. We formed methane hydrates in quartz sand from a methane-saturated aqueous solution and used magnetic resonance imaging to obtain time-resolved, three-dimensional maps of the gas hydrate saturation distribution. These maps were fed into 3-D finite element method simulations of the water flow. In our simulations, we tested the five most well-known permeability equations. All of the suitable permeability equations include the term (1-SH)n, where SH is the gas hydrate saturation and n is a parameter that needs to be constrained. The most basic equation describing the permeability behavior of water flow through gas hydrate bearing sand is k = k0 (1-SH)n. In our experiments, n was determined to be 11.4 (±0.3). Results from this study can be directly applied to bulk flow analysis under the assumption of homogeneous gas hydrate saturation and can be further used to derive effective permeability models for heterogeneous gas hydrate distributions at different scales.

A concentrated electrolyte for zinc hexacyanoferrate electrodes in aqueous rechargeable zinc-ion batteries

NASA Astrophysics Data System (ADS)

Kim, D.; Lee, C.; Jeong, S.

2018-01-01

In this study, a concentrated electrolyte was applied in an aqueous rechargeable zinc-ion battery system with a zinc hexacyanoferrate (ZnHCF) electrode to improve the electrochemical performance by changing the hydration number of the zinc ions. To optimize the active material, ZnHCF was synthesized using aqueous solutions of zinc nitrate with three different concentrations. The synthesized materials exhibited some differences in structure, crystallinity, and particle size, as observed by X-ray diffraction and scanning electron microscopy. Subsequently, these well-structured materials were applied in electrochemical tests. A more than two-fold improvement in the charge/discharge capacities was observed when the concentrated electrolyte was used instead of the dilute electrolyte. Additionally, the cycling performance observed in the concentrated electrolyte was superior to that in the dilute electrolyte. This improvement in the electrochemical performance may result from a decrease in the hydration number of the zinc ions in the concentrated electrolyte.

Resolution V fractional factorial design for screening of factors affecting weakly basic drugs liposomal systems.

PubMed

Nageeb El-Helaly, Sara; Habib, Basant A; Abd El-Rahman, Mohamed K

2018-07-01

This study aims to investigate factors affecting weakly basic drugs liposomal systems. Resolution V fractional factorial design (2 V 5-1 ) is used as an example of screening designs that would better be used as a wise step before proceeding with detailed factors effects or optimization studies. Five factors probable to affect liposomal systems of weakly basic drugs were investigated using Amisulpride as a model drug. Factors studied were; A: Preparation technique B: Phosphatidyl choline (PhC) amount (mg) C: Cholesterol: PhC molar ratio, D: Hydration volume (ml) and E: Sonication type. Levels investigated were; Ammonium sulphate-pH gradient technique or Transmembrane zinc chelation-pH gradient technique, 200 or 400 mg, 0 or 0.5, 10 or 20 ml and bath or probe sonication for A, B, C, D and E respectively. Responses measured were Particle size (PS) (nm), Zeta potential (ZP) (mV) and Entrapment efficiency percent (EE%). Ion selective electrode was used as a novel method for measuring unentrapped drug concentration and calculating entrapment efficiency without the need for liposomal separation. Factors mainly affecting the studied responses were Cholesterol: PhC ratio and hydration volume for PS, preparation technique for ZP and preparation technique and hydration volume for EE%. The applied 2 V 5-1 design enabled the use of only 16 trial combinations for screening the influence of five factors on weakly basic drugs liposomal systems. This clarifies the value of the use of screening experiments before extensive investigation of certain factors in detailed optimization studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis and Design of a Photonic Biosensor for Mild Traumatic Brain Injury

DTIC Science & Technology

2013-03-01

well developed. The basic process involves hydration of dry lipid, cholesterol, protein, or other component of the lipid membrane onto a vessel...surface from organic solvent (e.g., chloroform), thereby producing a thin film of dry lipid. This material is then hydrated to solution typically in an...such as by reaction with a polystyrene plate . A nucleic acid molecule may be aminated to promote binding to a polystyrene section of a housing via the

NO2 disproportionation for the IR characterisation of basic zeolites.

PubMed

Marie, Olivier; Malicki, Nicolas; Pommier, Catherine; Massiani, Pascale; Vos, Ann; Schoonheydt, Robert; Geerlings, Paul; Henriques, Carlos; Thibault-Starzyk, Fréderic

2005-02-28

NO2 disproportionation on alkaline zeolites is used to generate nitrosonium (NO+) and nitrate ions on the surface, and the infrared vibrations observed are very sensitive to the cation chemical hardness and to the basicity of zeolitic oxygen atoms.

A new estimate of the volume and distribution of gas hydrate in the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Majumdar, U.; Cook, A.

2016-12-01

In spite of the wealth of information gained over the last several decades about gas hydrate in the northern Gulf of Mexico, there is still considerable uncertainty about the distribution and volume of gas hydrate. In our assessment we build a dataset of basin-wide gas hydrate distribution and thickness, as appraised from publicly available petroleum industry well logs within the gas hydrate stability zone (HSZ), and subsequently develop a Monte Carlo to determine the volumetric estimate of gas hydrate using the dataset. We evaluate the presence of gas hydrate from electrical resistivity well logs, and categorized possible reservoir type (either sand or clay) based on the gamma ray response and resistivity curve characteristics. Out of the 798 wells with resistivity well log data within the HSZ we analyzed, we found evidence of gas hydrate in 124 wells. In this research we present a new stochastic estimate of the gas hydrate volume in the northern Gulf of Mexico guided by our well log dataset. For our Monte Carlo simulation, we divided our assessment area of 200,000 km2 into 1 km2 grid cells. Our volume assessment model incorporates variables unique to our well log dataset such as the likelihood of gas hydrate occurrence, fraction of the HSZ occupied by gas hydrate, reservoir type, and gas hydrate saturation depending on the reservoir, in each grid cell, in addition to other basic variables such as HSZ thickness and porosity. Preliminary results from our model suggests that the total volume of gas at standard temperature and pressure in gas hydrate in the northern Gulf of Mexico is in the range of 430 trillion cubic feet (TCF) to 730 TCF, with a mean volume of 585 TCF. While the reservoir distribution from our well log dataset found gas hydrate in sand reservoirs in 30 wells out of the 124 wells with evidence of gas hydrate ( 24%), we find sand reservoirs contain over half of the total volume of gas hydrate in the Gulf of Mexico, as a result of the relatively high gas hydrate saturation in sand.

A Copper-Sulfate-Based Inorganic Chemistry Laboratory for First-Year University Students That Teaches Basic Operations and Concepts.

ERIC Educational Resources Information Center

Rodriguez, Emilio; Vicente, Miguel Angel

2002-01-01

Presents a 10-hour chemistry experiment using copper sulfate that has three steps: (1) purification of an ore containing copper sulfate and insoluble basic copper sulfates; (2) determination of the number of water molecules in hydrated copper sulfate; and (3) recovery of metallic copper from copper sulfate. (Author/YDS)

METHOD OF SEPARATING PLUTONIUM

DOEpatents

Heal, H.G.

1960-02-16

BS>A method of separating plutonium from aqueous nitrate solutions of plutonium, uranium. and high beta activity fission products is given. The pH of the aqueous solution is adjusted between 3.0 to 6.0 with ammonium acetate, ferric nitrate is added, and the solution is heated to 80 to 100 deg C to selectively form a basic ferric plutonium-carrying precipitate.

Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

NASA Astrophysics Data System (ADS)

Park, T.; Kyung, D.; Lee, W.

2013-12-01

Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

Factors influencing protein tyrosine nitration – structure-based predictive models

PubMed Central

Bayden, Alexander S.; Yakovlev, Vasily A.; Graves, Paul R.; Mikkelsen, Ross B.; Kellogg, Glen E.

2010-01-01

Models for exploring tyrosine nitration in proteins have been created based on 3D structural features of 20 proteins for which high resolution X-ray crystallographic or NMR data are available and for which nitration of 35 total tyrosines has been experimentally proven under oxidative stress. Factors suggested in previous work to enhance nitration were examined with quantitative structural descriptors. The role of neighboring acidic and basic residues is complex: for the majority of tyrosines that are nitrated the distance to the heteroatom of the closest charged sidechain corresponds to the distance needed for suspected nitrating species to form hydrogen bond bridges between the tyrosine and that charged amino acid. This suggests that such bridges play a very important role in tyrosine nitration. Nitration is generally hindered for tyrosines that are buried and for those tyrosines where there is insufficient space for the nitro group. For in vitro nitration, closed environments with nearby heteroatoms or unsaturated centers that can stabilize radicals are somewhat favored. Four quantitative structure-based models, depending on the conditions of nitration, have been developed for predicting site-specific tyrosine nitration. The best model, relevant for both in vitro and in vivo cases predicts 30 of 35 tyrosine nitrations (positive predictive value) and has a sensitivity of 60/71 (11 false positives). PMID:21172423

Nitrate-based niche differentiation by distinct sulfate-reducing bacteria involved in the anaerobic oxidation of methane

PubMed Central

Green-Saxena, A; Dekas, A E; Dalleska, N F; Orphan, V J

2014-01-01

Diverse associations between methanotrophic archaea (ANME) and sulfate-reducing bacterial groups (SRB) often co-occur in marine methane seeps; however, the ecophysiology of these different symbiotic associations has not been examined. Here, we applied a combination of molecular, geochemical and Fluorescence in situ hybridization (FISH) coupled to nanoscale secondary ion mass spectrometry (FISH-NanoSIMS) analyses of in situ seep sediments and methane-amended sediment incubations from diverse locations (Eel River Basin, Hydrate Ridge and Costa Rican Margin seeps) to investigate the distribution and physiology of a newly identified subgroup of the Desulfobulbaceae (seepDBB) found in consortia with ANME-2c archaea, and compared these with the more commonly observed associations between the same ANME partner and the Desulfobacteraceae (DSS). FISH analyses revealed aggregates of seepDBB cells in association with ANME-2 from both environmental samples and laboratory incubations that are distinct in their structure relative to co-occurring ANME/DSS consortia. ANME/seepDBB aggregates were most abundant in shallow sediment depths below sulfide-oxidizing microbial mats. Depth profiles of ANME/seepDBB aggregate abundance revealed a positive correlation with elevated porewater nitrate relative to ANME/DSS aggregates in all seep sites examined. This relationship with nitrate was supported by sediment microcosm experiments, in which the abundance of ANME/seepDBB was greater in nitrate-amended incubations relative to the unamended control. FISH-NanoSIMS additionally revealed significantly higher 15N-nitrate incorporation levels in individual aggregates of ANME/seepDBB relative to ANME/DSS aggregates from the same incubation. These combined results suggest that nitrate is a geochemical effector of ANME/seepDBB aggregate distribution, and provides a unique niche for these consortia through their utilization of a greater range of nitrogen substrates than the ANME/DSS. PMID:24008326

A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

USGS Publications Warehouse

Sigman, D.M.; Casciotti, K.L.; Andreani, M.; Barford, C.; Galanter, M.; Böhlke, J.K.

2001-01-01

We report a new method for measurement of the isotopic composition of nitrate (NO3-) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N2O) generated from nitrate by denitrifying bacteria that lack N2O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

Perchlorate-Coupled Carbon Monoxide (CO) Oxidation: Evidence for a Plausible Microbe-Mediated Reaction in Martian Brines.

PubMed

Myers, Marisa R; King, Gary M

2017-01-01

The presence of hydrated salts on Mars indicates that some regions of its surface might be habitable if suitable metabolizable substrates are available. However, several lines of evidence have shown that Mars' regolith contains only trace levels of the organic matter needed to support heterotrophic microbes. Due to the scarcity of organic carbon, carbon monoxide (CO) at a concentration of about 700 parts per million (about 0.4 Pa) might be the single most abundant readily available substrate that could support near-surface bacterial activity. Although a variety of electron acceptors can be coupled to CO oxidation, perchlorate is likely the most abundant potential oxidant in Mars' brines. Whether perchlorate, a potent chaotrope, can support microbial CO oxidation has not been previously documented. We report here the first evidence for perchlorate-coupled CO oxidation based on assays with two distinct euryarchaeal extreme halophiles. CO oxidation occurred readily in 3.8 M NaCl brines with perchlorate concentrations from 0.01 to 1 M. Both isolates were able to couple CO with perchlorate or chlorate under anaerobic conditions with or without nitrate as an inducer for nitrate reductase, which serves as a perchlorate reductase in extreme halophiles. In the presence of perchlorate, CO concentrations were reduced to levels well below those found in Mars' atmosphere. This indicates that CO could contribute to the survival of microbial populations in hydrated salt formations or brines if water activities are suitably permissive.

X-Ray diffraction, spectroscopy and thermochemical characterization of the pharmaceutical paroxetine nitrate salt

NASA Astrophysics Data System (ADS)

Carvalho, Paulo S.; de Melo, Cristiane C.; Ayala, Alejandro P.; Ellena, Javier

2016-08-01

A comprehensive solid state study of Paroxetine nitrate hydrate, (PRX+·NO3-)H2O, is reported. This salt was characterized by a combination of methods, including Single crystal X-ray diffraction, Thermal analysis, Fourier transform infrared spectroscopy (FTIR) and Solubility measurements. (PRX+·NO3-)H2O crystallizes in the monoclinic C2 space group (Z‧ = 1) and its packing was analyzed in details, showing that the main supramolecular motif consists in a C22(4) chain formed by charge-assisted N+-H⋯O- hydrogen bonds. The salt formation and conformation features were also accuracy established via FTIR spectra. In comparison with the pharmaceutical approved (PRX+ṡCl-)ṡ0.5H2O, (PRX+ṡNO3-)ṡH2O showed a decrease of 24 °C in the drug melting peak and a slight reduction in its water solubility value.

PREPARATION OF DIBASIC ALUMINUM NITRATE

DOEpatents

Gresky, A.T.; Nurmi, E.O.; Foster, D.L.; Wischow, R.P.; Savolainen, J.E.

1960-04-01

A method is given for the preparation and recovery of basic aluminum nltrates having an OH: Al ratio of at least two, comprising two steps. First, metallic aluminum is dissolved in aqueous Al(NO/sub 3/)/sub 3/, in the presence of a small quantity of elemental or ionic mercury, to increase its Al: NO/sub 3/ ratio into the range 1 to 1.2. The resulting aqueous solution is then added to an excess of a special organic solvent, typically a mixture of five parts methanol and six parts diethyl ether, whereupon the basic aluminum nitrate, e.g. Al/sub 6/(OH)/sub 13/-(NO/sub 3/)/sub 5/, recoverably precipitates.

Lignin Depolymerization with Nitrate-Intercalated Hydrotalcite Catalysts

DOE PAGES

Kruger, Jacob S.; Cleveland, Nicholas S.; Zhang, Shuting; ...

2016-01-13

Hydrotalcites (HTCs) exhibit multiple adjustable parameters to tune catalytic activity, including interlayer anion composition, metal hydroxide layer composition, and catalyst preparation methods. Here in this paper, we report the influence of several of these parameters on β-O-4 bond scission in a lignin model dimer, 2-phenoxy-1-phenethanol (PE), to yield phenol and acetophenone. We find that the presence of both basic and NO 3– anions in the interlayer increases the catalyst activity by 2–3-fold. In contrast, other anions or transition metals do not enhance catalytic activity in comparison to blank HTC. The catalyst is not active for C–C bond cleavage on ligninmore » model dimers and has no effect on dimers without an α-OH group. Most importantly, the catalyst is highly active in the depolymerization of two process-relevant lignin substrates, producing a significant amount of low-molecular-weight aromatic species. The catalyst can be recycled until the NO 3– anions are depleted, after which the activity can be restored by replenishing the NO 3– reservoir and regenerating the hydrated HTC structure. These results demonstrate a route to selective lignin depolymerization in a heterogeneous system with an inexpensive, earth-abundant, commercially relevant, and easily regenerated catalyst.« less

Basic Research Plan, February 2003

DTIC Science & Technology

2003-02-01

consistent. This effort includes the nitration , crystallization, and coating of CL–20. Under Army sponsor- ship, a process for the nitration of CL–20 has...actuators • Multiscale computational design of structural materials with embedded functionality • Materials with embedded electrical/magnetic/optical...the innovative use of biology to produce unique materials and processes of mili- tary relevance; to increase economic and environmental affordability

Factors influencing protein tyrosine nitration--structure-based predictive models.

PubMed

Bayden, Alexander S; Yakovlev, Vasily A; Graves, Paul R; Mikkelsen, Ross B; Kellogg, Glen E

2011-03-15

Models for exploring tyrosine nitration in proteins have been created based on 3D structural features of 20 proteins for which high-resolution X-ray crystallographic or NMR data are available and for which nitration of 35 total tyrosines has been experimentally proven under oxidative stress. Factors suggested in previous work to enhance nitration were examined with quantitative structural descriptors. The role of neighboring acidic and basic residues is complex: for the majority of tyrosines that are nitrated the distance to the heteroatom of the closest charged side chain corresponds to the distance needed for suspected nitrating species to form hydrogen bond bridges between the tyrosine and that charged amino acid. This suggests that such bridges play a very important role in tyrosine nitration. Nitration is generally hindered for tyrosines that are buried and for those tyrosines for which there is insufficient space for the nitro group. For in vitro nitration, closed environments with nearby heteroatoms or unsaturated centers that can stabilize radicals are somewhat favored. Four quantitative structure-based models, depending on the conditions of nitration, have been developed for predicting site-specific tyrosine nitration. The best model, relevant for both in vitro and in vivo cases, predicts 30 of 35 tyrosine nitrations (positive predictive value) and has a sensitivity of 60/71 (11 false positives). Copyright © 2010 Elsevier Inc. All rights reserved.

Hydration dynamics promote bacterial coexistence on rough surfaces

PubMed Central

Wang, Gang; Or, Dani

2013-01-01

Identification of mechanisms that promote and maintain the immense microbial diversity found in soil is a central challenge for contemporary microbial ecology. Quantitative tools for systematic integration of complex biophysical and trophic processes at spatial scales, relevant for individual cell interactions, are essential for making progress. We report a modeling study of competing bacterial populations cohabiting soil surfaces subjected to highly dynamic hydration conditions. The model explicitly tracks growth, motion and life histories of individual bacterial cells on surfaces spanning dynamic aqueous networks that shape heterogeneous nutrient fields. The range of hydration conditions that confer physical advantages for rapidly growing species and support competitive exclusion is surprisingly narrow. The rapid fragmentation of soil aqueous phase under most natural conditions suppresses bacterial growth and cell dispersion, thereby balancing conditions experienced by competing populations with diverse physiological traits. In addition, hydration fluctuations intensify localized interactions that promote coexistence through disproportional effects within densely populated regions during dry periods. Consequently, bacterial population dynamics is affected well beyond responses predicted from equivalent and uniform hydration conditions. New insights on hydration dynamics could be considered in future designs of soil bioremediation activities, affect longevity of dry food products, and advance basic understanding of bacterial diversity dynamics and its role in global biogeochemical cycles. PMID:23051694

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.

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

PubMed Central

Barendt, Timothy A.; Docker, Andrew; Marques, Igor; Félix, Vítor

2016-01-01

Abstract The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1H NMR anion binding results. PMID:27436297

Effect of heavy metals and water content on the strength of magnesium phosphate cements.

PubMed

Buj, Irene; Torras, Josep; Casellas, Daniel; Rovira, Miquel; de Pablo, Joan

2009-10-15

In this paper the mechanical properties of magnesium potassium phosphate cements used for the Stabilization/Solidification (S/S) of galvanic wastes were investigated. Surrogate wastes (metal nitrate dissolutions) were employed containing Cd, Cr(III), Cu, Ni, Pb or Zn at a concentration of 25 g dm(-3) and different water-to-solid (W/S) ratios (0.3, 0.4, 0.5 and 0.6 dm(3)kg(-1)) have been employed. Cements were prepared by mixing hard burned magnesia of about 70% purity with potassium dihydrogen phosphate. Compressive strength and tensile strength of specimens were determined. In addition the volume of permeable voids was measured. It was found that when comparing pastes that the volume of permeable voids increases and mechanical strength decreases with the increase of water-to-solid ratio (W/S). Nevertheless pastes with the same material proportions containing different metals show different mechanical strength values. The hydration products were analyzed by XRD. With the increase of water content not previously reported hydration compound was detected: bobierrite.

Two basic bismuth nitrates: [Bi6O6(OH)2](NO3)4 · 2H2O with superior photodegradation activity for rhodamine B and [Bi6O5(OH)3](NO3)5 · 3H2O with ultrahigh adsorption capacity for methyl orange

NASA Astrophysics Data System (ADS)

Pang, Jiawei; Han, Qiaofeng; Liu, Weiqi; Shen, Zichen; Wang, Xin; Zhu, Junwu

2017-11-01

A novel basic bismuth nitrate, [Bi6O6(OH)2](NO3)4·2H2O (denoted as BiON-4N), was easily obtained at room temperature in the existence of 2-methoxyethanol (CH3OCH2CH2OH; 2ME) with a pH value ranging from 4.5 to 7.0. The morphology of BiON-4N could be easily tailored by changing the variety and amount of bases like urea, hexamethylenetetramine (HMTA), NaOH and NH3·H2O. When the solution pH was decreased lower than 4.5, another basic bismuth nitrate, [Bi6O5(OH)3](NO3)5·3H2O (denoted as BiON-5N), could be synthesized. Among those, BiON-4N nanoparticles obtained with 40 mmol of HMTA exhibited superior photocatalytic activity for rhodamine B (RhB) degradation with an efficiency of 100% within 4 min of UV light irradiation, which was much higher than that of commercial TiO2 (P25). The excellent photocatalytic performance of BiON-4N was mainly attributed to higher surface area (13.1 m2 g-1) in comparison with other basic bismuth nitrates. Furthermore, the as-prepared BiON-5N revealed excellent adsorption performance for the anions like methyl orange (MO) and K2Cr2O7, and especially for MO, the maximum adsorption capacity arrived up to 730 mg g-1, which should be relevant to highly positively charged surface. This work provides a new strategy for developing bismuth-based nanomaterials in the big bismuth family as potential photocatalyst and adsorbent for the removal of dyes and contaminants.

Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

PubMed Central

Paschalidis, Damianos G.; Harrison, William T. A.

2016-01-01

The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

Generation of highly stable and active strong base sites on organized nano-porous alumina by calcium oxide

NASA Astrophysics Data System (ADS)

Tarlani, Aliakbar; Zarabadi, Mir Pouyan

2013-02-01

In a new approach, strong basic sites has been successfully prepared by loading of calcium nitrate (Ca) on organized nano-porous alumina (ONPA). The prepared CaONPAs were characterized by low-angle X-ray diffraction (XRD), N2 adsorption-desorption isotherms (Brunauer-Emmett-Teller (BET)-Barret-Joyner-Halenda (BJH)), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Measuring of the amount of the basic sites and the basicity was carried out by titration method, temperature-programmed desorption (TPD-CO2) and Hammett indicators. Resistance of the basic sites was also tested by washing with water. N2 sorption measurements showed that supporting of the calcium nitrate on ONPA can lead to the bimodal porosity at lower loading. BET surface area of the bare ONPA was 212 m2/g which decreased to 111 m2/g for the 25% of loading of Ca (25CaONPA). The results pointed out that CaONPA samples have basicity between 18.4 < H_ < 22 for 15 and 25% of loadings and well-preserved of the basicity after washing with water especially for 5 and 15% samples. Also no crystalline phase of CaO was observed for 25CaONPA which was calcined at 600 °C.

From hydration repulsion to dry adhesion between asymmetric hydrophilic and hydrophobic surfaces

PubMed Central

Kanduč, Matej; Netz, Roland R.

2015-01-01

Using all-atom molecular dynamics (MD) simulations at constant water chemical potential in combination with basic theoretical arguments, we study hydration-induced interactions between two overall charge-neutral yet polar planar surfaces with different wetting properties. Whether the water film between the two surfaces becomes unstable below a threshold separation and cavitation gives rise to long-range attraction, depends on the sum of the two individual surface contact angles. Consequently, cavitation-induced attraction also occurs for a mildly hydrophilic surface interacting with a very hydrophobic surface. If both surfaces are very hydrophilic, hydration repulsion dominates at small separations and direct attractive force contribution can—if strong enough—give rise to wet adhesion in this case. In between the regimes of cavitation-induced attraction and hydration repulsion we find a narrow range of contact angle combinations where the surfaces adhere at contact in the absence of cavitation. This dry adhesion regime is driven by direct surface–surface interactions. We derive simple laws for the cavitation transition as well as for the transition between hydration repulsion and dry adhesion, which favorably compare with simulation results in a generic adhesion state diagram as a function of the two surface contact angles. PMID:26392526

Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study.

PubMed

Sato, Ryuhei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

2017-08-02

Hydration reactions on a carbonate-terminated cubic ZrO 2 (110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H 2 O molecules (Zr-OH 2 ) and monodentate hydroxyl groups (Zr-OH - ). Similar to a carbonate-free hydrated surface, Zr-OH 2 , Zr-OH - , and polydentate hydroxyl groups ([double bond splayed left]OH + ) were observed, while the ratio of acidic Zr-OH 2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO 2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr-OH 2 is not affected. As a result, protons released from [double bond splayed left]OH + react with Zr-OH - to form Zr-OH 2 , leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals

NASA Technical Reports Server (NTRS)

Clark, B. C.; Kenley, S. L.; Obrien, D. L.; Huss, G. R.; Mack, R.; Baird, A. K.

1979-01-01

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

Crystal structure of bis[bis(4-azaniumylphenyl) sulfone] tetranitrate monohydrate

PubMed Central

Benahsene, Amani Hind; Bendjeddou, Lamia; Merazig, Hocine

2017-01-01

In the title compound, the hydrated tetra­(nitrate) salt of dapsone (4,4′-di­amino­diphenyl­sulfone), 2C12H14N2O2S2+·4NO3 −·H2O {alternative name: bis[bis­(4,4′-di­aza­niumylphen­yl) sulfone] tetra­nitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18) and 69.69 (19)°. In the crystal, mixed cation–anion–water mol­ecule layers lying parallel to the (001) plane are formed through N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding inter­actions and these layers are further extended into an overall three-dimensional supra­molecular network structure. Inter-ring π–π inter­actions are also present [minimum ring centroid separation = 3.693 (3) Å]. PMID:29152359

Experimental Study of Goaf Filling Materials Based on Red Mud

NASA Astrophysics Data System (ADS)

Mu, Mangen; Gao, Xiaozhen; Guo, Taoming; Hu, Xinping

2018-01-01

Red mud as soild waste is difficult to treatment. Goaf filling materials can make a large use of red mud. By the experimental study,we find that the red mud, fly ash, ground slag and desulfida-tion gypsum can be used to make goaf filling materials based on the principle of alkali excitation and metalion stability.Through the control variable method, we find that the optimal proportion of goaf filling materials based on red mud is red mud 55%, fly ash 30%, cement 7.5%, fly ash 2.5%, desulfurization gypsum 5%, admixture 1%, and water solid ratio=1:1.2.The 28days final material strength was 2.0 MPa,which achives the technical specification requirements.Through the test of SEM, XRD and IR, it is indicated that the strength formation of goaf filling material based on red mud is from the unformed linking hydration products of amorphous alkali excitation system. With curing time from 3 to 7 days, the unformed linking hydration products grown a lot of vitreous hydration products. When hydration reaction basicly finished after 28 days, the hydration products have developed into a large volume of massive vitreous with an extremely dense structure. The Ca2SiO3 mineral phase is significantly reduced, which is participate in hydration reactions. The decrease of Ca2SiO3 indicates that the Si-O bond in the system have been ruptured and reorganized.

Key Role of Nitrate in Phase Transitions of Urban Particles: Implications of Important Reactive Surfaces for Secondary Aerosol Formation

NASA Astrophysics Data System (ADS)

Sun, Jiaxing; Liu, Lei; Xu, Liang; Wang, Yuanyuan; Wu, Zhijun; Hu, Min; Shi, Zongbo; Li, Yongjie; Zhang, Xiaoye; Chen, Jianmin; Li, Weijun

2018-01-01

Ammonium sulfate (AS) and ammonium nitrate (AN) are key components of urban fine particles. Both field and model studies showed that heterogeneous reactions of SO2, NO2, and NH3 on wet aerosols accelerated the haze formation in northern China. However, little is known on phase transitions of AS-AN containing haze particles. Here hygroscopic properties of laboratory-generated AS-AN particles and individual particles collected during haze events in an urban site were investigated using an individual particle hygroscopicity system. AS-AN particles showed a two-stage deliquescence at mutual deliquescence relative humidity (MDRH) and full deliquescence relative humidity (DRH) and three physical states: solid before MDRH, solid-aqueous between MDRH and DRH, and aqueous after DRH. During hydration, urban haze particles displayed a solid core and aqueous shell at RH = 60-80% and aqueous phase at RH > 80%. Most particles were in aqueous phase at RH > 50% during dehydration. Our results show that AS content in individual particles determines their DRH and AN content determines their MDRH. AN content increase can reduce MDRH, which indicates occurrence of aqueous shell at lower RH. The humidity-dependent phase transitions of nitrate-abundant urban particles are important to provide reactive surfaces of secondary aerosol formation in the polluted air.

Groundwater quality, age, and susceptibility and vulnerability to nitrate contamination with linkages to land use and groundwater flow, Upper Black Squirrel Creek Basin, Colorado, 2013

USGS Publications Warehouse

Wellman, Tristan P.; Rupert, Michael G.

2016-03-03

The results of this investigation offer the foundational information needed for developing best management practices to mitigate nitrate contamination, basic concepts on water quality to aid public education, and information to guide regulatory measures if policy makers determine this is warranted. Science-based decision making will require continued monitoring and analysis of water quality in the future.

Numerical Simulations for Enhanced Methane Recovery from Gas Hydrate Accumulations by Utilizing CO2 Sequestration

NASA Astrophysics Data System (ADS)

Sridhara, Prathyusha

In 2013, the International Energy Outlook (EIA, 2013) projected that global energy demand will grow by 56% between 2010 and 2040. Despite strong growth in renewable energy supplies, much of this growth is expected to be met by fossil fuels. Concerns ranging from greenhouse gas emissions and energy security are spawning new interests for other sources of energy including renewable and unconventional fossil fuel such as shale gas and oil as well as gas hydrates. The production methods as well as long-term reservoir behavior of gas hydrate deposits have been under extensive investigation. Reservoir simulators can be used to predict the production potentials of hydrate formations and to determine which technique results in enhanced gas recovery. In this work, a new simulation tool, Mix3HydrateResSim (Mix3HRS), which accounts for complex thermodynamics of multi-component hydrate phase comprised of varying hydrate solid crystal structure, is used to perform the CO2-assisted production technique simulations from CH4 hydrate accumulations. The simulator is one among very few reservoir simulators which can simulate the process of CH4 substitution by CO2 (and N2 ) in the hydrate lattice. Natural gas hydrate deposits around the globe are categorized into three different classes based on the characteristics of the geological sediments present in contact with the hydrate bearing deposits. Amongst these, the Class 2 hydrate accumulations predominantly confirmed in the permafrost and along seashore, are characterized by a mobile aqueous phase underneath a hydrate bearing sediment. The exploitation of such gas hydrate deposits results in release of large amounts of water due to the presence of permeable water-saturated sediments encompassing the hydrate deposits, thus lowering the produced gas rates. In this study, a suite of numerical simulation scenarios with varied complexity are considered which aimed at understanding the underlying changes in physical, thermodynamic and transport properties with change in pressure and temperature due to the presence of the simple CO2-hydrate and mixed hydrates (mainly CH4-CO2 hydrate and CH4 -CO2-N2 hydrate) in the porous geologic media. These simulations on CO2/ CH4-CO2 hydrate reservoirs provided a basic insight to formulate and interpret a novel technological approach. This approach aims at prediction of enhanced gas production profiles from Class 2 hydrate accumulations by utilizing CO2 sequestration. The approach also offers a possibility to permanently store CO 2 in the geologic formation to a greater extent compared to a direct injection of CO2 into gas hydrate sediments. The production technique implies a three-stage approach using one vertical well design. In Stage I, the CO2 is injected into the underlying aquifer. In Stage II, the well is shut in and injected CO2 is allowed to be converted into immobile CO2 hydrate. Finally, during Stage III, decomposition of CH4 hydrate is induced by the depressurization method. The gas production potential is estimated over 15 years. The results reveal that methane production is increased together with simultaneous reduction of concomitant water production rate comparing to a conventional Class 2 reservoir production.

A New Critical State Model for Geomechanical Behavior of Methane Hydrate-Bearing Sands

NASA Astrophysics Data System (ADS)

Lin, J. S.; Xing, P.; Rutqvist, J.; Seol, Y.; Choi, J. H.

2014-12-01

Methane hydrate bearing sands behave like sands once the hydrate has dissociated, but could exhibit a substantial increase in the shear strength, stiffness and dilatancy as the degree of hydrate saturation increases. A new critical state model was developed that incorporates the spatially mobilized plane (SMP) concept, which has been proven effective in modeling mechanical behavior of sands. While this new model was built on the basic constructs of the critical state model, important enhancements were introduced. The model adopted the t-stress concept, which defined the normal and shear stress on the SMP, in describing the plastic behavior of the soil. In this connection the versatile Matsuoka-Nakai yield criterion was also employed, which defined the general three dimensional yield behavior. The resulting constitutive law was associated in the t-stress space, but became non-associated in the conventional p-q stress space as it should be for sands. The model also introduced a generalized degree of hydrate saturation concept that was modified from the pioneering work of the Cambridge group. The model gives stress change when the sands are subjected to straining, and/or to hydrate saturation changes. The performance of the model has been found satisfactory using data from laboratory triaxial tests on reconstituted samples and core samples taken from Nankai Trough, Japan. The model has been implemented into FLAC3D. A coupling example with the multiphase flow code, TOUGH+, is presented which simulates the mechanical behavior of a sample when the surrounding temperature has been raised, and the hydrate undergoes state change and no longer resides in the stability zone.

Methane Hydrates: Chapter 8

USGS Publications Warehouse

Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

2008-01-01

Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be produced through exploratory drilling programs; (2) the tools for gas hydrate detection and characterisation from remote sensing data; (3) the details of gas hydrate reservoir production behaviour through additional, well-monitored and longer duration field tests and (4) the understanding of the potential environmental impacts of gas hydrate resource development. The results of future production tests, in the context of varying market and energy supply conditions around the globe, will be the key to determine the ultimate timing and scale of the commercial production of natural gas from gas hydrates.

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

PubMed

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Islamic views on artificial nutrition and hydration in terminally ill patients.

PubMed

Alsolamy, Sami

2014-02-01

Withholding and withdrawing artificial nutrition and hydration from terminally ill patients poses many ethical challenges. The literature provides little information about the Islamic beliefs, attitudes, and laws related to these challenges. Artificial nutrition and hydration may be futile and reduce quality of life. They can also harm the terminally ill patient because of complications such as aspiration pneumonia, dyspnea, nausea, diarrhea, and hypervolemia. From the perspective of Islam, rules governing the care of terminally ill patients are derived from the principle that injury and harm should be prevented or avoided. The hastening of death by the withdrawal of food and drink is forbidden, but Islamic law permits the withdrawal of futile, death-delaying treatment, including life support. Nutritional support is considered basic care and not medical treatment, and there is an obligation to provide nutrition and hydration for the dying person unless it shortens life, causes more harm than benefit, or is contrary to an advance directive that is consistent with Islamic law. The decision about withholding or withdrawing artificial nutrition and hydration from the terminally ill Muslim patient is made with informed consent, considering the clinical context of minimizing harm to the patient, with input from the patient, family members, health care providers, and religious scholars. © 2012 John Wiley & Sons Ltd.

Simultaneous removal of colour, phosphorus and disinfection from treated wastewater using an agent synthesized from amorphous silica and hydrated lime.

PubMed

Yamashita, Takahiro; Aketo, Tsuyoshi; Minowa, Nobutaka; Sugimoto, Kiyomi; Yokoyama, Hiroshi; Ogino, Akifumi; Tanaka, Yasuo

2013-01-01

An agent synthesized from amorphous silica and hydrated lime (CSH-lime) was investigated for its ability to simultaneously remove the colour, phosphorus and disinfection from the effluents from wastewater treatment plants on swine farms. CSH-lime removed the colour and phosphate from the effluents, with the colour-removal effects especially high at pH 12, and phosphorous removal was more effective in strongly alkaline conditions (pH > 10). Colour decreased from 432 +/-111 (mean +/- SD) to 107 +/- 41 colour units and PO4(3-)P was reduced from 45 +/- 39 mg/L to undetectable levels at the CSH-lime dose of 2.0% w/v. Moreover, CSH-lime reduced the total organic carbon from 99.0 to 37.9 mg/L at the dose of 2.0% w/v and was effective at inactivating total heterotrophic and coliform bacteria. However, CSH-lime did not remove nitrogen compounds such as nitrite, nitrate and ammonium. Colour was also removed from dye solutions by CSH-lime, at the same dose.

DNA under Force: Mechanics, Electrostatics, and Hydration.

PubMed

Li, Jingqiang; Wijeratne, Sithara S; Qiu, Xiangyun; Kiang, Ching-Hwa

2015-02-25

Quantifying the basic intra- and inter-molecular forces of DNA has helped us to better understand and further predict the behavior of DNA. Single molecule technique elucidates the mechanics of DNA under applied external forces, sometimes under extreme forces. On the other hand, ensemble studies of DNA molecular force allow us to extend our understanding of DNA molecules under other forces such as electrostatic and hydration forces. Using a variety of techniques, we can have a comprehensive understanding of DNA molecular forces, which is crucial in unraveling the complex DNA functions in living cells as well as in designing a system that utilizes the unique properties of DNA in nanotechnology.

Localized corrosion of 316L stainless steel with SiO2-CaO films obtained by means of sol-gel treatment.

PubMed

Vallet-Regí, M; Izquierdo-Barba, I; Gil, F J

2003-11-01

Sol-gel films on austenitic stainless steel (AISI 316L) polished wafer were prepared from sono-sols obtained from tetraethylorthosilane and hydrated calcium nitrate. However, pitting was observed in different places on the stainless steel surfaces. The corrosion resistance was evaluated by the polarization resistance in simulated body fluid environment at 37 degrees C. The critical current density, the passive current density, the corrosion potential, and the critical pitting potential were studied. The austenitic stainless steel 316L treated presents important electrochemical corrosion and consequently its application as endosseous implants is not possible. Copyright 2003 Wiley Periodicals, Inc.

[Withdrawal of artificial nutrition and hydration in severe stroke: medical, legal and ethical considerations].

PubMed

Tannier, C; Crozier, S; Zuber, M; Constantinides, Y; Delezie, E; Gisquet, E; Grignoli, N; Lamy, C; Louvet, F; Pinel, J-F

2015-02-01

In the majority of cases, severe stroke is accompanied by difficulty in swallowing and an altered state of consciousness requiring artificial nutrition and hydration. Because of their artificial nature, nutrition and hydration are considered by law as treatment rather basic care. Withdrawal of these treatments is dictated by the refusal of unreasonable obstinacy enshrined in law and is justified by the risk of severe disability and very poor quality of life. It is usually the last among other withholding and withdrawal decisions which have already been made during the long course of the disease. Reaching a collegial consensus on a controversial decision such as artificial nutrition and hydration withdrawal is a difficult and complex process. The reluctance for such decisions is mainly due to the symbolic value of food and hydration, to the fear of "dying badly" while suffering from hunger and thirst, and to the difficult distinction between this medical act and euthanasia. The only way to overcome such reluctance is to ensure flawless accompaniment, associating sedation and appropriate comfort care with a clear explanation (with relatives but also caregivers) of the rationale and implications of this type of decision. All teams dealing with this type of situation must have thoroughly thought through the medical, legal and ethical considerations involved in making this difficult decision. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

A contribution to the characterization of the silicate-water interface - Part I: Implication of a new polished sample hydration technique.

PubMed

Sowoidnich, T; Gordon, L; Naber, C; Bellmann, F; Neubauer, J; Joester, D

2018-06-11

The analysis of the atomic composition of the interface between tricalcium silicate (C 3 S), the main compound of Ordinary Portland Cement, and surrounding solution is still a challenging task. At the same time, that knowledge is of profound importance for describing the basic processes during hydration. By means of Scanning Electron Microscopy (SEM) and Atom Probe Tomography (APT) we combine modern techniques in order to shed light on this topic in the present study. The results of these methods are compared with conduction calorimetry as a standard technique to study the hydration kinetics of cement. The tests were carried out on powders as well as on polished C 3 S samples. Results indicate that the progress of hydration is strongly increased when the C 3 S is used in the form of polished specimen. First C-S-H phases are detected in the powder 2.2 h after contact with water, on the polished section after 5 min. Besides SEM, the formation of C-S-H phases can be detected by APT, leading to an advantageous atomic resolution compared to EDX analysis. We propose that the use of APT will lead to deeper insights on the hydration progress and on the composition of the sensitive C-S-H phases based on these first results. Copyright © 2018 Elsevier Ltd. All rights reserved.

Stop "Poking the Bear": Dealing with Violence in the Family

ERIC Educational Resources Information Center

Kent, Marcia

2013-01-01

A child and adolescent psychiatrist describes the dyadic nature of family conflict and provides practical strategies for preventing and managing interpersonal aggression. When parents ignore basic needs such as sleep, hunger, hydration, safety, and security, their children are likely to display qualities like hyperactivity, hypervigilance. and…

Procedure for rapid determination of δ15N and δ18O values of nitrate: development and application to an irrigated rice paddy watershed.

PubMed

Yada, Saeko; Nakajima, Yasuhiro; Itahashi, Sunao; Asada, Kei; Yoshikawa, Seiko; Eguchi, Sadao

2016-01-01

The dual isotope approach using the stable isotope ratios of nitrate nitrogen (δ(15)N(NO3)) and oxygen (δ(18)O(NO3)) is a strong tool for identifying the history of nitrate in various environments. Basically, a rapid procedure for determining δ(15)N(NO3) and δ(18)O(NO3) values is required to analyze many more samples quickly and thus save on the operational costs of isotope-ratio mass spectrometry (IRMS). We developed a new rapid procedure to save time by pre-treating consecutive samples of nitrous oxide microbially converted from nitrate before IRMS determination. By controlling two six-port valves of the pre-treatment system separately, IRMS determination of the current sample and backflush during the next sample pre-treatment period could be conducted simultaneously. A set of 89 samples was analyzed precisely during a 25-h continuous run (17 min per sample), giving the fastest reported processing time, and simultaneously reducing liquid nitrogen and carrier helium gas consumption by 35%. Application of the procedure to an irrigated rice paddy watershed suggested that nitrate concentrations in river waters decreased in a downstream direction, mainly because of the mixing of nitrate from different sources, without distinct evidence of denitrification. Our procedure should help with more detailed studies of nitrate formation processes in watersheds.

Simulation of subsea gas hydrate exploitation

NASA Astrophysics Data System (ADS)

Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

2014-05-01

The recovery of methane from gas hydrate layers that have been detected in several subsea sediments and permafrost regions around the world is a promising perspective to overcome future shortages in natural gas supply. Being aware that conventional natural gas resources are limited, research is going on to develop technologies for the production of natural gas from such new sources. Thus various research programs have started since the early 1990s in Japan, USA, Canada, India, and Germany to investigate hydrate deposits and develop required technologies. In recent years, intensive research has focussed on the capture and storage of CO2 from combustion processes to reduce climate impact. While different natural or man-made reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid CO2, the storage of CO2 as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in the form of hydrates. Regarding technological implementation many problems have to be overcome. Especially mixing, heat and mass transfer in the reservoir are limiting factors causing very long process times. Within the scope of the German research project »SUGAR« different technological approaches for the optimized exploitation of gas hydrate deposits are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical processes are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs. Simulations based on geological field data have been carried out. The studies focus on the potential of gas production from turbidites and their fitness for CO2 storage. The effects occurring during gas production and CO2 storage within a hydrate deposit are identified and described for various scenarios. The behavior of relevant process parameters such as pressure, temperature and phase saturations is discussed and compared for different strategies: simple depressurization, simultaneous and subsequent methane production together with CO2 injection.

Emissions of fine particulate nitrated phenols from the burning of five common types of biomass.

PubMed

Wang, Xinfeng; Gu, Rongrong; Wang, Liwei; Xu, Wenxue; Zhang, Yating; Chen, Bing; Li, Weijun; Xue, Likun; Chen, Jianmin; Wang, Wenxing

2017-11-01

Nitrated phenols are among the major constituents of brown carbon and affect both climates and ecosystems. However, emissions from biomass burning, which comprise one of the most important primary sources of atmospheric nitrated phenols, are not well understood. In this study, the concentrations and proportions of 10 nitrated phenols, including nitrophenols, nitrocatechols, nitrosalicylic acids, and dinitrophenol, in fine particles from biomass smoke were determined under three different burning conditions (flaming, weakly flaming, and smoldering) with five common types of biomass (leaves, branches, corncob, corn stalk, and wheat straw). The total abundances of fine nitrated phenols produced by biomass burning ranged from 2.0 to 99.5 μg m -3 . The compositions of nitrated phenols varied with biomass types and burning conditions. 4-nitrocatechol and methyl nitrocatechols were generally most abundant, accounting for up to 88-95% of total nitrated phenols in flaming burning condition. The emission ratios of nitrated phenols to PM 2.5 increased with the completeness of combustion and ranged from 7 to 45 ppmm and from 239 to 1081 ppmm for smoldering and flaming burning, respectively. The ratios of fine nitrated phenols to organic matter in biomass burning aerosols were comparable to or lower than those in ambient aerosols affected by biomass burning, indicating that secondary formation contributed to ambient levels of fine nitrated phenols. The emission factors of fine nitrated phenols from flaming biomass burning were estimated based on the measured mass fractions and the PM 2.5 emission factors from literature and were approximately 0.75-11.1 mg kg -1 . According to calculations based on corn and wheat production in 31 Chinese provinces in 2013, the total estimated emission of fine nitrated phenols from the burning of corncobs, corn stalks, and wheat straw was 670 t. This work highlights the apparent emission of methyl nitrocatechols from biomass burning and provides basic data for modeling studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

The bZIP transcription factor MdHY5 regulates anthocyanin accumulation and nitrate assimilation in apple.

PubMed

An, Jian-Ping; Qu, Feng-Jia; Yao, Ji-Fang; Wang, Xiao-Na; You, Chun-Xiang; Wang, Xiao-Fei; Hao, Yu-Jin

2017-01-01

The basic leucine zipper (bZIP) transcription factor HY5 plays a multifaceted role in plant growth and development. Here the apple MdHY5 gene was cloned based on its homology with Arabidopsis HY5 . Expression analysis demonstrated that MdHY5 transcription was induced by light and abscisic acid treatments. Electrophoretic mobility shift assays and transient expression assays subsequently showed that MdHY5 positively regulated both its own transcription and that of MdMYB10 by binding to E-box and G-box motifs, respectively. Furthermore, we obtained transgenic apple calli that overexpressed the MdHY5 gene, and apple calli coloration assays showed that MdHY5 promoted anthocyanin accumulation by regulating expression of the MdMYB10 gene and downstream anthocyanin biosynthesis genes. In addition, the transcript levels of a series of nitrate reductase genes and nitrate uptake genes in both wild-type and transgenic apple calli were detected. In association with increased nitrate reductase activities and nitrate contents, the results indicated that MdHY5 might be an important regulator in nutrient assimilation. Taken together, these results indicate that MdHY5 plays a vital role in anthocyanin accumulation and nitrate assimilation in apple.

Ab initio molecular dynamic study of solid-state transitions of ammonium nitrate

PubMed Central

Yu, Hongyu; Duan, Defang; Liu, Hanyu; Yang, Ting; Tian, Fubo; Bao, Kuo; Li, Da; Zhao, Zhonglong; Liu, Bingbing; Cui, Tian

2016-01-01

High-pressure polymorphism and phase transitions have wide ranging consequences on the basic properties of ammonium nitrate. However, the phase diagram of ammonium nitrate at high pressure and high temperature is still under debate. This study systematically investigates the phase transitions and structural properties of ammonium nitrate at a pressure range of 5–60 GPa and temperature range of 250–400 K by ab initio molecular dynamics simulations. Two new phases are identified: one corresponds to the experimentally observed phase IV’ and the other is named AN-X. Simultaneously, the lattice strains play a significant role in the formation and stabilization of phase IV’, providing a reasonable explanation for experimental observation of phase IV-IV’ transition which only appears under nonhydrostatic pressure. In addition, 12 O atoms neighboring the NH (N atom in ammonium cation) atom are selected as reference system to clearly display the tanglesome rotation of ammonium cation. PMID:26754622

Design and basic properties of ternary gypsum-based mortars

NASA Astrophysics Data System (ADS)

Doleželová, M.; Vimmrová, A.

2017-10-01

Ternary mortars, prepared from gypsum, hydrated lime and three types of pozzolan were designed and tested. As a pozzolan admixture crushed ceramic, silica fume and granulated blast slag were used. The amount of pozzolans in the mixtures was determined according to molar weight of amorphous SiO2 in the material. The samples were stored under the water. The basic physical properties and mechanical properties were measured. The properties were compared with the properties of material without pozzolan. The best results in the water environment were achieved by the samples with silica fume.

An Outlook on Biothermodynamics: Needs, Problems, and New Developments. I. Stability and Hydration of Proteins

NASA Astrophysics Data System (ADS)

Keller, Jürgen U.

2008-12-01

The application of concepts, principles, and methods of thermodynamics of equilibria and processes to bioengineering systems has led to a new and growing field: engineering biothermodynamics. This article, which is meant as the first in a series, gives an outline of basic aspects, changes, and actual examples in this field. After a few introductory remarks, the basic concepts and laws of thermodynamics extended to systems with internal variables, which serve as models for biofluids and other biosystems, are given. The method of thermodynamics is then applied to the problem of thermal stability of aqueous protein solutions, especially to that of myoglobin solutions. After this, the phenomenon of hydration of proteins by adsorption and intrusion of water molecules is considered. Several other phenomena like the adsorption of proteins on solid surfaces or cell membranes and their temperature and pressure-related behavior represented by an equation of state, or the thermodynamics of bacterial solutions including chemical reactions like wine fermentation, etc., will be presented in Parts II and III of this article.

Synthesis of galium nitride thin films using sol-gel dip coating method

NASA Astrophysics Data System (ADS)

Hamid, Maizatul Akmam Ab; Ng, Sha Shiong

2017-12-01

In this research, gallium nitride (GaN) thin film were grown on silicon (Si) substrate by a low-cost sol-gel dip coating deposition method. The GaN precursor solution was prepared using gallium (III) nitrate hydrate powder, ethanol and diethanolamine as a starting material, solvent and surfactant respectively. The structural, morphological and optical characteristics of the deposited GaN thin film were investigated. Field-emission scanning electron microscopy observations showed that crack free and dense grains GaN thin films were formed. Energy dispersive X-ray analysis confirmed that the oxygen content in the deposited films was low. X-ray diffraction results revealed that deposited GaN thin films have hexagonal wurtzite structure.

Construction, in vitro and in vivo evaluation of an in-house conductance meter for measurement of skin hydration.

PubMed

Hamed, Saja H; Altrabsheh, Bilal; Assa'd, Tareq; Jaradat, Said; Alshra'ah, Mohammad; Aljamal, Abdulfattah; Alkhatib, Hatim S; Almalty, Abdul-Majeed

2012-12-01

Different probes are used in dermato-cosmetic research to measure the electrical properties of the skin. The principle governing the choice of the geometry and material of the measuring probe is not well defined in the literature and some device's measuring principles are not accessible for the scientific community. The purpose of this work was to develop a simple inexpensive conductance meter for the objective in vivo evaluation of skin hydration. The conductance meter probe was designed using the basic equation governing wave propagation along Transverse Electromagnetic transmission lines. It consisted of two concentric copper circular electrodes printed on FR4 dielectric material. The performance of the probe was validated by evaluating its measurement depth, its ability to monitor in vitro water sorption-desorption and in vivo skin hydration effect in comparison to that of the Corneometer CM 825. The measurement depth of the probe, 15 μm, was comparable to that of CM 825. The in vitro readings of the probe correlated strongly with the amount of water adsorbed on filter paper. Skin hydration after application of a moisturizer was monitored effectively by the new probe with good correlation to the results of CM 825. In conclusion, a simple probe for evaluating skin hydration was made from off-the-shelf materials and its performance was validated in comparison to a commercially available probe. Copyright © 2012 IPEM. Published by Elsevier Ltd. All rights reserved.

[Hydration in clinical practice].

PubMed

Maristany, Cleofé Pérez-Portabella; Segurola Gurruchaga, Hegoi

2011-01-01

Water is an essential foundation for life, having both a regulatory and structural function. The former results from active and passive participation in all metabolic reactions, and its role in conserving and maintaining body temperature. Structurally speaking it is the major contributer to tissue mass, accounting for 60% of the basis of blood plasma, intracellular and intersticial fluid. Water is also part of the primary structures of life such as genetic material or proteins. Therefore, it is necessary that the nurse makes an early assessment of patients water needs to detect if there are signs of electrolyte imbalance. Dehydration can be a very serious problem, especially in children and the elderly. Dehydrations treatment with oral rehydration solution decreases the risk of developing hydration disorders, but even so, it is recommended to follow preventive measures to reduce the incidence and severity of dehydration. The key to having a proper hydration is prevention. Artificial nutrition encompasses the need for precise calculation of water needs in enteral nutrition as parenteral, so the nurse should be part of this process and use the tools for calculating the patient's requirements. All this helps to ensure an optimal nutritional status in patients at risk. Ethical dilemmas are becoming increasingly common in clinical practice. On the subject of artificial nutrition and hydration, there isn't yet any unanimous agreement regarding hydration as a basic care. It is necessary to take decisions in consensus with the health team, always thinking of the best interests of the patient.

"Cooking the sample": radiofrequency induced heating during solid-state NMR experiments.

PubMed

d'Espinose de Lacaillerie, Jean-Baptiste; Jarry, Benjamin; Pascui, Ovidiu; Reichert, Detlef

2005-09-01

Dissipation of radiofrequency (RF) energy as heat during continuous wave decoupling in solid-state NMR experiment was examined outside the conventional realm of such phenomena. A significant temperature increase could occur while performing dynamic NMR measurements provided the sample contains polar molecules and the sequence calls for relatively long applications of RF power. It was shown that the methyl flip motion in dimethylsulfone (DMS) is activated by the decoupling RF energy conversion to heat during a CODEX pulse sequence. This introduced a significant bias in the correlation time-temperature dependency measurement used to obtain the activation energy of the motion. By investigating the dependency of the temperature increase in hydrated lead nitrate on experimental parameters during high-power decoupling one-pulse experiments, the mechanisms for the RF energy deposition was identified. The samples were heated due to dissipation of the energy absorbed by dielectric losses, a phenomenon commonly known as "microwave" heating. It was thus established that during solid-state NMR experiments at moderate B0 fields, RF heating could lead to the heating of samples containing polar molecules such as hydrated polymers and inorganic solids. In particular, this could result in systematic errors for slow dynamics measurements by solid-state NMR.

Study of transmittance and reflectance spectra of the cornea and the sclera in the THz frequency range

NASA Astrophysics Data System (ADS)

Iomdina, Elena N.; Goltsman, Gregory N.; Seliverstov, Sergey V.; Sianosyan, Alisa A.; Teplyakova, Kseniya O.; Rusova, Anastasia A.

2016-09-01

An adequate water balance (hydration extent) is one of the basic factors of normal eye function, including its external shells: the cornea and the sclera. Adequate control of corneal and scleral hydration is very important for early diagnosis of a variety of eye diseases, stating indications for and contraindications against keratorefractive surgeries and the choice of contact lens correction solutions. THz systems of creating images in reflected beams are likely to become ideal instruments of noninvasive control of corneal and scleral hydration degrees. This paper reports on the results of a study involving transmittance and reflectance spectra for the cornea and the sclera of rabbit and human eyes, as well as those of the rabbit eye, in the frequency range of 0.13 to 0.32 THz. The dependence of the reflectance coefficient of these tissues on water mass percentage content was determined. The experiments were performed on three corneas, three rabbit scleras, two rabbit eyes, and three human scleras. The preliminary results demonstrate that the proposed technique, based on the use of a continuous THz radiation, may be utilized to create a device for noninvasive control of corneal and scleral hydration, which has clear potential of broad practical application.

Electromarking solution

DOEpatents

Bullock, Jonathan S.; Harper, William L.; Peck, Charles G.

1976-06-22

This invention is directed to an aqueous halogen-free electromarking solution which possesses the capacity for marking a broad spectrum of metals and alloys selected from different classes. The aqueous solution comprises basically the nitrate salt of an amphoteric metal, a chelating agent, and a corrosion-inhibiting agent.

Nitrate Remediation of Soil and Groundwater Using Phytoremediation: Transfer of Nitrogen Containing Compounds from the Subsurface to Surface Vegetation

NASA Astrophysics Data System (ADS)

Nelson, Sheldon

2013-04-01

Nitrate Remediation of Soil and Groundwater Using Phytoremediation: Transfer of Nitrogen Containing Compounds from the Subsurface to Surface Vegetation Sheldon Nelson Chevron Energy Technology Company 6001 Bollinger Canyon Road San Ramon, California 94583 snne@chevron.com The basic concept of using a plant-based remedial approach (phytoremediation) for nitrogen containing compounds is the incorporation and transformation of the inorganic nitrogen from the soil and/or groundwater (nitrate, ammonium) into plant biomass, thereby removing the constituent from the subsurface. There is a general preference in many plants for the ammonium nitrogen form during the early growth stage, with the uptake and accumulation of nitrate often increasing as the plant matures. The synthesis process refers to the variety of biochemical mechanisms that use ammonium or nitrate compounds to primarily form plant proteins, and to a lesser extent other nitrogen containing organic compounds. The shallow soil at the former warehouse facility test site is impacted primarily by elevated concentrations of nitrate, with a minimal presence of ammonium. Dissolved nitrate (NO3-) is the primary dissolved nitrogen compound in on-site groundwater, historically reaching concentrations of 1000 mg/L. The initial phases of the project consisted of the installation of approximately 1750 trees, planted in 10-foot centers in the areas impacted by nitrate and ammonia in the shallow soil and groundwater. As of the most recent groundwater analytical data, dissolved nitrate reductions of 40% to 96% have been observed in monitor wells located both within, and immediately downgradient of the planted area. In summary, an evaluation of time series groundwater analytical data from the initial planted groves suggests that the trees are an effective means of transfering nitrogen compounds from the subsurface to overlying vegetation. The mechanism of concentration reduction may be the uptake of residual nitrate from the vadose zone, the direct uptake of dissolved constituent from the upper portion of the saturated zone/capillary fringe, or a combination of these two processes.

Simulation of natural gas production from submarine gas hydrate deposits combined with carbon dioxide storage

NASA Astrophysics Data System (ADS)

Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

2013-04-01

The recovery of methane from gas hydrate layers that have been detected in several submarine sediments and permafrost regions around the world so far is considered to be a promising measure to overcome future shortages in natural gas as fuel or raw material for chemical syntheses. Being aware that natural gas resources that can be exploited with conventional technologies are limited, research is going on to open up new sources and develop technologies to produce methane and other energy carriers. Thus various research programs have started since the early 1990s in Japan, USA, Canada, South Korea, India, China and Germany to investigate hydrate deposits and develop technologies to destabilize the hydrates and obtain the pure gas. In recent years, intensive research has focussed on the capture and storage of carbon dioxide from combustion processes to reduce climate change. While different natural or manmade reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid carbon dioxide, the storage of carbon dioxide as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in form of hydrates. This has been shown in several laboratory tests and simulations - technical field tests are still in preparation. Within the scope of the German research project »SUGAR«, different technological approaches are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical effects are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs like CMG STARS and COMSOL Multiphysics. New simulations based on field data have been carried out. The studies focus on the evaluation of the gas production potential from turbidites and their ability for carbon dioxide storage. The effects occurring during gas production and CO2 storage within a hydrate deposit are identified and described for various scenarios. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is discussed and compared for different production strategies: depressurization, CO2 injection after depressurization and simultaneous methane production and CO2 injection.

Solubilities of Some Strong Electrolytes in the Hydrogen Peroxide-Water System. II. Rubidium and Cesium Nitrates

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

Everhard, Martin E.; Gross, Paul M.

1962-03-01

Solubilities of RbNO/sub 3/ and CsNO/sub 3/ were examined as well as the nature of the solid phases in equilibrium with these systems in order to study the possible role of cation size. The formation of hydroperoxidates and the increase in solibility of the salts with larger cations in hydrogen peroxide- rich solutions indicate preferential solvation of the ions by H/sub 2/O/sub 2/ rather than by H/sub 2/O. Conversely, the formation of hydrates and lower solubility in hydrogen peroxide-rich solutions of the smaller cation salts indicate preferential solvation of the ions by water. The deviation of the molal solubility, M',more » of the alkali nitrates in H/sub 2/O/sub 2/ from that in H/sub 2/O (M/sub H /sub 2/O/sub 2/) at ' =33.5r - 39.7 ( plus or minus 0.03 in M'), where r is the radius of the cation. CsNO/sub 3/, however, did not fall on the line, which probably is due to the lower charge density of the cesium ion. (P.C.H.)« less

Study of quantitative interactions of potato and corn starch granules with ions in diluted solutions of heavy metal salts.

PubMed

Szymońska, Joanna; Molenda, Marcin; Wieczorek, Jerzy

2015-12-10

Interactions of potato and corn starch granules with ions in diluted solutions of silver, lead, copper or iron salts were investigated. It was shown experimentally that granules accumulated the cations in amounts depending on the granule structure and water content as well as a type of both metal and counter-ions present in solution. Potato starch retained almost three times more cations compared to corn starch what was proportional to the total phosphorous content in these starches. Quantity of milligrams of cations bound by 1g of starch was inversely correlated with the cation hydration. Ag(+), Pb(2+) and Cu(2+) were connected in stoichiometric amounts of moles to semicrystalline and amorphous parts of the granules. Fe(3+) ions were accumulated in higher than stoichiometric quantities mainly in granule amorphous regions. Metal ions penetrated into granules together with anions except nitrates which remained on surface of potato starch granules. Cations facilitated the starch thermal decomposition in accordance with values of their standard redox potentials. Nitrates supported this process only in the presence of base metal cations. Copyright © 2015 Elsevier Ltd. All rights reserved.

Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ke, Haochen; van der Linde, Christian; Lisy, James M.

2014-06-01

Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy.

PubMed

Marutschke, Christoph; Walters, Deron; Walters, Deron; Hermes, Ilka; Bechstein, Ralf; Kühnle, Angelika

2014-08-22

Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic - yet decisive - question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface.

Long term mechanical properties of alkali activated slag

NASA Astrophysics Data System (ADS)

Zhu, J.; Zheng, W. Z.; Xu, Z. Z.; Leng, Y. F.; Qin, C. Z.

2018-01-01

This article reports a study on the microstructural and long-term mechanical properties of the alkali activated slag up to 180 days, and cement paste is studied as the comparison. The mechanical properties including compressive strength, flexural strength, axis tensile strength and splitting tensile strength are analyzed. The results showed that the alkali activated slag had higher compressive and tensile strength, Slag is activated by potassium silicate (K2SiO3) and sodium hydroxide (NaOH) solutions for attaining silicate modulus of 1 using 12 potassium silicate and 5.35% sodium hydroxide. The volume dosage of water is 35% and 42%. The results indicate that alkali activated slag is a kind of rapid hardening and early strength cementitious material with excellent long-term mechanical properties. Single row of holes block compressive strength, single-hole block compressive strength and standard solid brick compressive strength basically meet engineering requirements. The microstructures of alkali activated slag are studied by X-ray diffraction (XRD). The hydration products of alkali-activated slag are assured as hydrated calcium silicate and hydrated calcium aluminate.

Tracing Nitrate Contributions to Streams During Varying Flow Regimes at the Sleepers River Research Watershed, Vermont, USA

NASA Astrophysics Data System (ADS)

Sebestyen, S. D.; Shanley, J. B.; Boyer, E. W.; Ohte, N.; Doctor, D. H.; Kendall, C.

2003-12-01

Quantifying sources and transformations of nitrate in headwater catchments is fundamental to understanding the movement of nitrogen to streams. At the Sleepers River Research Watershed in northeastern Vermont (USA), we are using multiple chemical tracer and mixing model approaches to quantify sources and transport of nitrate to streams under varying flow regimes. We sampled streams, lysimeters, and wells at nested locations from the headwaters to the outlet of the 41 ha W-9 watershed under the entire range of flow regimes observed throughout 2002-2003, including baseflow and multiple events (stormflow and snowmelt). Our results suggest that nitrogen sources, and consequently stream nitrate concentrations, are rapidly regenerated during several weeks of baseflow and nitrogen is flushed from the watershed by stormflow events that follow baseflow periods. Both basic chemistry data (anions, cations, & dissolved organic carbon) and isotopic data (nitrate, dissolved organic carbon, and dissolved inorganic carbon) indicate that nitrogen source contributions vary depending upon the extent of saturation in the watershed, the initiation of shallow subsurface water inputs, and other hydrological processes. Stream nitrate concentrations typically peak with discharge and are higher on the falling than the rising limb of the hydrograph. Our data also indicate the importance of terrestrial and aquatic biogeochemical processes, in addition to hydrological connectivity in controlling how nitrate moves from the terrestrial landscape to streams. Our detailed sampling data from multiple flow regimes are helping to identify and quantify the "hot spots" and "hot moments" of biogeochemical and hydrological processes that control nitrogen fluxes in streams.

Method for dispersing catalyst onto particulate material and product thereof

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

Method for dispersing catalyst onto particulate material

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

Elastomer coated filler and composites thereof comprising at least 60% by weight of a hydrated filler and an elastomer containing an acid substituent

NASA Technical Reports Server (NTRS)

Mueller, W. A.; Ingham, J. D.; Reilly, W. W. (Inventor)

1983-01-01

The impact resistance of flame retardant composites, especially thermoplastic molding: compounds containing over 60% hydrated mineral filler such as Al(OH)3 or Mg(OH)2 as improved by coating the filler with 1 to 20% of an elastomer. The composite will fail by crazing or shearing rather than by brittle fracture. A well bonded elastomeric interphase resulted by utilizing acidic substituted resins such as ethyl-hexyl acrylate-acrylic acid copolymers which bond to and are cross-linked by the basic filler particles. Further improvement in impact resistance was provided by incorporating 1 to 10% of a resin fiber reinforcement such as polyvinyl alcohol fibers that decompose to yield at least 30% water when heated to decomposition temperature.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

2016-12-06

Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

Hydration structure of the α-chymotrypsin substrate binding pocket: the impact of constrained geometry

NASA Astrophysics Data System (ADS)

Carey, Christina; Cheng, Yuen-Kit; Rossky, Peter J.

2000-08-01

The concave substrate binding pocket of α-chymotrypsin binds specifically hydrophobic side chains. In order to understand the hydration structure present in the absence of substrate, and elucidate the character of the solvent displaced on binding, molecular dynamics computer simulation of the solvent in a fully hydrated protein has been carried out and analyzed. The pocket is found to be characterized in terms of a mixed polar and apolar macromolecular surface. It is shown that the simulated solvent structure within it is spatially consistent with that seen via crystallography. The solvent structure is energetically characterized by large losses in hydrogen bonding among solvent molecules except at the mouth of the pocket where exposure to bulk-like solvent is possible. The loss in hydrogen bonding is attributed to the highly constrained geometry available to the solvent, preventing formation of a hydrogen bonding network, with only partial compensation by interactions with the macromolecular surface. The solvent displacement concomitant with substrate binding will therefore be associated with a large enthalpic driving force. This result is at the extreme of a continuum of variable cases of "hydrophobic" hydration, which differ most basically in surface curvature. These range from convex solute surfaces, inducing clathrate-like structures, with negligible hydrogen bond loss, to flat surfaces with significant interfacial loss, to the present concave case with hydrogen bonding losses exceeding 50%.

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

NASA Astrophysics Data System (ADS)

Iannarelli, R.; Rossi, M. J.

2015-11-01

Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

Selective retention of basic compounds by metal aquo-ion affinity chromatography.

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical study on the interactions between chlordecone hydrate and acidic surface groups of activated carbon under basic pH conditions.

PubMed

Melchor-Rodríguez, Kenia; Gamboa-Carballo, Juan José; Ferino-Pérez, Anthuan; Passé-Coutrin, Nady; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

2018-05-01

A theoretical study of the influence of acidic surface groups (SG) of activated carbon (AC) on chlordecone hydrate (CLDh) adsorption is presented, in order to help understanding the adsorption process under basic pH conditions. A seven rings aromatic system (coronene) with a functional group in the edge was used as a simplified model of AC to evaluate the influence of SG in the course of adsorption from aqueous solution at basic pH conditions. Two SG were modeled in their deprotonated form: carboxyl and hydroxyl (COO - and O - ), interacting with CLDh. In order to model the solvation process, all systems under study were calculated with up to three water molecules. Multiple Minima Hypersurface (MMH) methodology was employed to study the interactions of CLDh with SG on AC using PM7 semiempirical Hamiltonian, to explore the potential energy surfaces of the systems and evaluate their thermodynamic association energies. The re-optimization of representative structures obtained from MMH was done using M06-2X Density Functional Theory. The Quantum Theory of Atoms in Molecules (QTAIM) was used to characterize the interaction types. As result, the association of CLDh with acidic SG at basic pH conditions preferentially occurs between the two alcohol groups of CLDh with COO - and O - groups and by dispersive interactions of chlorine atoms of CLDh with the graphitic surface. On the other hand, the presence of covalent interactions between the negatively charged oxygen of SG and one hydrogen atom of CLDh alcohol groups (O - ⋯HO interactions) without water molecules, was confirmed by QTAIM study. It can be concluded that the interactions of CLDh with acidic SG of AC under basic pH conditions confirms the physical mechanisms of adsorption process. Copyright © 2018 Elsevier Inc. All rights reserved.

Self-Healing Phase Change Salogels with Tunable Gelation Temperature.

PubMed

Karimineghlani, Parvin; Palanisamy, Anbazhagan; Sukhishvili, Svetlana A

2018-05-02

Chemically cross-linked polymer matrices have demonstrated strong potential for shape stabilization of molten phase change materials (PCM). However, they are not designed to be fillable and removable from a heat exchange module for an easy replacement with new PCM matrices and lack self-healing capability. Here, a new category of shapeable, self-healing gels, "salogels", is introduced. The salogels reversibly disassemble in a high-salinity environment of a fluid inorganic PCM [lithium nitrate trihydrate (LNH)], at a preprogrammed temperature. LNH was employed as a high latent heat PCM and simultaneously as a solvent, which supported the formation of a network of polyvinyl alcohol (PVA) chains via physical cross-linking through poly(amidoamine) dendrimers of various generations. The existence of hydrogen bonding and the importance of low-hydration state of PVA for the efficient gelation were experimentally confirmed. The thermal behavior of PCM salogels was highly reversible and repeatable during multiple heating/cooling cycles. Importantly, the gel-sol transition temperature could be precisely controlled within a range of temperature above LNH's melting point by the choice of dendrimer generation and their concentration. Shape stabilization and self-healing properties of the salogels, taken together with tunability of their temperature-induced fluidization make these materials attractive for thermal energy storage applications that require on-demand removal and replacement of used inorganic PCM salt hydrates.

Environmental impact studies for gas hydrate production test in the Ulleung Basin, East Sea of Korea

NASA Astrophysics Data System (ADS)

Ryu, Byong-Jae

2017-04-01

To develop potential future energy resources, the Korean National Gas Hydrate Program has been carried out since 2005. The program has been supported by the Ministry of Trade, Industry and Energy (MOTIE), and carried out by the Korea Institute of Geoscience and Mineral Resources (KIGAM), the Korea Gas Corporation (KOGAS) and the Korea National Oil Corporation (KNOC) under the management of Gas Hydrate R&D Organization (GHDO). As a part of this national program, geophysical surveys, geological studies on gas hydrates and two deep drilling expeditions were performed. Gas hydrate-bearing sand layers suitable for production using current technologies were found during the Second Ulleung Basin Gas Hydrate Drilling Expedition (UBGH2) in 2010. Environmental impact studies (EIS) also have been carried out since 2012 by KIGAM in cooperation with domestic and foreign universities and research organizations to ensure safe production test that will be performed in near future. The schedule of production test is being planned. The EIS includes assessment of environmental risks, examination on domestic environmental laws related with production test, collection of basic oceanographic information, and baseline and monitoring surveys. Oceanographic information and domestic environmental laws are already collected and analyzed. Baseline survey has been performed using the in-house developed system, KIGAM Seafloor Observation System (KISOS) since 2013. It will also be performed. R/V TAMHAE II of KIGAM used for KISOS operation. As a part of this EIS, pseudo-3D Chirp survey also was carried out in 2014 to determine the development of fault near the potential testing site. Using KIGAM Seafloor Monitoring System (KIMOS), monitoring survey is planned to be performed from three month before production test to three months after production test. The geophysical survey for determining the change of gas hydrate reservoirs and production-efficiency around the production well would also be conducted before and after the production test. KIMOS will be developed as the planning that was drawn up already. A period for monitoring survey and geophysical survey type, such as AUV or EM surveys will be decided according to the budget.

Tissue fluid pressures - From basic research tools to clinical applications

NASA Technical Reports Server (NTRS)

Hargens, Alan R.; Akeson, Wayne H.; Mubarak, Scott J.; Owen, Charles A.; Gershuni, David H.

1989-01-01

This paper describes clinical applications of two basic research tools developed and refined in the past 20 years: the wick catheter (for measuring tissue fluid pressure) and the colloid osmometer (for measuring osmotic pressure). Applications of the osmometer include estimations of the reduced osmotic pressure of sickle-cell hemoglobin with deoxygenation, and of reduced swelling pressure of human nucleus pulposus with hydration or upon action of certain enzymes. Clinical uses of the wick-catheter technique include an improvement of diagnosis and treatment of acute and chronic compartment syndromes, the elucidation of the tissue pressure thresholds for neuromuscular dysfunction, and the development of a better tourniquet for orthopedics.

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.

Hydration of polar and nonpolar molecules at the surface of amorphous solid water

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

Souda, Ryutaro

2004-10-15

On the basis of time-of-flight secondary ion mass spectrometry, properties of amorphous solid water above the glass transition temperature (136 K) and the hydration of polar (HCOOH,C{sub 3}H{sub 7}OH) and nonpolar (C{sub 6}H{sub 14},C{sub 6}F{sub 14}) molecules on the D{sub 2}O-ice surface have been investigated. No evidence was obtained for the irreversible transition of the amorphous solid water into the crystalline phase: the self-diffusion of water molecules occurs above 140 K irrespective of the preparation temperatures of the water-ice film ranging from 15 K to 165 K, whereas the morphology of the film changes drastically at 165 K due tomore » the evolution of liquidlike water. It is also demonstrated that the change in conformation of the hydrated HCOOH molecule, as well as the occurrence of hydrophilic/hydrophobic hydration of the C{sub 3}H{sub 7}OH molecule, can be analyzed successfully from the temperature evolutions of the secondary-ion intensities. These polar molecules basically stay on the surface and tend to quench the morphological change of the water film due to the reduction of surface tension. The nonpolar C{sub 6}H{sub 14} and C{sub 6}F{sub 14} molecules readily dissolve in the D{sub 2}O layer below 100 K and dehydration of the incorporated molecules occurs at 165 K concomitantly with the evolution of the liquidlike water. It is thus concluded that the hydrophobic hydration of nonpolar molecules is intimately related to the properties of water films.« less

Preliminary Study of Radioactive Waste Package Made of High-Strength and Ultra Low-Permeability Concrete for Geological Disposal of TRU Wastes

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

Matsuo, T.; Kawasaki, T.; Sakamoto, H.

2003-02-27

We have been developing a radioactive waste package made of high-strength and ultra low-permeability concrete (HSULPC) for geological disposal of TRU wastes, which is expected to be much more impervious to water than conventional concrete. In this study, basic data for the HSULPC regarding its the impervious character and the thermodynamics during cement hydration were obtained through water permeability measurements using cold isostatic pressing (CIP) and adiabatic concrete hydration experiments, respectively. Then, a prediction tool to find concrete package construction conditions to avoid thermal cracking was developed, which could deal with coupled calculations of cement hydration, heat transfer, stress, andmore » cracking. The developed tool was applied to HSULPC hydration on a small-scale cylindrical model to examine whether there was any effect on cracking which depended on the ratio of concrete cylinder thickness to its inner diameter. The results were compared to experiments. For concrete with a compressive strength of 200MPa, the water permeability coefficient was 4 x 10{sup 19} m/s. Dependences of activation energy and frequency factor on degree of cement hydration had a sharp peaking due to the nucleation rate-determining step, and a gradual increase region due to the diffusion rate-determining step. From analyses of the small-scale cylindrical model, dependences of the maximum principal stress on the radius were obtained. When the ratio of the concrete thickness to the heater diameter was around 1, the risk of cracking was predicted to be minimized. These numerical predictions from the developed tool were verified by experiments.« less

Fluoride, Nitrate, and Dissolved-Solids Concentrations in Ground Waters of Washington

USGS Publications Warehouse

Lum, W. E.; Turney, Gary L.

1984-01-01

This study provides basic data on ground-water quality throughout the State. It is intended for uses in planning and management by agencies and individuals who have responsibility for or interest in, public health and welfare. It also provides a basis for directing future studies of ground-water quality toward areas where ground-water quality problems may already exist. The information presented is a compilation of existing data from numerous sources including: the Washington Departments of Ecology and Social and Health Services, the Environmental Protection Agency, as well as many other local, county, state and federal agencies and private corporations. Only data on fluoride, nitrate, and dissolved-solids concentrations in ground water are presented, as these constituents are among those commonly used to determine the suitability of water for drinking or other purposes. They also reflect both natural and man-imposed effects on water quality and are the most readily available water-quality data for the State of Washington. The percentage of wells with fluoride, nitrate, or dissolved-solids concentrations exceeding U.S. Environmental Protection Agency Primary and Secondary Drinking Water Regulations were about 1, about 3, and about 3, respectively. Most high concentrations occurred in widely separated wells. Two exceptions were: high concentrations of nitrate and dissolved solids in wells on the Hanford Department of Energy Facility and high concentrations of nitrate in the lower Yakima River basin. (USGS)

Near quantitative agreement of model free DFT- MD predictions with XAFS observations of the hydration structure of highly charged transition metal ions

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

Fulton, John L.; Bylaska, Eric J.; Bogatko, Stuart A.

DFT-MD simulations (PBE96 and PBE0) with MD-XAFS scattering calculations (FEFF9) show near quantitative agreement with new and existing XAFS measurements for a comprehensive series of transition metal ions which interact with their hydration shells via complex mechanisms (high spin, covalency, charge transfer, etc.). This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the U.S. DOE by Battelle. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the U.S. DOE's Office ofmore » Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

Anisotropic mechanical behaviors and their structural dependences of crossed-lamellar structure in a bivalve shell.

PubMed

Jiao, D; Liu, Z Q; Qu, R T; Zhang, Z F

2016-02-01

Crossed-lamellar structure is one of the most common organizations found in mollusk shells and may serve as a natural mimetic model for designing bio-inspired synthetic materials. Nonetheless, the mechanical behaviors and corresponding mechanisms have rarely been investigated for individual macro-layer of such structure. The integrated effects of orientation and hydration also remain unclear. In this study, the mechanical behaviors and their structural dependences of pure crossed-lamellar structure in Saxidomus purpuratus shell were systematically examined by three-point bending and compression tests. Mechanical properties and fracture mechanisms were revealed to depend strongly on the orientation, hydration state and loading condition. Three basic cracking modes of inter-platelet, trans-platelet, and along the interfaces between first-order lamellae were identified, and the interfacial separation was enhanced by hydration. Macroscopic compressive fracture was accomplished through axial splitting during which multiple toughening mechanisms were activated. The competition among different cracking modes was quantitatively evaluated by analyzing their driving stresses and resistances from fundamental mechanics. This study helps to clarify the mechanical behaviors of naturally occurring crossed-lamellar structure, and accordingly, aids in designing new bio-inspired synthetic materials by mimicking it. Copyright © 2015 Elsevier B.V. All rights reserved.

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

PubMed

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

Metabolism of nitrate in fermented meats: the characteristic feature of a specific group of fermented foods.

PubMed

Hammes, Walter P

2012-04-01

Within the universe of food fermentation processes the multi-purpose use of nitrate and/or nitrite is a unique characteristic of meat fermentations. These curing agents play a decisive role in obtaining the specific sensory properties, stability and hygienic safety of products such as fermented sausages, ham and, more recently, emulsion type of sausages. The use of nitrate is the traditional method in curing processes and requires its reduction to reactive nitrite. Thus, nitrate reduction is the key event that is exclusively performed by microorganisms. Under controlled fermentation conditions starter cultures are used that contain staphylococci and/or Kocuria varians, which in addition to strongly affecting sensory properties exhibit efficient nitrate reductase activity. To obtain clean label products some plant sources of nitrate have been in use. When producing thermally treated sausages (e.g. of emulsion type), starter cultures are used that form nitrite before cooking takes place. Staphylococci reduce nitrite to ammonia after nitrate has been consumed. K. varians is devoid of nitrite reductase activity. Nitrate and nitrite reductases are also present in certain strains of lactobacilli. It was shown that their application as starter cultures warrants efficient activity in sausages made with either nitrate or nitrite. NO is formed from nitrite in numerous chemical reactions among which disproportionation and reaction with reductants either added or endogenous in meat are of practical importance. Numerous nitrosation and nitrosylation reactions take place in the meat matrix among which the formation of nitrosomyoglobin is of major sensory importance. Safety considerations in meat fermentation relate to the safe nature of the starter organisms and to the use of nitrate/nitrite. Staphylococci ("micrococci") in fermented meat have a long tradition in food use but have not received the QPS status from the EFSA. They require, therefore, thorough assessment with regard to toxigenicity and pathogenicity determinants as well as presence of transferable antibiotic resistance. Nitrate and nitrite are still considered basically undesired in food. The main objections are based on their potential to form nitrosamines with carcinogenic potential. In view of new results from intensive research of NO, potential risks are opposed by positive effects on human health. Copyright © 2011 Elsevier Ltd. All rights reserved.

Gas Hydrate Characterization in the GoM using Marine EM Methods

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

Constable, Steven

In spite of the importance of gas hydrate as a low-carbon fuel, a possible contributor to rapid climate change, and a significant natural hazard, our current understanding about the amount and distribution of submarine gas hydrate is somewhat poor; estimates of total volume vary by at least an order of magnitude, and commercially useful concentrations of hydrate have remained an elusive target. This is largely because conventional geophysical tools have intrinsic limitations in their ability to quantitatively image hydrate. It has long been known from well logs that gas hydrate is resistive compared to the host sediments, and electrical andmore » electromagnetic methods have been proposed and occasionally used to image hydrates. This project seeks to expand our capabilities to use electromagnetic methods to explore for gas hydrate in the marine environment. An important basic science aspect of our work was to quantify the resistivity of pure gas hydrate as a function of temperature at seafloor pressures. We designed, constructed, and tested a highpressure cell in which hydrate could be synthesized and then subjected to electrical conductivity measurements. Impedance spectroscopy at frequencies between 20 Hz and 2 MHz was used to separate the effect of the blocking electrodes from the intrinsic conductivity of the hydrate. We obtained very reproducible results that showed that pure methane hydrate was several times more resistive than the water ice that seeded the synthesis, 20,000 {Ohm}m at 0{degrees} C, and that the activation energy is 30.6 kJ/mol over the temperature range of -15 to 15{degrees} C. Adding silica sand to the hydrate, however, showed that the addition of the extra phase caused the conductivity of the assemblage to increase in a counterintuitive way. The fact that the increased conductivity collapsed after a percolation threshold was reached, and that the addition of glass beads does not produce a similar increase in conductivity, together suggest that while the surface of the gas hydrate grains are not intrinsically conductive, the presence of sand does increase their conductivity. In the field component of this project, we carried out an 18day cruise on the R.V. Roger Revelle in the Gulf of Mexico from 7th-26th October 2008 to collect controlled-source electromagnetic (CSEM) data over four hydrate prospects; blocks AC 818, WR 313, GC 955, and MC 118. During these surveys we deployed 30 ocean bottom electromagnetic (OBEM) recorders a total of 94 times at four survey areas and towed the Scripps Undersea Electromagnetic Source Instrument (SUESI) a total of 103 hours. SUESI transmission was 200 A on a 50 m dipole antenna at heights of 70-100 m above the seafloor. We also towed a neutrally buoyant 3-axis electric field recorder behind the SUESI antenna at a constant offset of 300 m. The use of a towed receiver that is "flown" above the seafloor allowed us to operate in areas where seafloor infrastructure such as wellheads, pipelines, and installed scientific equipment existed. We reduced the data to apparent resistivity psuedosections. The most compelling results come from the hydrate observatory at MC 118, where a localized resistivity anomaly is clearly identified under the southeast crater in an otherwise uniform 1 {Ohm}m background. The data from MC 118 also show that authigenic carbonate does not necessarily express itself as a confounding resistor, as was feared at the start of this project. While the results from the other prospects are much more complicated, the data are well correlated with known geology, and line to line agreement is good. Although these data are not amenable to 1D inversion as was initially hoped, we expect to use a newly developed 2D CSEM inversion code to continue to get useful information from this rich data set.« less

The hydration ability of three commercially available sports drinks and water.

PubMed

Hill, Rebecca J; Bluck, Leslie J C; Davies, Peter S W

2008-04-01

This paper compares the hydration ability of three commercially-available sports drinks with water under conditions of rest and exercise, using a deuterium dilution technique. For the rest group, 0.05g/kg of body weight of deuterium, contained in gelatine capsules, was ingested with one of the test solutions and saliva samples were collected every five minutes for an hour while the subject remained seated. The deuterium was administered as above for the exercise group but sample collection was during one hour of exercise on a treadmill at 55% of the subject's maximum heart rate. The enrichment data for each subject were mathematically modelled to describe the kinetics of hydration and the parameters obtained were compared across drinks using a basic Anova. At rest, significant differences were found for t(1), t(1/2), and the percent of drink absorbed at t(1). The differences between drinks were not significant for t(2) or the maximum absorption rate. For the exercise group, the only significant difference was found between water and the sports drinks at t(1). Therefore, we conclude that labelling with a deuterium tracer is a good measure of the relative rate ingested fluids are absorbed by the body. Because of the lack of differences found at t(2), which is indicative of the 100% absorption time, both at rest and during exercise, it may be speculated that, compared to water, the sports drinks studied in this paper did not hydrate the body at a faster rate.

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s the different phases were studied by infrared transmission spectroscopy, but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparationmore » and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with but one in the hexahydrate.« less

Time-resolved infrared reflectance studies of the dehydration-induced transformation of uranyl nitrate hexahydrate to the trihydrate form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-09-08

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO 2(NO 3) 2(H 2O) 6] often called UNH), the trihydrate [UO 2(NO 3) 2(H 2O) 3 or UNT], and in very dry environments the dihydrate form [UO 2(NO 3) 2(H 2O) 2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples formore » transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N 2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO 2(NO 3) 2(H 2O) 6 has a distinct uranyl asymmetric stretch band at 949.0 cm –1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm –1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a structural and morphological change that has the lustrous lime green UO 2(NO 3) 2(H 2O) 6 crystals changing to the matte greenish yellow of the trihydrate solid. As a result, the phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.« less

Physical properties of organic fullerene cocrystals

NASA Astrophysics Data System (ADS)

Macovez, Roberto

2017-12-01

The basic facts and fundamental properties of binary fullerene cocrystals are reviewed, focusing especially on solvates and salts of Buckminsterfullerene (C60), and hydrates of hydrophilic C60 derivatives. The examined properties include the lattice structure and the presence of orientational disorder and/or rotational dynamics (of both fullerenes and cocrystallizing moieties), thermodynamic properties such as decomposition enthalpies, and charge transport properties. Both thermodynamic properties and molecular orientational disorder shed light on the extent of intermolecular interactions in these binary solid-state systems. Comparison is carried out also with pristine fullerite and with the solid phases of functionalized C60. Interesting experimental findings on binary fullerene cocrystals include the simultaneous occurrence of rotations of both constituent molecular species, crystal morphologies reminiscent of quasi-crystalline behaviour, the observation of proton conduction in hydrate solids of hydrophilic fullerene derivatives, and the production of super-hard carbon materials by application of high pressures on solvated fullerene crystals.

Abundances and implications of volatile-bearing species from evolved gas analysis of the Rocknest aeolian deposit, Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Archer, Paul Douglas; Franz, Heather B.; Sutter, Brad; Arevalo, Ricardo D.; Coll, Patrice; Eigenbrode, Jennifer L.; Glavin, Daniel P.; Jones, John J.; Leshin, Laurie A.; Mahaffy, Paul R.; McAdam, Amy C.; McKay, Christopher P.; Ming, Douglas W.; Morris, Richard V.; Navarro-González, Rafael; Niles, Paul B.; Pavlov, Alex; Squyres, Steven W.; Stern, Jennifer C.; Steele, Andrew; Wray, James J.

2014-01-01

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity detected evolved gases during thermal analysis of soil samples from the Rocknest aeolian deposit in Gale Crater. Major species detected (in order of decreasing molar abundance) were H2O, SO2, CO2, and O2, all at the µmol level, with HCl, H2S, NH3, NO, and HCN present at the tens to hundreds of nmol level. We compute weight % numbers for the major gases evolved by assuming a likely source and calculate abundances between 0.5 and 3 wt.%. The evolution of these gases implies the presence of both oxidized (perchlorates) and reduced (sulfides or H-bearing) species as well as minerals formed under alkaline (carbonates) and possibly acidic (sulfates) conditions. Possible source phases in the Rocknest material are hydrated amorphous material, minor clay minerals, and hydrated perchlorate salts (all potential H2O sources), carbonates (CO2), perchlorates (O2 and HCl), and potential N-bearing materials (e.g., Martian nitrates, terrestrial or Martian nitrogenated organics, ammonium salts) that evolve NH3, NO, and/or HCN. We conclude that Rocknest materials are a physical mixture in chemical disequilibrium, consistent with aeolian mixing, and that although weathering is not extensive, it may be ongoing even under current Martian surface conditions.

Silver deposition and tissue staining associated with wound dressings containing silver.

PubMed

Walker, Michael; Cochrane, Christine A; Bowler, Philip G; Parsons, David; Bradshaw, Peter

2006-01-01

Argyria is the general term used to denote a clinical condition in which excessive administration and deposition of silver causes a permanent irreversible gray-blue discoloration of the skin or mucous membranes. The amount of discoloration usually depends on the route of silver delivery (ie, oral or topical administration) along with the body's ability to absorb and excrete the administered silver compound. Argyria is accepted as a rare dermatosis but once silver particles are deposited, they remain immobile and may accumulate during the aging process. Topical application of silver salts (eg, silver nitrate solution) may lead to transient skin staining. To investigate their potential to cause skin staining, two silver-containing dressings (Hydrofiber and nanocrystalline) were applied to human skin samples taken from electively amputated lower limbs. The potential for skin discoloration was assayed using atomic absorption spectroscopy. When the dressings were hydrated with water, a significantly higher amount of silver was released from the nanocrystalline dressing compared to the Hydrofiber dressing (P <0.005), which resulted in approximately 30 times more silver deposition. In contrast, when saline was used as the hydration medium, the release rates were low for both dressings and not significantly different (silver deposition was minimal). Controlling the amount of silver released from silver-containing dressings should help reduce excessive deposition of silver into wound tissue and minimize skin staining.

Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-12-01

Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Research on A3 steel corrosion behavior of basic magnesium sulfate cement

NASA Astrophysics Data System (ADS)

Xing, Sainan; Wu, Chengyou; Yu, Hongfa; Jiang, Ningshan; Zhang, Wuyu

2017-11-01

In this paper, Tafel polarization technique is used to study the corrosion behavior of A3 steel basic magnesium sulfate, and then analyzing the ratio of raw materials cement, nitrites rust inhibitor and wet-dry cycle of basic magnesium sulfate corrosion of reinforced influence, and the steel corrosion behavior of basic magnesium sulfate compared with magnesium oxychloride cement and Portland cement. The results show that: the higher MgO/MgSO4 mole ratio will reduce the corrosion rate of steel; Too high and too low H2O/MgSO4 mole ratio may speed up the reinforcement corrosion effect; Adding a small amount of nitrite rust and corrosion inhibitor, not only can obviously reduce the alkali type magnesium sulfate in the early hydration of cement steel bar corrosion rate, but also can significantly reduce dry-wet circulation under the action of alkali type magnesium sulfate cement corrosion of reinforcement effect. Basic magnesium sulfate cement has excellent ability to protect reinforced, its long-term corrosion of reinforcement effect and was equal to that of Portland cement. Basic magnesium sulfate corrosion of reinforced is far below the level in the MOC in the case.

Mechanochemical approach for synthesis of layered double hydroxides

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqing; Li, Shuping

2013-06-01

In this paper, a mechanochemical approach is used to prepare layered double hydroxides (LDHs). This approach involves manually grinding the precursor, nitrates and then the hydrothermal treatment. The study indicates that grinding leads to the incomplete formation of LDHs phase, LDHs-M. The reaction degree of precursor salts to LDHs after grinding depends on the melting points of the precursors. As expected, hydrothermal treatment is beneficial for the good crystallization and regularity of LDHs. Especially, the effect of hydrothermal treatment has been emphatically explored. The hydration of LDHs-M, increment of zeta potentials and the complete exchange of NO3- by CO32- anions occur successively or in parallel during the hydrothermal treatment. It can be found that combination of grinding and hydrothermal treatment gives rise to the formation of uniform and monodispersed particles of LDHs.

Characterization of Surface and Bulk Nitrates of γ-Al2O3-Supported Alkaline Earth Oxides using Density Functional Theory

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

Mei, Donghai; Ge, Qingfeng; Kwak, Ja Hun

2009-05-14

“Surface" and "bulk" nitrates formed on a series of alkaline earth oxides (AEOs), AE(NO3)2, were investigated using first-principles density functional theory calculations. The formation of these surface and bulk nitrates was modeled by the adsorption of NO2+NO3 pairs on gamma-Al2O3-supported monomeric AEOs (MgO, CaO, SrO, and BaO) and on the extended AEO(001) surfaces, respectively. The calculated vibrational frequencies of the surface and bulk nitrates based on our proposed models are in good agreement with experimental measurements of AEO/gamma-Al2O3 materials after prolonged NO2 exposure. This indicates that experimentally observed "surface" nitrates are most likely formed with isolated two dimensional (including monomeric)more » AEO clusters on the gamma-Al2O3 substrate, while the "bulk" nitrates are formed on exposed (including (001)) surfaces (and likely in the bulk as well) of large three dimensional AEO particles supported on the gamma-Al2O3 substrate. Also in line with the experiments, our calculations show that the low and high frequency components of the vibrations for both surface and bulk nitrates are systematically red shifted with the increasing basicity and cationic size of the AEOs. The adsorption strengths of NO2+NO3 pairs are nearly the same for the series of alumina-supported monomeric AEOs, while the adsorption strengths of NO2+NO3 pairs on the AEO surfaces increase in the order of MgO < CaO < SrO ~ BaO. Compared to the NO2+NO3 pair that only interacts with monomeric AEOs, the stability of NO2+NO3 pairs that interact with both the monomeric AEO and the gamma-Al2O3 substrate is enhanced by about 0.5 eV. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Protein pharmacophore selection using hydration-site analysis

PubMed Central

Hu, Bingjie; Lill, Markus A.

2012-01-01

Virtual screening using pharmacophore models is an efficient method to identify potential lead compounds for target proteins. Pharmacophore models based on protein structures are advantageous because a priori knowledge of active ligands is not required and the models are not biased by the chemical space of previously identified actives. However, in order to capture most potential interactions between all potentially binding ligands and the protein, the size of the pharmacophore model, i.e. number of pharmacophore elements, is typically quite large and therefore reduces the efficiency of pharmacophore based screening. We have developed a new method to select important pharmacophore elements using hydration-site information. The basic premise is that ligand functional groups that replace water molecules in the apo protein contribute strongly to the overall binding affinity of the ligand, due to the additional free energy gained from releasing the water molecule into the bulk solvent. We computed the free energy of water released from the binding site for each hydration site using thermodynamic analysis of molecular dynamics (MD) simulations. Pharmacophores which are co-localized with hydration sites with estimated favorable contributions to the free energy of binding are selected to generate a reduced pharmacophore model. We constructed reduced pharmacophore models for three protein systems and demonstrated good enrichment quality combined with high efficiency. The reduction in pharmacophore model size reduces the required screening time by a factor of 200–500 compared to using all protein pharmacophore elements. We also describe a training process using a small set of known actives to reliably select the optimal set of criteria for pharmacophore selection for each protein system. PMID:22397751

Vanishing amplitude of backbone dynamics causes a true protein dynamical transition: H2 NMR studies on perdeuterated C-phycocyanin

NASA Astrophysics Data System (ADS)

Kämpf, Kerstin; Kremmling, Beke; Vogel, Michael

2014-03-01

Using a combination of H2 nuclear magnetic resonance (NMR) methods, we study internal rotational dynamics of the perdeuterated protein C-phycocyanin (CPC) in dry and hydrated states over broad temperature and dynamic ranges with high angular resolution. Separating H2 NMR signals from methyl deuterons, we show that basically all backbone deuterons exhibit highly restricted motion occurring on time scales faster than microseconds. The amplitude of this motion increases when a hydration shell exists, while it decreases upon cooling and vanishes near 175 K. We conclude that the vanishing of the highly restricted motion marks a dynamical transition, which is independent of the time window and of a fundamental importance. This conclusion is supported by results from experimental and computational studies of the proteins myoglobin and elastin. In particular, we argue based on findings in molecular dynamics simulations that the behavior of the highly restricted motion of proteins at the dynamical transition resembles that of a characteristic secondary relaxation of liquids at the glass transition, namely the nearly constant loss. Furthermore, H2 NMR studies on perdeuterated CPC reveal that, in addition to highly restricted motion, small fractions of backbone segments exhibit weakly restricted dynamics when temperature and hydration are sufficiently high.

A cohesive-frictional force field (CFFF) for colloidal calcium-silicate-hydrates

NASA Astrophysics Data System (ADS)

Palkovic, Steven D.; Yip, Sidney; Büyüköztürk, Oral

2017-12-01

Calcium-silicate-hydrate (C-S-H) gel is a cohesive-frictional material that exhibits strength asymmetry in compression and tension and normal-stress dependency of the maximum shear strength. Experiments suggest the basic structural component of C-S-H is a colloidal particle with an internal layered structure. These colloids form heterogeneous assemblies with a complex pore network at the mesoscale. We propose a cohesive-frictional force field (CFFF) to describe the interactions in colloidal C-S-H materials that incorporates the strength anisotropy fundamental to the C-S-H molecular structure that has been omitted from recent mesoscale models. We parameterize the CFFF from reactive force field simulations of an internal interface that controls mechanical performance, describing the behavior of thousands of atoms through a single effective pair interaction. We apply the CFFF to study the mesoscale elastic and Mohr-Coulomb strength properties of C-S-H with varying polydispersity and packing density. Our results show that the consideration of cohesive-frictional interactions lead to an increase in stiffness, shear strength, and normal-stress dependency, while also changing the nature of local deformation processes. The CFFF and our coarse-graining approach provide an essential connection between nanoscale molecular interactions and macroscale continuum behavior for hydrated cementitious materials.

Effects of cosmetics on the skin microbiome of facial cheeks with different hydration levels.

PubMed

Lee, Hyo Jung; Jeong, Sang Eun; Lee, Soyoun; Kim, Sungwoo; Han, Hyuntak; Jeon, Che Ok

2018-04-01

Basic cosmetics was used by volunteers belonging to high (HHG) and low (LHG) hydration groups for 4 weeks, and bacterial communities and biophysical parameters in facial skin were analyzed. Hydration level increases and transepidermal water loss and roughness decreases were observed in both groups after cosmetic use. Bacterial diversity was greater in LHG than HHG, and increased after cosmetic use in both groups. Bray-Curtis dissimilarities that were higher in LHG than HHG increased in HHG after cosmetic use, whereas they decreased in LHG. The phyla Actinobacteria, Proteobacteria, Firmicutes, and Bacteroidetes and the genera Propionibacterium, Ralstonia, Burkholderia, Staphylococcus, Corynebacterium, Cupriavidus, and Pelomonas were identified as common groups and they were not significantly different between LHG and HHG except for Propionibacterium that was more abundant in HHG. After cosmetic use, Propionibacterium, Staphylococcus, and Corynebacterium decreased, whereas Ralstonia, not a core genus, increased, as did KEGG categories of lipid metabolism and xenobiotics biodegradation and metabolism, suggesting that Ralstonia in skin may have the ability to metabolize cosmetics components. Bacterial communities after cosmetic use were different from those in both LHG and HHG before the cosmetic use, indicating that bacterial communities in LHG were not shifted to resemble those in HHG by cosmetics use. © 2017 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

Unraveling the Decomposition Process of Lead(II) Acetate: Anhydrous Polymorphs, Hydrates, and Byproducts and Room Temperature Phosphorescence.

PubMed

Martínez-Casado, Francisco J; Ramos-Riesco, Miguel; Rodríguez-Cheda, José A; Cucinotta, Fabio; Matesanz, Emilio; Miletto, Ivana; Gianotti, Enrica; Marchese, Leonardo; Matěj, Zdeněk

2016-09-06

Lead(II) acetate [Pb(Ac)2, where Ac = acetate group (CH3-COO(-))2] is a very common salt with many and varied uses throughout history. However, only lead(II) acetate trihydrate [Pb(Ac)2·3H2O] has been characterized to date. In this paper, two enantiotropic polymorphs of the anhydrous salt, a novel hydrate [lead(II) acetate hemihydrate: Pb(Ac)2·(1)/2H2O], and two decomposition products [corresponding to two different basic lead(II) acetates: Pb4O(Ac)6 and Pb2O(Ac)2] are reported, with their structures being solved for the first time. The compounds present a variety of molecular arrangements, being 2D or 1D coordination polymers. A thorough thermal analysis, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), was also carried out to study the behavior and thermal data of the salt and its decomposition process, in inert and oxygenated atmospheres, identifying the phases and byproducts that appear. The complex thermal behavior of lead(II) acetate is now solved, finding the existence of another hydrate, two anhydrous enantiotropic polymorphs, and some byproducts. Moreover, some of them are phosphorescent at room temperature. The compounds were studied by TGA, DSC, X-ray diffraction, and UV-vis spectroscopy.

Kinetic Studies and Product Characterization during the Basic Hydrolysis of Glyceryl Nitrate Esters

DTIC Science & Technology

1979-08-01

elaborate instrumentation, which was considered too time consuming and costly to construct for this study. 25 The quantitative estimation of the calcium...0.6 [ l-exp(- Kfc ) 1 Figure 21. Formation of N03~ during hydrolysis of 1-MNG in aqueous Ca(0H)2 solution at 25°C (See Tables 2 and 8) 6 5

IDAHO CHEMICAL PROCESSING PLANT TECHNICAL PROGRESS REPORT FOR APRIL THROUGH JUNE 1958

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

Stevenson, C.E.

1958-11-01

Processing of uranium -aluminum alloy was continued with slight process modifications. Means for recovering rare gases from dissolver off-gas are described. Results of extensive decontamination procedures required to enable entrance to the continuous dissolver cell are also indicated. Pilot plant studies of dissolving aluminum continuously showed that rates of dissolution were decreased by factors of 2 to 4 as the concentration of nitric acid fed was increased from 5.4 to 11N. The rate of aluminum dissolution was found to be proportional to initial area exposed for pieces of different shape. It was found possible to produce a highly basic aluminummore » nitrate solution at a reasonable rate by dissolving to low concentration in dilute acid, followed by evaporation to the desired level. Uranium exchange rate measurements for the TBP extraction process are described. A canned rotor pump under test with graphite bearings operated 6000 hours with nominal wear. Difficulties were experienced in testing a nutating disc pump. Measurements of the potential of zirconium in hydrofluoric acid as a function of pH confirmed the predicted equation. In teflon vessels, zirconium dissolves a little more rapidly in nitric-hydrofluoric acid mixtures than in glass vessels, presumably due to reaction of fluoride with silica. Titunium alloy Types 55A and 75A were found to resist corrosion by certain boiling nitric-hydrochloric acid mixtures. Initial tests have commenced with a NaK-heated 100 liter/hour pilot plant aluminum nitrate calciner to continue process demonstration. In tests in the smaller pilot plant unit, increasing feed spray air ratio was found to increase particle loading in the cyclone effluent. Laboratory studies indicated that a venturi scrubber using dilute nitric acid at 80 C should remove ruthenium effectively from calciner off-gas. In a pilot plant test in which a significant fraction of ruthenium feed was retained by the alumina, substantial absorption of volatilized ruthenium was obtained. Thermal conductivity of alumina near 3000 F was about 0.26 Btu/hr)(ft)( F). In leaching studies, very little strontium or plutonium was removed by water from alumina calcined at 550 C. Dilute nitric acid, however, extracted strontium from this material to the same degree (~ 50 percent) as from material calcined at 400 C. Concentrated basic aluminum nitrate was produced from simulated aluminum nitrate waste by slow hydrolysis with urea followed by evaporation. Aluminum was efficiently extracted from buffered aluminum nitrate solution by acetylacetone and was stripped back into nitric acid. A filterable aluminum phosphate was precipituted from aluminum nitrate solution by urea hydrolysis; the phosphate effectively carried fission products, however. Spectrophotometric methods were developed for macro and micro quantities of uranium, in the presence of high concentrations of other ions, based on tetrapropylammonium nitrate extraction. (For preceding period see ID0-14443.) (auth)« less

Influence of hydroponic and soil cultivation on quality and shelf life of ready-to-eat lamb's lettuce (Valerianella locusta L. Laterr).

PubMed

Manzocco, Lara; Foschia, Martina; Tomasi, Nicola; Maifreni, Michela; Dalla Costa, Luisa; Marino, Marilena; Cortella, Giovanni; Cesco, Stefano

2011-06-01

Nowadays, there is an increasing interest in the hydroponic floating system to cultivate leafy vegetables for ready-to-eat salads. It is reasonable that different growing systems could affect the quality and shelf life of these salads. The quality and shelf life of ready-to-eat lamb's lettuce grown in protected environment in soil plot or in soil-less system over hydroponic solution with or without the addition of 30 µmol L⁻¹ silicon were evaluated. Minimum effects were observed on colour, firmness and microbial counts. Hydroponic cultivation largely affected plant tissue hydration, leading to weight loss and structural modifications during refrigerated storage. The shelf life of lamb's lettuce was limited by the development of visually detectable unpleasant sensory properties. Shelf life, calculated by survival analysis of consumer acceptability data, resulted about 7 days for soil-cultivated salad and 2 days for the hydroponically grown ones. The addition of silicon to the hydroponic solution resulted in an interesting strategy to increase plant tissue yield and reduce nitrate accumulation. Although hydroponic cultivation may have critical consequences on product quality and shelf life, these disadvantages could be largely counterbalance by increased yield and a reduction of nitrate accumulation when cultivation is performed on nutritive solutions with supplemental addition of silicon. Copyright © 2011 Society of Chemical Industry.

Synthesis and theoretical studies on nitrogen-rich salts of bis[4-nitraminofurazanyl-3-azoxy]azofurazan (ADNAAF).

PubMed

Zheng, Chunmei; Chu, Yuting; Xu, Liwen; Lei, Wu; Wang, Fengyun; Xia, Mingzhu

2017-01-01

Multi-furazan compounds bis[4-nitramino- furazanyl-3-azoxy]azofurazan (ADNAAF) and its derivatives were first synthesized by our research group, and their structures were characterized by IR, 1 H-NMR, 13 C-NMR spectrums, and element analysis. ADNAAF was synthesized by nitration reaction of bis[4-aminofurazanyl-3-azoxy]azofurazan (ADAAF), and then reacted with ammonium hydroxide, hydrazine hydrate, and guanidine nitrate to obtain three salts marked as salt 1, 2, and 3, respectively. The thermal stabilities of the three salts were supported by the results of DSC analysis, which shows the decomposition temperatures are all above 190 °C. Their densities, enthalpies of formation, and detonation properties were studied by density functional theory (DFT) method. Salt 1 has the best detonation pressure (P), 37.42 GPa, and detonation velocity (D), 8.88 km/s, while salt 2 has the best nitrogen content and heat of detonation (Q), 1.27 kcal mol -1 . The detonation properties of salt 1 is similar to that of 1,3,5-trinitro-1,3,5-triazineane (RDX). It means that the ammonium cation can provide the better D and P than the cation of hydrazine and guanidine. The three cations offer the enthalpies of formations in the order of hydrazinium > guanidinium > ammonium. Graphical Abstract Nitrogen-rich salts of bis[4-nitraminofurazanyl-3-azoxy]azofurazan(ADNAAF).

Geochemical impacts of waste disposal on the abyssal seafloor

NASA Astrophysics Data System (ADS)

Jahnke, Richard A.

1998-05-01

The response of pore water oxygen, nitrate, sulfate, sulfide, ammonium and methane and particulate organic carbon distributions to the input of 8.5 million m 3 (3.8×10 12 g) of organic-rich waste materials is simulated. The deposit is assumed to be conical with a maximum thickness of approximately 20 m. Remineralization reactions within the deposit rapidly deplete any initially available pore water oxidants such as oxygen, nitrate and sulfate, and are subsequently dominated by fermentation reactions. Diffusion downward of reduced metabolites, sulfide, ammonium and methane, depletes the available oxidants in the pore waters below the waste pile, increasing the thickness of the anoxic layer. While the impacted region is limited to essentially the deposition site, recovery of the pore waters is estimated to be >10 4 years. The overall computational results are corroborated by the pore water distributions observed at turbidite boundaries. Numerous uncertainties in the parameterizations limit the overall accuracy of the calculations presented. The most significant of these are: (1) A quantitatively accurate assessment of the remineralization rate of the deposited organic matter including its rate of inoculation by abyssal microorganisms; (2) a detailed assessment of potential non-diffusive pore water transport processes including advection due to compaction and buoyancy-driven flows and enhanced exchange due to macrobenthic irrigation activities and (3) an assessment of the potential alteration of pore space and methane reactivity due to gas hydrate formation.

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.

Effects of dietary nitrate supplementation on symptoms of acute mountain sickness and basic physiological responses in a group of male adolescents during ascent to Mount Everest Base Camp.

PubMed

Hennis, Philip J; Mitchell, Kay; Gilbert-Kawai, Edward; Bountziouka, Vassiliki; Wade, Angie; Feelisch, Martin; Grocott, Michael P; Martin, Daniel S

2016-11-30

The purpose of this study was to investigate the effects of dietary nitrate supplementation, in the form of beetroot juice, on acute mountain sickness (AMS) symptoms and physiological responses, in a group of young males trekking to Mount Everest Base Camp (EBC). Forty healthy male students (mean age (SD): 16 (1) yrs) trekked to EBC over 11 days. Following an overnight fast, each morning participants completed the Lake Louise AMS questionnaire and underwent a series of physiological tests: resting blood pressure as well as resting and exercising heart rate, respiratory rate, and peripheral oxygen saturation. The exercise test consisted of a standardised 2-min stepping protocol and measurements were taken in the last 10 s. Participants in the intervention arm of the study consumed 140 ml of concentrated beetroot juice daily, containing approximately 10 mmol of nitrate, while those in the control arm consumed 140 ml of concentrated blackcurrant cordial with negligible nitrate content. Drinks were taken for the first seven days at high altitude (days 2-8), in two equal doses; one with breakfast, and one with the evening meal. Mixed modelling revealed no significant between-groups difference in the incidence of AMS (Odds Ratio - nitrate vs. 1.16 (95% CI: 0.59; 2.29)). Physiological changes occurring during ascent to high altitude generally were not significantly different between the two groups (Model Coef (95% CI) - average difference nitrate vs. systolic blood pressure, 0.16 (-4.47; 4.79); peripheral oxygen saturation, 0.28 (-0.85; 1.41); heart rate, -0.48 (-8.47; 7.50) (Model Coef (95% CI) - relative difference nitrate vs. ventilatory rate, 0.95 (0.82; 1.08)). Modelling revealed that diastolic blood pressure was 3.37 mmHg (0.24; 6.49) higher for participants in the beetroot juice, however this difference was no larger than that found at baseline and no interaction effect was observed. Supplementation with dietary nitrate did not significantly change symptoms of AMS or alter key physiological variables, in a group of adolescent males during a high altitude trekking expedition. There was no evidence of harm from dietary nitrate supplementation in this context. Given the wide confidence intervals in all models, a larger sample size would be required to exclude a false negative result. Our data suggest that prolonged oral nitrate supplementation is safe and feasible at altitude but has little physiological or clinical effect. Copyright © 2016 Elsevier Inc. All rights reserved.

Environmentally Benign Stab Detonators

DTIC Science & Technology

2006-07-11

composition. In addition we will work with our DoD partner TACOM-ARDEC in identifying and testing more environmentally suitable replacement transfer...components identified is shown in Figure 1 below. Figure 1. Photo of M55 stab detonator Al cup with initiation train and components. Common...primer mixes, such as NOL-130, are made up of lead styphnate (basic) 40%, lead azide ( dextrinated ) 20%, barium nitrate 20%, antimony sulfide 15%, and

Note: Real time optical sensing of alpha-radiation emitting radioactive aerosols based on solid state nuclear track detector.

PubMed

Kulkarni, A; Ha, S; Joshirao, P; Manchanda, V; Bak, M S; Kim, T

2015-06-01

A sensitive radioactive aerosols sensor has been designed and developed. Its design guidance is based on the need for a low operational cost and reliable measurements to provide daily aerosol monitoring. The exposure of diethylene-glycol bis (allylcarbonate) to radiation causes modification of its physico-chemical properties like surface roughness and reflectance. In the present study, optical sensor based on the reflectance measurement has been developed with an aim to monitor real time presence of alpha radioactive aerosols emitted from thorium nitrate hydrate. The results shows that the fabricated sensor can detect 0.0157 kBq to 0.1572 kBq of radio activity by radioactive aerosols generated from (Th(NO3)4 ⋅ 5H2O) at 0.1 ml/min flow rate. The proposed instrument will be helpful to monitor radioactive aerosols in/around a nuclear facility, building construction sites, mines, and granite polishing factories.

Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2015-05-22

We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation ofmore » four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.« less

Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

PubMed

Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

2018-05-23

Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

Moisturizing and Antiinflammatory Properties of Cosmetic Formulations Containing Centella asiatica Extract

PubMed Central

Ratz-Łyko, A.; Arct, J.; Pytkowska, K.

2016-01-01

Centella asiatica extract is a rich source of natural bioactive substances, triterpenoid saponins, flavonoids, phenolic acids, triterpenic steroids, amino acids and sugars. Thus, many scavenging free radicals, exhibit antiinflammatory activity and affect on the stratum corneum hydration and epidermal barrier function. The aim of the present study was to evaluate the in vivo moisturizing and antiinflammatory properties of cosmetic formulations (oil-in-water emulsion cream and hydrogel) containing different concentrations of Centella asiatica extract. The study was conducted over four weeks on a group of 25 volunteers after twice a day application of cosmetic formulations with Centella asiatica extract (2.5 and 5%, w/w) on their forearms. The measurement of basic skin parameters (stratum corneum hydration and epidermal barrier function) was performed once a week. The in vivo antiinflammatory activity based on the methyl nicotinate model of microinflammation in human skin was evaluated after four weeks application of tested formulations. In vivo tests formulations containing 5% of Centella asiatica extract showed the best efficacy in improving skin moisture by increase of skin surface hydration state and decrease in transepidermal water loss as well as exhibited antiinflammatory properties based on the methyl nicotinate model of microinflammation in human skin. Comparative tests conducted by corneometer, tewameter and chromameter showed that cosmetic formulations containing Centella asiatica extract have the moisturizing and antiinflammatory properties. PMID:27168678

Anoxic control of odour and corrosion from sewer networks.

PubMed

Yang, W; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Anoxic processes can effectively control odour and corrosion in sewer networks. However, the absence of fundamental knowledge on the kinetics of anoxic transformation of sewage prevents the engineering applications of anoxic control in sewers. This paper focuss on a basic understanding of the anoxic transformations needed for a conceptual simulation of the water phase processes. Experiments conducted in batch reactors have shown that nitrite builds up in wastewater during denitrification. Part of the nitrate-reducing biomass is capable of utilizing nitrite after nitrate is depleted. Compared with aerobic transformation, anoxic processes have low values of maximum growth rate of the biomass and also a low endogenous respiration rate. Heterotrophic yield determined under anoxic conditions, at level of 0.25 mmol e-eq (mmol e-eq)(-1), accounted for less than 40% of the corresponding aerobic values.

Hydrogeochemistry of groundwaters in and below the base of thick permafrost at Lupin, Nunavut, Canada

NASA Astrophysics Data System (ADS)

Stotler, Randy L.; Frape, Shaun K.; Ruskeeniemi, Timo; Ahonen, Lasse; Onstott, Tullis C.; Hobbs, Monique Y.

2009-06-01

SummaryShield fluids are commonly understood to evolve through water-rock interaction. However, fluids may also concentrate during ice formation. Very little is currently known about groundwater conditions beneath thick permafrost in crystalline environments. This paper evaluates three possible Shield fluid evolution pathways at a crystalline Shield location currently under 500+ meters of permafrost, including surfical cryogenic concentration of seawater, in situ cryogenic concentration and water-rock interaction. A primary goal of this study was to further scientific understanding of permafrost and its role in influencing deep flow system evolution, fluid movement and chemical evolution of waters in crystalline rocks. Precipitation, surface, permafrost and subpermafrost water samples were collected, as well as dissolved and free gas samples, fracture fillings and matrix fluid samples to characterize the site. Investigations of groundwater conditions beneath thick permafrost provides valuable information which can be applied to safety assessment of deep, underground nuclear waste repositories, effects of long-term mining in permafrost areas and understanding analogues to potential life-bearing zones on Mars. The study was conducted in the Lupin gold mine in Nunavut, Canada, located within the zone of continuous permafrost. Through-taliks beneath large lakes in the area provided potential hydraulic connections through the permafrost. Na-Cl and Na-Cl-SO 4 type permafrost waters were contaminated by mining activities, affecting the chloride and nitrate concentrations. High nitrate concentrations (423-2630 mg L -1) were attributed to remnants of blasting. High sulfate concentrations in the permafrost (578-5000 mg L -1) were attributed to naturally occurring and mining enhanced sulfide oxidation. Mine dewatering created an artificial hydraulic gradient, resulting in methane hydrate dissociation at depth. Less contaminated basal waters had medium sulfate concentrations and were Ca-Na dominated, similar to deeper subpermafrost waters. Subpermafrost waters had a wide range of salinities (2.6-40 g L -1). It was unclear from this investigation what impact talik waters would have on deep groundwaters in undisturbed environments. In situ cryogenic concentration due to ice and methane hydrate formation may have concentrated the remaining fluids, however there was no evidence that infiltration of cryogenically concentrated seawater occurred since the last glacial maximum. Matrix waters were dilute and unable to affect groundwater salinity. Fracture infillings were scarce, but calcite fluid inclusion microthermometry indicated a large range in salinities, potentially an additional source of salinity to the system.

A Comprehensive Review of the Treatment of Atopic Eczema

PubMed Central

Lee, Ji Hyun

2016-01-01

Atopic eczema (AE) is a chronic, inflammatory skin disorder which usually develops in early childhood. In spite of intensive investigations, the causes of AE remain unclear, but are likely to be multifactorial in nature. Environmental factors or genetic-environmental interactions seem to play a key role in disease progression. Among various measures of AE managment, cutaneous hydration, which improves barrier function and relieve itchiness, may be helpful to reduce the need for topical steroid use and therefore should be used as a basic treatment. Avoiding aggravating factors is also a basic treatment of AE. Standard medical treatment with a pharmacologic approach may be necessary if basic treatment fails to control symptoms satisfactorily. Recently, more attention is given to a proactive therapeutic by regular intermittent application of low potency steroids or topical calcineurin inhibitors to prevent new flares. Furthermore, various targeted biologics are being introduced for AE control and are proposed as promising therapies. This paper provides a summary of the recent literature on the manangement of AE and a treatment guideline. PMID:26922927

NO2 uptake under practically relevant conditions on BaO/Pt(111)

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

Mudiyanselage, Kumudu; Szanyi, János

2012-02-01

The formation of nitrites and nitrates (Ba(NOx)2) under practically relevant conditions (PNO2 up to 1.0 Torr and T = 500 K) and their thermal decomposition on BaO (>20 monolayer equivalent (MLE))/Pt(1 1 1) were studied using temperature programmed desorption (TPD), infrared reflection absorption (IRA), and Xray photoelectron (XP) spectroscopies. The exposure of BaO to 1.0 × 10-8 Torr NO2 at 500 K leads to the formation of a Ba(NOx)2 layer with small, disordered crystalline nitrate clusters. Under these conditions (PNO2 = 1.0 × 10-8 Torr and T = 500 K) only the top portion of the BaO layer converts tomore » Ba(NOx)2 and the nitrites in this Ba(NOx)2 layer stay without converting completely to nitrates even after 100 min of NO2 exposure. In the thermal decomposition of Ba(NOx)2, first nitrites decompose, releasing NO and then the decomposition of nitrates occurs via two pathways releasing NO2 and NO + O2. At 500 K and PNO2 ≥ 1.0 × 10-7 Torr, first NO2 reacts with BaO to form small disordered crystalline Ba(NO3)2 particles and then these particles agglomerate to form large, well-ordered (bulk-like) crystalline nitrates as the NO2 exposure increases. The thermal decomposition of these well-ordered, bulk-like crystalline nitrate aggregates occurs in two steps releasing NO2 and NO + O2 in each step in two different temperature regions. NO2 pressure ≥1.0 × 10-5 Torr is required for the complete oxidation of initially formed nitrites to nitrates and the full nitration of the BaO layer at 500 K sample temperature. We gratefully acknowledge the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.« less

Understanding ethylammonium nitrate stabilized cytochrome c - Molecular dynamics and experimental approach

NASA Astrophysics Data System (ADS)

Jaganathan, Maheshkumar; Ramakrishnan, C.; Velmurugan, D.; Dhathathreyan, Aruna

2015-02-01

For a conceptual understanding of how an ionic liquid stabilizes a solvated protein, in this study, using new force field parameters, a molecular dynamics simulation (MDS) of the loop and helical regions of hydrated Cytochrome c (cyt c) and its interaction with the ionic liquid ethylammonium nitrate (EAN) have been studied. For a simulation trajectory of 100 ns, the changes in network of water around the protein due to EAN and subsequent reorganization of the protein have been analyzed. The radii of gyration of solvated cyt c (13.7 Å) and cyt c + EAN (13.4 Å) at the end of the trajectory are higher than the protein in its crystalline state (12.64 Å) suggesting enhanced stability of the protein due to tightly organized assembly of EAN near the solvated cyt c. This increase in stability of the protein has been verified experimentally using fluorescence, circular dichroic spectroscopy and differential scanning calorimetry. With increasing EAN in cyt c + EAN, protein conformation shows unusually high β strand population. To check whether the beta strand is an intermediate or a local minimum state, denaturation of cyt c with urea in the presence of EAN has been undertaken. Results show that EAN helps in renaturation of the protein by forming a tightly organized assembly around the protein with the beta strand state appearing as a local minimum energy state. Thus the feasibility of using ionic liquids to form networks around the protein and their possible applications in stabilization of the proteins has been demonstrated.

Electron spin resonance. Part two: a diagnostic method in the environmental sciences.

PubMed

Rhodes, Christopher J

2011-01-01

A review is presented of some of the ways in which electron spin resonance (ESR) spectroscopy may be useful to investigate systems of relevance to the environmental sciences. Specifically considered are: quantititave ESR, photocatalysis for pollution control; sorption and mobility of molecules in zeolites; free radicals produced by mechanical action and by shock waves from explosives; measurement of peroxyl radicals and nitrate radicals in air; determination of particulate matter polyaromatic hydrocarbons (PAH), soot and black carbon in air; estimation of nitrate and nitrite in vegetables and fruit; lipid-peroxidation by solid particles (silica, asbestos, coal dust); ESR of soils and other biogenic substances: formation of soil organic matter carbon capture and sequestration (CCS) and no-till farming; detection of reactive oxygen species in the photosynthetic apparatus of higher plants under light stress; molecular mobility and intracellular glasses in seeds and pollen; molecular mobility in dry cotton; characterisation of the surface of carbon black used for chromatography; ESR dating for archaeology and determining seawater levels; measurement of the quality of tea-leaves by ESR; green-catalysts and catalytic media; studies of petroleum (crude oil); fuels; methane hydrate; fuel cells; photovoltaics; source rocks; kerogen; carbonaceous chondrites to find an ESR-based marker for extraterrestrial origin; samples from the Moon taken on the Apollo 11 and Apollo 12 missions to understand space-weathering; ESR studies of organic matter in regard to oil and gas formation in the North Sea; solvation by ionic liquids as green solvents, ESR in food and nutraceutical research.

Determining Roles of Accessory Genes in Denitrification by Mutant Fitness Analyses

PubMed Central

Vaccaro, Brian J.; Thorgersen, Michael P.; Lancaster, W. Andrew; Price, Morgan N.; Wetmore, Kelly M.; Poole, Farris L.; Deutschbauer, Adam; Arkin, Adam P.

2015-01-01

Enzymes of the denitrification pathway play an important role in the global nitrogen cycle, including release of nitrous oxide, an ozone-depleting greenhouse gas. In addition, nitric oxide reductase, maturation factors, and proteins associated with nitric oxide detoxification are used by pathogens to combat nitric oxide release by host immune systems. While the core reductases that catalyze the conversion of nitrate to dinitrogen are well understood at a mechanistic level, there are many peripheral proteins required for denitrification whose basic function is unclear. A bar-coded transposon DNA library from Pseudomonas stutzeri strain RCH2 was grown under denitrifying conditions, using nitrate or nitrite as an electron acceptor, and also under molybdenum limitation conditions, with nitrate as the electron acceptor. Analysis of sequencing results from these growths yielded gene fitness data for 3,307 of the 4,265 protein-encoding genes present in strain RCH2. The insights presented here contribute to our understanding of how peripheral proteins contribute to a fully functioning denitrification pathway. We propose a new low-affinity molybdate transporter, OatABC, and show that differential regulation is observed for two MoaA homologs involved in molybdenum cofactor biosynthesis. We also propose that NnrS may function as a membrane-bound NO sensor. The dominant HemN paralog involved in heme biosynthesis is identified, and a CheR homolog is proposed to function in nitrate chemotaxis. In addition, new insights are provided into nitrite reductase redundancy, nitric oxide reductase maturation, nitrous oxide reductase maturation, and regulation. PMID:26452555

SURVEY OF RECENT DEVELOPMENTS IN SOLVENT EXTRACTION WITH TRIBUTYL PHOSPHATE

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

Blanco, R.E.; Blake, C.A. Jr.; Davis, W. Jr.

Tributyl phosphate can be used for extraction in processing all current power reactor fuels. Nitric acid is the only salting agent required. Typical flowsheets are presented. In aluminum nitrate systems which are more than 0.1 M acid deficient, the uranium distribution coefficient is a function of pH and independent of aluminum concentration; the coefficient remains constant at one in fluoride systems when the nitrate to fluoride ratio is approximates 3.5. Many objectionable properties of degraded diluents are ascribed to nitroparaffins. Aliphatic diluents with the least branching are the most stable to nitration. The nitration stability of aromatic diluents varies withmore » structure, e.g., stabilities of diethylbenzenes decrease as meta >> ortho > para. Solvent purification by flash distillation appears superior to other methods. The stability of Amsco 125-82 was permanently improved by treatment with sulfuric acid. The radiation stability of TBP was approximates 2 times higher in an aromatic diluent than in Amsco 125-82. The G decomposition value for 1 M TBP in Amsco alone was approximates 0.9; whereas in 1 to 3 M HNO/sub 3/ it was 1 to 5 and G (--HNO/sub 3/ org phase) was 3 to 20. Variation of uranium--thorium separation factors with structure of some neutral organophosphorus reagents is presented. Basic studies include measurement of activities in multicomponent solutions and description of aqueous activity coefficients by an extended Debye- Huckel equation. (auth)« less

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

Vaccaro, Brian J.; Thorgersen, Michael P.; Lancaster, W. Andrew

Enzymes of the denitrification pathway play an important role in the global nitrogen cycle, including release of nitrous oxide, an ozone-depleting greenhouse gas. In addition, nitric oxide reductase, maturation factors, and proteins associated with nitric oxide detoxification are used by pathogens to combat nitric oxide release by host immune systems. While the core reductases that catalyze the conversion of nitrate to dinitrogen are well understood at a mechanistic level, there are many peripheral proteins required for denitrification whose basic function is unclear. A bar-coded transposon DNA library fromPseudomonas stutzeristrain RCH2 was grown under denitrifying conditions, using nitrate or nitrite asmore » an electron acceptor, and also under molybdenum limitation conditions, with nitrate as the electron acceptor. Analysis of sequencing results from these growths yielded gene fitness data for 3,307 of the 4,265 protein-encoding genes present in strain RCH2. The insights presented here contribute to our understanding of how peripheral proteins contribute to a fully functioning denitrification pathway. We propose a new low-affinity molybdate transporter, OatABC, and show that differential regulation is observed for two MoaA homologs involved in molybdenum cofactor biosynthesis. We also propose that NnrS may function as a membrane-bound NO sensor. Finally, the dominant HemN paralog involved in heme biosynthesis is identified, and a CheR homolog is proposed to function in nitrate chemotaxis. In addition, new insights are provided into nitrite reductase redundancy, nitric oxide reductase maturation, nitrous oxide reductase maturation, and regulation.« less

Long-term record of atmospheric and snow surface nitrate from Dome C (Central Antarctica)

NASA Astrophysics Data System (ADS)

Traversi, Rita; Becagli, Silvia; Brogioni, Marco; Caiazzo, Laura; Ciardini, Virginia; Giardi, Fabio; Legrand, Michel; Macelloni, Giovanni; Petkov, Boyan; Preunkert, Suzanne; Scarchilli, Claudio; Severi, Mirko; Vitale, Vito; Udisti, Roberto

2017-04-01

Nitrate is the end product of the oxidation of atmospheric nitrogen oxides and one of the most abundant ions present in polar ice and snow, mainly as nitric acid in present-climate conditions. Nitrate stratigraphies from snow and ice layers have the potential to provide records of past changes in atmospheric composition, including atmospheric NOx cycling and oxidative capacity, as well as past solar activity or major variations in Earth's magnetic field. Nevertheless, in order to exploit such a potential, chemical concentrations in the air, snow, firn and ice core need to be correlated. Hence, the knowledge of the link between atmosphere and snow composition at the time of deposition is basic to reconstruct past climate and past atmospheric chemical composition. The extent of such knowledge depends on whether the species of interest are gaseous or in the condensed phase, and if they are reversible and/or irreversibly deposited to snow. In order to provide a contribution to their air-to-snow exchange in the Antarctic plateau, as well as to the understanding of dominant sources and sinks of nitrate, we present here nitrate records in atmospheric aerosol and surface snow sampled at high resolution, all year-round, at Dome C along 9 years (November 2004 - November 2013). This represents the longest and most highly resolved record from continental Antarctica, where continuous and long-term atmosphere and snow samplings are particularly difficult due to the extreme meteorological conditions and, at the same time, need of extra-care in avoiding contamination due to the low level of ion concentrations. Results confirm, on a larger statistical data set with respect to previous observations, nitrate seasonal pattern with summer maxima both for aerosol and surface snow, in-phase with UV solar irradiance. Such a temporal pattern is likely a combination of nitrate sources and post-depositional processes that enhance during summer. Moreover, a case study of synoptic analysis for a major nitrate event showed the occurrence of a stratosphere-troposphere exchange in the sampled days. The sampling of both matrices carried out at high resolution at the same time allowed detecting a recurring lag, about one-month long, of summer maxima in snow with respect to aerosol. Such a temporal shift can be explained only by taking into account deposition and post-deposition processes taking place at the atmosphere-snow interface, including likely both a net uptake of gaseous nitric acid and a replenishment of the uppermost surface layers driven by a larger temperature gradient in summer. Such a possibility was tested in a preliminary way by a comparison with measurements of surface layers temperature carried out in 2012-13 time period. A comparison with nitrate concentration in the gas phase and total nitrate obtained from Dome C (2012-13) showed the major role of gaseous HNO3 to total nitrate budget hinting to the need of further investigation of the gas-to-particle conversion processes.

The Pd-Catalyzed Conversion of Aryl Chlorides, Triflates, and Nonaflates to Nitroaromatics

PubMed Central

Fors, Brett P.; Buchwald, Stephen L.

2009-01-01

An efficient Pd-catalyst for the transformation of aryl chlorides, triflates and nonaflates to nitroaromatics has been developed. This reaction proceeds under weekly basic conditions and displays a broad scope and excellent functional group compatibility. Moreover, this method allows for the synthesis of aromatic nitro compounds that cannot be accessed efficiently via other nitration protocols. Mechanistic insight into the trasmetallation step of the catalytic process is also reported. PMID:19737014

Hydration of dicalcium silicate and diffusion through neo-formed calcium-silicate-hydrates at weathered surfaces control the long-term leaching behaviour of basic oxygen furnace (BOF) steelmaking slag.

PubMed

Stewart, Douglas I; Bray, Andrew W; Udoma, Gideon; Hobson, Andrew J; Mayes, William M; Rogerson, Mike; Burke, Ian T

2018-04-01

Alkalinity generation and toxic trace metal (such as vanadium) leaching from basic oxygen furnace (BOF) steel slag particles must be properly understood and managed by pre-conditioning if beneficial reuse of slag is to be maximised. Water leaching under aerated conditions was investigated using fresh BOF slag at three different particle sizes (0.5-1.0, 2-5 and 10 × 10 × 20 mm blocks) and a 6-month pre-weathered block. There were several distinct leaching stages observed over time associated with different phases controlling the solution chemistry: (1) free-lime (CaO) dissolution (days 0-2); (2) dicalcium silicate (Ca 2 SiO 4 ) dissolution (days 2-14) and (3) Ca-Si-H and CaCO 3 formation and subsequent dissolution (days 14-73). Experiments with the smallest size fraction resulted in the highest Ca, Si and V concentrations, highlighting the role of surface area in controlling initial leaching. After ~2 weeks, the solution Ca/Si ratio (0.7-0.9) evolved to equal those found within a Ca-Si-H phase that replaced dicalcium silicate and free-lime phases in a 30- to 150-μm altered surface region. V release was a two-stage process; initially, V was released by dicalcium silicate dissolution, but V also isomorphically substituted for Si into the neo-formed Ca-Si-H in the alteration zone. Therefore, on longer timescales, the release of V to solution was primarily controlled by considerably slower Ca-Si-H dissolution rates, which decreased the rate of V release by an order of magnitude. Overall, the results indicate that the BOF slag leaching mechanism evolves from a situation initially dominated by rapid hydration and dissolution of primary dicalcium silicate/free-lime phases, to a slow diffusion limited process controlled by the solubility of secondary Ca-Si-H and CaCO 3 phases that replace and cover more reactive primary slag phases at particle surfaces.

Quantum Calculations on Salt Bridges with Water: Potentials, Structure, and Properties

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

Liao, Sing; Green, Michael E.

2011-01-01

Salt bridges are electrostatic links between acidic and basic amino acids in a protein; quantum calculations are used here to determine the energetics and other properties of one form of these species, in the presence of water molecules. The acidic groups are carboxylic acids (aspartic and glutamic acids); proteins have two bases with pK above physiological pH: one, arginine, with a guanidinium basic group, the other lysine, which is a primary amine. Only arginine is modeled here, by ethyl guanidinium, while propionic acid is used as a model for either carboxylic acid. The salt bridges are accompanied by 0-12 watermore » molecules; for each of the 13 systems, the energy-bond distance relation, natural bond orbitals (NBO), frequency calculations allowing thermodynamic corrections to room temperature, and dielectric constant dependence, were all calculated. The water molecules were found to arrange themselves in hydrogen bonded rings anchored to the oxygens of the salt bridge components. This was not surprising in itself, but it was found that the rings lead to a periodicity in the energy, and to a 'water addition' rule. The latter shows that the initial rings, with four oxygen atoms, become five member rings when an additional water molecule becomes available, with the additional water filling in at the bond with the lowest Wiberg index, as calculated using NBO. The dielectric constant dependence is the expected hyperbola, and the fit of the energy to the inverse dielectric constant is determined. There is an energy periodicity related to ring formation upon addition of water molecules. When 10 water molecules have been added, all spaces near the salt bridge are filled, completing the first hydration shell, and a second shell starts to form. The potentials associated with salt bridges depend on their hydration, and potentials assigned without regard to local hydration are likely to cause errors as large as or larger than kBT, thus suggesting a serious problem if these potentials are used in Molecular Dynamics simulations.« less

Nutritional Supplements to Enhance Recovery

NASA Astrophysics Data System (ADS)

Ziegenfuss, Tim N.; Landis, Jamie; Greenwood, Mike

The ability to recover from intense exercise often separates good athletes from great ones. In the past, "recovery" often simply included rest, physical modalities (e.g., massage, hydration therapy) and meeting basic nutritional needs for fluid and energy intake. Today, athletes have a number of additional options to help them recover from high intensity training, one of which includes the judicious use of dietary supplements. This chapter briefly reviews nutritional strategies that have a strong theoretical background for enhancing rehydration/electrolyte balance, replenishing energy reserves, minimizing oxidative damage, and stimulating muscle repair.

Modified silica-based heterogeneous catalysts for etherification of glycerol

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

Gholami, Zahra, E-mail: zahra.gholami@petronas.com.my; Abdullah, Ahmad Zuhairi, E-mail: chzuhairi@usm.my; Gholami, Fatemeh, E-mail: fgholami59@gmail.com

2015-07-22

The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product.more » The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca{sub 1.6}La{sub 0.6}/MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%.« less

Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Dai, S.; Seol, Y.

2015-12-01

In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

Hydrate morphology: Physical properties of sands with patchy hydrate saturation

USGS Publications Warehouse

Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.

2012-01-01

The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

Nasogastric Hydration in Infants with Bronchiolitis Less Than 2 Months of Age.

PubMed

Oakley, Ed; Bata, Sonny; Rengasamy, Sharmila; Krieser, David; Cheek, John; Jachno, Kim; Babl, Franz E

2016-11-01

To determine whether nasogastric hydration can be used in infants less than 2 months of age with bronchiolitis, and characterize the adverse events profile of these infants compared with infants given intravenous (IV) fluid hydration. A descriptive retrospective cohort study of children with bronchiolitis under 2 months of age admitted for hydration at 3 centers over 3 bronchiolitis seasons was done. We determined type of hydration (nasogastric vs IV fluid hydration) and adverse events, intensive care unit admission, and respiratory support. Of 491 infants under 2 months of age admitted with bronchiolitis, 211 (43%) received nonoral hydration: 146 (69%) via nasogastric hydration and 65 (31%) via IV fluid hydration. Adverse events occurred in 27.4% (nasogastric hydration) and 23.1% (IV fluid hydration), difference of 4.3%; 95%CI (-8.2 to 16.9), P = .51. The majority of adverse events were desaturations (21.9% nasogastric hydration vs 21.5% IV fluid hydration, difference 0.4%; [-11.7 to 12.4], P = .95). There were no pulmonary aspirations in either group. Apneas and bradycardias were similar in each group. IV fluid hydration use was positively associated with intensive care unit admission (38.5% IV fluid hydration vs 19.9% nasogastric hydration; difference 18.6%, [5.1-32.1], P = .004); and use of ventilation support (27.7% IV fluid hydration vs 15.1% nasogastric hydration; difference 12.6 [0.3-23], P = .03). Fewer infants changed from nasogastric hydration to IV fluid hydration than from IV fluid hydration to nasogastric hydration (12.3% vs 47.7%; difference -35.4% [-49 to -22], P < .001). Nasogastric hydration can be used in the majority of young infants admitted with bronchiolitis. Nasogastric hydration and IV fluid hydration had similar rates of complications. Copyright © 2016 Elsevier Inc. All rights reserved.

Hydration and ion pair formation in aqueous Y(3+)-salt solutions.

PubMed

Rudolph, Wolfram W; Irmer, Gert

2015-11-14

Raman spectra of aqueous yttrium perchlorate, triflate (trifluoromethanesulfonate), chloride and nitrate solutions were measured over a broad concentration range (0.198-3.252 mol L(-1)). The spectra range from low wavenumbers to 4200 cm(-1). A very weak mode at 384 cm(-1) with a full width at half height at 50 cm(-1) in the isotropic spectrum suggests that the Y(3+)- octa-aqua ion is thermodynamically stable in dilute perchlorate solutions (∼0.5 mol L(-1)) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The octa-hydrate, [Y(OH2)8](3+) was also detected in a 1.10 mol L(-1) aqueous Y(CF3SO3)3 solution. Furthermore, very weak and broad depolarized modes could be detected which are assigned to [Y(OH2)8](3+)(aq) at 100, 166, 234 and 320 cm(-1) confirming that a hexa-hydrate is not compatible with the hydrated species in solution. In yttrium chloride solutions contact ion pair formation was detected over the measured concentration range from 0.479-3.212 mol L(-1). The contact ion pairs in YCl3(aq) are fairly weak and disappear with dilution. At a concentration <0.2 mol L(-1) almost all complexes have disappeared. In YCl3 solutions, with additional HCl, chloro-complexes of the type [Y(OH2)8-nCln](+3-n) (n = 1,2) are formed. The Y(NO3)3(aq) spectra were compared with a spectrum of a dilute NaNO3 solution and it was concluded that in Y(NO3)3(aq) over the concentration range from 2.035-0.198 mol L(-1) nitrato-complexes [Y(OH2)8-n(NO3)ln](+3-n) (n = 1,2) are formed. The nitrato-complexes are weak and disappear with dilution <0.1 mol L(-1). DFT geometry optimizations and frequency calculations are reported for both the yttrium-water cluster in the gas phase and the cluster within a polarizable continuum model in order to implicitly describe the presence of the bulk solvent. The bond distance and angle for the square antiprismatic cluster geometry of [Y(OH2)8](3+) with the polarizable dielectric continuum is in good agreement with data from recent structural experimental measurements. The DFT frequency of the Y-O stretching mode of the [Y(OH2)8](3+) cluster, in a polarizable continuum, is at 372 cm(-1) in satisfactory agreement with the experimental value.

Determination of the microenvironment-pH and charge and size characteristics of amino acids through their electrophoretic mobilities determined by CZE.

PubMed

Piaggio, Maria V; Peirotti, Marta B; Deiber, Julio A

2007-10-01

Effective electrophoretic mobility data of 20 amino acids reported in the literature are analyzed and interpreted through simple physicochemical models, which are able to provide estimates of coupled quantities like hydrodynamic shape factor, equivalent hydrodynamic radius (size), net charge, actual pK values of ionizing groups, partial charges of ionizing groups, hydration number, and pH near molecule (microenvironment-pH of the BGE). It is concluded that the modeling of the electrophoretic mobility of these analytes requires a careful consideration of hydrodynamic shape coupled to hydration. In the low range of pH studied here, distinctive hydrodynamic behaviors of amino acids are found. For instance, amino acids with basic polar and ionizing side chain remain with prolate shape for pH values varying from 1.99 to 3.2. It is evident that as the pH increases from low values, amino acids get higher hydrations as a consequence each analyte total charge also increases. This result is consistent with the monotonic increase of the hydrodynamic radius, which accounts for both the analyte and the quite immobilized water molecules defining the electrophoretic kinematical unit. It is also found that the actual or effective pK value of the alpha-carboxylic ionizing group of amino acids increases when the pH is changed from 1.99 to 3.2. Several limitations concerning the simple modeling of the electrophoretic mobility of amino acids are presented for further research.

Increasing Gas Hydrate Formation Temperature for Desalination of High Salinity Produced Water with Secondary Guests

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

Cha, Jong-Ho; Seol, Yongkoo

We suggest a new gas hydrate-based desalination process using water-immiscible hydrate formers; cyclopentane (CP) and cyclohexane (CH) as secondary hydrate guests to alleviate temperature requirements for hydrate formation. The hydrate formation reactions were carried out in an isobaric condition of 3.1 MPa to find the upper temperature limit of CO2 hydrate formation. Simulated produced water (8.95 wt % salinity) mixed with the hydrate formers shows an increased upper temperature limit from -2 °C for simple CO2 hydrate to 16 and 7 °C for double (CO2 + CP) and (CO2 + CH) hydrates, respectively. The resulting conversion rate to double hydratemore » turned out to be similar to that with simple CO2 hydrate at the upper temperature limit. Hydrate formation rates (Rf) for the double hydrates with CP and CH are shown to be 22 and 16 times higher, respectively, than that of the simple CO2 hydrate at the upper temperature limit. Such mild hydrate formation temperature and fast formation kinetics indicate increased energy efficiency of the double hydrate system for the desalination process. Dissociated water from the hydrates shows greater than 90% salt removal efficiency for the hydrates with the secondary guests, which is also improved from about 70% salt removal efficiency for the simple hydrates.« less

Dead Pericarps of Dry Fruits Function as Long-Term Storage for Active Hydrolytic Enzymes and Other Substances That Affect Germination and Microbial Growth

PubMed Central

Godwin, James; Raviv, Buzi; Grafi, Gideon

2017-01-01

It is commonly assumed that dead pericarps of dry indehiscent fruits have evolved to provide an additional physical layer for embryo protection and as a means for long distance dispersal. The pericarps of dry fruits undergo programmed cell death (PCD) during maturation whereby most macromolecules such DNA, RNA, and proteins are thought to be degraded and their constituents remobilized to filial tissues such as embryo and endosperm. We wanted to test the hypothesis that the dead pericarp represents an elaborated layer that is capable of storing active proteins and other substances for increasing survival rate of germinating seeds. Using in gel assays we found that dead pericarps of both dehiscent and indehiscent dry fruits of various plant species including Arabidopsis thaliana and Sinapis alba release upon hydration multiple active hydrolytic enzymes that can persist in an active form for decades, including nucleases, proteases, and chitinases. Proteomic analysis of indehiscent pericarp of S. alba revealed multiple proteins released upon hydration, among them proteases and chitinases, as well as proteins involved in reactive oxygen species (ROS) detoxification and cell wall modification. Pericarps appear to function also as a nutritional element-rich storage for nitrate, potassium, phosphorus, sulfur, and others. Sinapis alba dehiscent and indehiscent pericarps possess germination inhibitory substances as well as substances that promote microbial growth. Collectively, our study explored previously unknown features of the dead pericarp acting also as a reservoir of biological active proteins, and other substances capable of “engineering” the microenvironment for the benefit of the embryo. PMID:29257090

Toward better understanding of chloral hydrate stability in water: Kinetics, pathways, and influencing factors.

PubMed

Ma, Shengcun; Guo, Xiaoqi; Chen, Baiyang

2016-08-01

Chloral hydrate (CH) is a disinfection byproduct commonly found in disinfected water, and once formed, CH may undergo several transformation processes in water distribution system. In order to understand its fate and occurrence in water, this study examined several factors that may affect the stability of CH in water, including pH, temperature, initial CH concentration, typical anions, and the presence of free chlorine and monochloramine. The results indicated that CH was a relatively stable compound (half-life ∼7 d for 20 μg/L) in ambient pH (7) and temperature (20 °C) conditions. However, the hydrolysis rate can be greatly facilitated by increasing pH (from 7 to 12) and temperature (from 20 to 60 °C) or decreasing initial CH concentration (from 10 mg/L to 20 μg/L). To quantify the influences of these factors on the CH hydrolysis rate constant (k, 1/h), which spans five orders of magnitude, this study developed a multivariate model that predicts literature and this study's data well (R(2) = 0.90). In contrast, the presence of chloride, nitrate, monochloramine, and free chlorine exhibited no significant impacts on the degradation of CH, while the CH loss in non-buffered waters spiked with sodium hypochlorite was driven by alkaline hydrolysis. In terms of reaction products, CH hydrolysis yielded mostly chloroform and formic acid and a few chloride, which confirmed decarburization as a dominant pathway and dehalogenation as a noticeable coexisting reaction. Copyright © 2016. Published by Elsevier Ltd.

A versatile tripodal amide receptor for the encapsulation of anions or hydrated anions via formation of dimeric capsules.

PubMed

Arunachalam, M; Ghosh, Pradyut

2010-02-01

A bowl-shaped tripodal receptor with an appropriately positioned amide functionality on the benzene platform and electron-withdrawing p-nitrophenyl terminals (L(1)) has been designed, synthesized, and studied for the anion binding properties. The single-crystal X-ray crystallographic analysis on crystals of L(1) with tetrabutylammonium salts of nitrate (1), acetate (2), fluoride (3), and chloride (4) obtained in moist dioxane medium showed encapsulation of two NO(3)(-), [(AcO)(2)(H(2)O)(4)](2-), [F(2)(H(2)O)(6)](2-), and [Cl(2)(H(2)O)(4)](2-) respectively as the anionic guests inside the staggered dimeric capsular assembly of L(1). The p-nitro substitution in the aryl terminals assisted the formation of dimeric capsular assembly of L(1) exclusively upon binding/encapsulating above different guests. Though L(1) demonstrates capsule formation upon anion or hydrated anion complexation for all of the anions studied here, its positional isomer with the o-nitro-substituted tripodal triamide receptor L(2) selectively formed the dimeric capsular assembly upon encapsulation of [F(2)(H(2)O)(6)](2-) and noncapsular aggregates in the cases of other anions such as Cl(-), NO(3)(-), and AcO(-). Interestingly, structural investigations upon anion exchange of the complexes revealed that both isomers have selectivity toward the formation of a [F(2)(H(2)O)(6)](2-) encapsulated dimeric capsule. In contrast, solution-state (1)H NMR titration studies of L(1) and L(2) in DMSO-d(6) with AcO(-) indicated 1:3 (host:guest) binding.

Improvement of gas hydrate preservation by increasing compression pressure to simple hydrates of methane, ethane, and propane

NASA Astrophysics Data System (ADS)

Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro

2017-09-01

In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.

Proceedings of International Pyrotechnics Seminar (4th), Held at Steamboat Village, Colorado, 22-26 July 1974

DTIC Science & Technology

1974-06-17

10-1 I1. Burning Rate Modifiers, D.R. Dillehay ............................. 11-1 12. Spectroscopic Analysis of Azide Decomposition Products for use...solid, and Pit that they ignite a short distance from the surface. Further- more, decomposition of sodium nitrate, which produces the gas to blow the...decreasing U the thermal conductivity of the basic binary. Class 2 compounds, con- sisting of nanganese oxides, catalyze the normal decomposition of

Basic Research in Microplasmas

DTIC Science & Technology

2012-03-29

concentrations of nitrate anions (NO3-) and nitrite anions (NO2-) in sterile water were measured with a high-performance liquid chromatography , HPLC ( Dionex ...ICS-2500 equipped with an ED50 electrochemical detector and a DIONEX ASRS 4-mm suppressor module). 25 μL samples were injected into the system for...the very few of He* atoms were used for the Penning ionization of the N2 molecule(reaction 6), because no N2 + ion (391nm) were detected in side-on

Using Bayesian hierarchical models to better understand nitrate sources and sinks in agricultural watersheds.

PubMed

Xia, Yongqiu; Weller, Donald E; Williams, Meghan N; Jordan, Thomas E; Yan, Xiaoyuan

2016-11-15

Export coefficient models (ECMs) are often used to predict nutrient sources and sinks in watersheds because ECMs can flexibly incorporate processes and have minimal data requirements. However, ECMs do not quantify uncertainties in model structure, parameters, or predictions; nor do they account for spatial and temporal variability in land characteristics, weather, and management practices. We applied Bayesian hierarchical methods to address these problems in ECMs used to predict nitrate concentration in streams. We compared four model formulations, a basic ECM and three models with additional terms to represent competing hypotheses about the sources of error in ECMs and about spatial and temporal variability of coefficients: an ADditive Error Model (ADEM), a SpatioTemporal Parameter Model (STPM), and a Dynamic Parameter Model (DPM). The DPM incorporates a first-order random walk to represent spatial correlation among parameters and a dynamic linear model to accommodate temporal correlation. We tested the modeling approach in a proof of concept using watershed characteristics and nitrate export measurements from watersheds in the Coastal Plain physiographic province of the Chesapeake Bay drainage. Among the four models, the DPM was the best--it had the lowest mean error, explained the most variability (R 2  = 0.99), had the narrowest prediction intervals, and provided the most effective tradeoff between fit complexity (its deviance information criterion, DIC, was 45.6 units lower than any other model, indicating overwhelming support for the DPM). The superiority of the DPM supports its underlying hypothesis that the main source of error in ECMs is their failure to account for parameter variability rather than structural error. Analysis of the fitted DPM coefficients for cropland export and instream retention revealed some of the factors controlling nitrate concentration: cropland nitrate exports were positively related to stream flow and watershed average slope, while instream nitrate retention was positively correlated with nitrate concentration. By quantifying spatial and temporal variability in sources and sinks, the DPM provides new information to better target management actions to the most effective times and places. Given the wide use of ECMs as research and management tools, our approach can be broadly applied in other watersheds and to other materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

Direct measurements of the interactions between clathrate hydrate particles and water droplets.

PubMed

Liu, Chenwei; Li, Mingzhong; Zhang, Guodong; Koh, Carolyn A

2015-08-14

Clathrate hydrate particle agglomeration is often considered to be one of the key limiting factors in plug formation. The hydrate particle-water interaction can play a critical role in describing hydrate agglomeration, yet is severely underexplored. Therefore, this work investigates the interactions between water droplets and cyclopentane hydrate particles using a micromechanical force (MMF) apparatus. Specifically, the effect of contact time, temperature/subcooling, contact area, and the addition of Sorbitane monooleate (Span 80) surfactant on the water droplet-hydrate particle interaction behavior are studied. The measurements indicate that hydrate formation during the measurement would increase the water-hydrate interaction force significantly. The results also indicate that the contact time, subcooling and concentration of cyclopentane, which determine the hydrate formation rate and hydrate amount, will affect the hydrate-water interaction force. In addition, the interaction forces also increase with the water-hydrate contact area. The addition of Span 80 surfactant induces a change in the hydrate morphology and renders the interfaces stable versus unstable (leading to coalescence), and the contact force can affect the hydrate-water interaction behavior significantly. Compared with the hydrate-hydrate cohesion force (measured in cyclopentane), the hydrate-water adhesion force is an order of magnitude larger. These new measurements can help to provide new and critical insights into the hydrate agglomeration process and potential strategies to control this process.

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).

Determining Roles of Accessory Genes in Denitrification by Mutant Fitness Analyses

DOE PAGES

Vaccaro, Brian J.; Thorgersen, Michael P.; Lancaster, W. Andrew; ...

2015-10-09

Enzymes of the denitrification pathway play an important role in the global nitrogen cycle, including release of nitrous oxide, an ozone-depleting greenhouse gas. In addition, nitric oxide reductase, maturation factors, and proteins associated with nitric oxide detoxification are used by pathogens to combat nitric oxide release by host immune systems. While the core reductases that catalyze the conversion of nitrate to dinitrogen are well understood at a mechanistic level, there are many peripheral proteins required for denitrification whose basic function is unclear. A bar-coded transposon DNA library fromPseudomonas stutzeristrain RCH2 was grown under denitrifying conditions, using nitrate or nitrite asmore » an electron acceptor, and also under molybdenum limitation conditions, with nitrate as the electron acceptor. Analysis of sequencing results from these growths yielded gene fitness data for 3,307 of the 4,265 protein-encoding genes present in strain RCH2. The insights presented here contribute to our understanding of how peripheral proteins contribute to a fully functioning denitrification pathway. We propose a new low-affinity molybdate transporter, OatABC, and show that differential regulation is observed for two MoaA homologs involved in molybdenum cofactor biosynthesis. We also propose that NnrS may function as a membrane-bound NO sensor. Finally, the dominant HemN paralog involved in heme biosynthesis is identified, and a CheR homolog is proposed to function in nitrate chemotaxis. In addition, new insights are provided into nitrite reductase redundancy, nitric oxide reductase maturation, nitrous oxide reductase maturation, and regulation.« less

Nanoporous nickel microspheres: synthesis and application for the electrocatalytic oxidation and determination of acyclovir.

PubMed

Heli, Hossein; Pourbahman, Fatemeh; Sattarahmady, Naghmeh

2012-01-01

Nickel microspheres were synthesized via a water-in-oil reverse nanoemulsion system using nickel nitrate as the nickel precursor and hydrazine hydrate as the reducing agent. The nanoemulsion was a triton X-100/cyclohexane/water ternary system. The surface morphology of the nickel microspheres was studied by scanning electron microscopy, which indicated that the microspheres had a nanoporous structure. The electrochemical behavior of the nanoporous nickel microspheres were studied in alkaline solution and were then employed to fabricate a modified carbon paste electrode in order to investigate the electrocatalytic oxidation of the drug acyclovir. The oxidation process involved, and its kinetics were investigated using cyclic voltammetry and chronoamperometry. The rate constant of the catalytic oxidation of acyclovir and the electron-transfer coefficient are reported. A sensitive, simple and time-saving amperometric procedure was developed for the analysis of acyclovir. The proposed amperometric method was also applied to determine acyclovir in tablets and topical cream.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

Hydrothermal synthesis of nanostructured Y2O3 and (Y0.75Gd0.25)2O3 based phosphors

NASA Astrophysics Data System (ADS)

Mančić, Lidija; Lojpur, Vesna; Marinković, Bojan A.; Dramićanin, Miroslav D.; Milošević, Olivera

2013-08-01

Examples of (Y2O3-Gd2O3):Eu3+ and Y2O3:(Yb3+/Er3+) rare earth oxide-based phosphors are presented to highlight the controlled synthesis of 1D and 2D nanostructures through simple hydrothermal method. Conversion of the starting nitrates mixture into carbonate hydrate phase is performed with the help of ammonium hydrogen carbonate solution during hydrothermal treatment at 200 °C/3 h. Morphological architectures of rare earth oxides obtained after subsequent powders thermal treatment at 600 and 1100 °C for 3 and 12 h and their correlation with the optical characteristics are discussed based on X-ray powder diffractometry, field emission scanning electron microscopy, infrared spectroscopy and photoluminescence measurements. Strong red and green emission followed by the superior decay times are attributed to the high powders purity and homogeneous dopants distribution over the host lattice matrix.

Hygroscopic analysis of individual Beijing haze aerosol particles by environmental scanning electron microscopy

NASA Astrophysics Data System (ADS)

Bai, Zhangpeng; Ji, Yuan; Pi, Yiqun; Yang, Kaixiang; Wang, Li; Zhang, Yinqi; Zhai, Yadi; Yan, Zhengguang; Han, Xiaodong

2018-01-01

Investigating the hygroscopic behavior of haze aerosol particles is essential for understanding their physicochemical properties and their impacts on regional weather and visibility. An environmental scanning electron microscope equipped with a home-made transmission-scattering electron imaging setup and an energy dispersive spectrometer was used for in-situ observations of pure water-soluble (WS) salts and Beijing haze particles. This imaging setup showed obvious advantages for improving the resolution and acquiring internal information of mixed particles in hydrated environments. We measured the deliquescence relative humidity of pure NaCl, NH4NO3, and (NH4)2SO4 by deliquescence-crystallization processes with an accuracy of up to 0.3% RH. The mixed haze particles showed hygroscopic activation like water uptake and morphological changes when they included WS components such as nitrates, sulfates, halides, ammoniums, and alkali metal salts. In addition, the hygroscopic behavior provides complementary information for analyzing possible phases in mixed haze particles.

Synthesis and characterization of CdO nano particles by the sol-gel method

NASA Astrophysics Data System (ADS)

Vadgama, V. S.; Vyas, R. P.; Jogiya, B. V.; Joshi, M. J.

2017-05-01

Cadmium Oxide (CdO) is an inorganic compound and one of the main precursors to other cadmium compounds. It finds applications in cadmium plating, storage batteries, in transparent conducting film, etc. Here, an attempt is made to synthesize CdO nano particles by sol-gel technique. The gel was prepared using cadmium nitrate tetra hydrate (Cd(NO3)2.4H2O) and aqueous ammonium hydroxide (NH4OH) as a precursor. The synthesized powder is further characterized by techniques like Powder X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Thermal gravimetric analysis (TGA). Powder XRD analysis suggested the nano-crystalline nature of the sample with the cubic crystal system. Nano scaled particles of spherical morphology with the size ranging from 50-100 nm are observed from TEM images. While, FT-IR study is used to confirm the presence of different functional groups. Thermo-gravimetric analysis suggests the highly thermally stable nature of the samples. The results are discussed.

One-step synthesis of layered yttrium hydroxides in immiscible liquid-liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

NASA Astrophysics Data System (ADS)

Watanabe, Mebae; Fujihara, Shinobu

2014-02-01

Inorganic-organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid-liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu3+ ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect.

Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

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

B. J. Mincher; S. K. Cole; W. J. Cooper

2007-02-01

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

Effect of oxidizer to fuel molar ratio on particle size and DC conductivity of CeO{sub 2} nanoparticles

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

Harish, B. M.; Rajeeva, M. P.; Naveen, C. S.

2016-05-06

Cerium oxide nanoparticles were synthesized by solution combustion method with varying the oxidizer (cerium nitrate hexa hydrate) to fuel (Glycine) molar ratio. The prepared samples were characterized by UV-visible spectrometer, X-ray diffractometer (XRD), Scanning electron microscope (SEM) and Energy dispersive X-Ray analysis (EDAX). XRD pattern reveals the formation of cubic fluorite structure of CeO{sub 2}. It was observed that finest crystallites were found at extreme fuel-deficient condition and it is good enough to produce favorable powder characteristics. The average crystallite size was found to be 14.46 nm to 21.57 nm. The temperature dependent dc conductivity was carried out using Keithleymore » source meter between the temperature range from 300 K to 573 K. From this study it was found that the conductivity increases with increase of temperature due to semiconducting behavior of CeO{sub 2} and it decreases with particle size due to increase in the energy band gap.« less

Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

NASA Astrophysics Data System (ADS)

Farzin Nejad, N.; Shams, E.; Amini, M. K.

2015-09-01

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption-desorption isotherm and transmission electron microscopy. Nitrogen adsorption-desorption measurement revealed the high surface area (810 m2 g-1), maxima pore size of 3.3 nm and large pore volume (1.01 cm3 g-1) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g-1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles.

Proton transport in functionalised additives for PEM fuel cells: contributions from atomistic simulations.

PubMed

Tölle, Pia; Köhler, Christof; Marschall, Roland; Sharifi, Monir; Wark, Michael; Frauenheim, Thomas

2012-08-07

The conventional polymer electrolyte membrane (PEM) materials for fuel cell applications strongly rely on temperature and pressure conditions for optimal performance. In order to expand the range of operating conditions of these conventional PEM materials, mesoporous functionalised SiO(2) additives are developed. It has been demonstrated that these additives themselves achieve proton conductivities approaching those of conventional materials. However, the proton conduction mechanisms and especially factors influencing charge carrier mobility under different hydration conditions are not well known and difficult to separate from concentration effects in experiments. This tutorial review highlights contributions of atomistic computer simulations to the basic understanding and eventual design of these materials. Some basic introduction to the theoretical and computational framework is provided to introduce the reader to the field, the techniques are in principle applicable to a wide range of other situations as well. Simulation results are directly compared to experimental data as far as possible.

Seeding hydrate formation in water-saturated sand with dissolved-phase methane obtained from hydrate dissolution: A progress report

USGS Publications Warehouse

Waite, William F.; Osegovic, J.P.; Winters, William J.; Max, M.D.; Mason, David H.

2008-01-01

An isobaric flow loop added to the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) is being investigated as a means of rapidly forming methane hydrate in watersaturated sand from methane dissolved in water. Water circulates through a relatively warm source chamber, dissolving granular methane hydrate that was pre-made from seed ice, then enters a colder hydrate growth chamber where hydrate can precipitate in a water-saturated sand pack. Hydrate dissolution in the source chamber imparts a known methane concentration to the circulating water, and hydrate particles from the source chamber entrained in the circulating water can become nucleation sites to hasten the onset of hydrate formation in the growth chamber. Initial results suggest hydrate grows rapidly near the growth chamber inlet. Techniques for establishing homogeneous hydrate formation throughout the sand pack are being developed.

Apportionment of sources of fine and coarse particles in four major Australian cities by positive matrix factorisation

NASA Astrophysics Data System (ADS)

Chan, Yiu-Chung; Cohen, David D.; Hawas, Olga; Stelcer, Eduard; Simpson, Rod; Denison, Lyn; Wong, Neil; Hodge, Mary; Comino, Eva; Carswell, Stewart

In this study, 437 days of 6-daily, 24-h samples of PM 2.5, PM 2.5-10 and PM 10 were collected over a 12-month period during 2003-2004 in Melbourne, Sydney, Brisbane and Adelaide. The elemental, ionic and polycyclic aromatic hydrocarbon composition of the particles were determined. Source apportionment was carried out by using the positive matrix factorisation software (PMF2). Eight factors were identified for the fine particle samples including 'motor vehicles', 'industry', 'other combustion sources', 'ammonium sulphates', 'nitrates', 'marine aerosols', 'chloride depleted marine aerosols' and 'crustal/soil dust'. On average combustion sources, secondary nitrates/sulphates and natural origin dust contributed about 46%, 25% and 26% of the mass of the fine particle samples, respectively. 'Crustal/soil dust', 'marine aerosols', 'nitrates' and 'road side dust' were the four factors identified for the coarse particle samples. On average natural origin dust contributed about 76% of the mass of the coarse particle samples. The contributions of the sources to the sample mass basically reflect the emission source characteristics of the sites. Secondary sulphates and nitrates were found to spread out evenly within each city. The average contribution of secondary nitrates to fine particles was found to be rather uniform in different seasons, rather than higher in winter as found in other studies. This could be due to the low humidity conditions in winter in most of the Australian cities which made the partitioning of the particle phase less favourable in the NH 4NO 3 equilibrium system. A linear relationship was found between the average contribution of marine aerosols and the distance of the site from the bay side. Wind erosion was found associated with higher contribution of crustal dust on average and episodes of elevated concentration of coarse particles in spring and summer.

Superimpose signal processing method for micro-scale thermal imaging of solar salts at high temperature

NASA Astrophysics Data System (ADS)

Morikawa, Junko; Zamengo, Massimiliano; Kato, Yukitaka

2016-05-01

The global interest in energy applications activates the advanced study about the molten salts in the usage of fluids in the power cycle, such as for transport and heat storage in solar power facilities. However, the basic properties of molten salts show a general scattering in characterization especially in thermal properties. It is suggested that new studies are required on the measurement of thermal properties of solar salts using recent technologies. In this study, micro-scale heat transfer and phase change in molten salts are presented using our originally developed device: the micro-bolometer Infrared focal plane arrays (IR FPA) measuring system is a portable type instrument, which is re-designed to measure the thermal phenomena in high temperature up to 700 °C or higher. The superimpose system is newly setup adjusted to the signal processing in high temperature to realize the quantitative thermal imaging, simultaneously. The portable type apparatus for a quantitative micro-scale thermography using a micro-bolometer has been proposed based on an achromatic lens design to capture a micro-scale image in the long-wave infrared, a video signal superimposing for the real time emissivity correction, and a pseudo acceleration of a timeframe. Combined with the superimpose technique, the micro-scale thermal imaging in high temperature is achieved and the molten flows of the solar salts, sodium nitrate, and potassium nitrate are successfully observed. The solar salt, the mixture of sodium nitrate and potassium nitrate, shows a different shape of exothermic heat front morphology in the lower phase transition (solidification) temperature than the nitrates on cooling. The proposed measuring technique will be utilized to accelerate the screening step to determine the phase diagram and the eutectics of the multiple mixtures of candidate molten salts, which may be used as heat transport medium from the concentrated solar power to a processing plant for thermal energy storage.

Strength Estimation for Hydrate-Bearing Sediments From Direct Shear Tests of Hydrate-Bearing Sand and Silt

NASA Astrophysics Data System (ADS)

Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu

2018-01-01

Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation Sh ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available.

Quantifying Hydrate Formation in Gas-rich Environments Using the Method of Characteristics

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.; DiCarlo, D. A.

2015-12-01

Methane hydrates hold a vast amount of methane globally, and have huge energy potential. Methane hydrates in gas-rich environments are the most promising production targets. We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation in such environments (Figure 1). Our solution shows that hydrate saturation is constant with time and space in a homogeneous system. Hydrate saturation is controlled by the initial thermodynamic condition of the system, and changed by the gas fractional flow. Hydrate saturation increases with the initial distance from the hydrate phase boundary. Different gas fractional flows behind the hydrate solidification front lead to different gas saturations at the hydrate solidification front. The higher the gas saturation at the front, the less the volume available to be filled by hydrate, and hence the lower the hydrate saturation. The gas fractional flow depends on the relative permeability curves, and the forces that drive the flow. Viscous forces (the drive for flow induced from liquid pressure gradient) dominate the flow, and hydrate saturation is independent on the gas supply rates and the flow directions at high gas supply rates. Hydrate saturation can be estimated as one minus the ratio of the initial to equilibrium salinity. Gravity forces (the drive for flow induced from the gravity) dominate the flow, and hydrate saturation depends on the flow rates and the flow directions at low gas supply rates. Hydrate saturation is highest for upward flow, and lowest for downward flow. Hydrate saturation decreases with the flow rate for upward flow, and increases with the flow rate for downward flow. This analytical solution illuminates how hydrate is formed by gas (methane, CO2, ethane, propane) flowing into brine-saturated sediments at both the laboratory and geological scales (Figure 1). It provides an approach to generalize the understanding of hydrate solidification in gas-rich environments, although complicated numerical models have been developed previously. Examples of gas expulsion into hydrate stability zones and the associated hydrate formation in both laboratory and geological scales, and CO2 sequestration into CO2-hydrates near the seafloor and under the permafrost will be presented.

Some thermodynamical aspects of protein hydration water

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

Mallamace, Francesco, E-mail: francesco.mallamace@unime.it; Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139; Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215

2015-06-07

We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

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.

Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties

USGS Publications Warehouse

Lee, J.Y.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

2010-01-01

The small-strain mechanical properties (e.g., seismic velocities) of hydrate-bearing sediments measured under laboratory conditions provide reference values for calibration of logging and seismic exploration results acquired in hydrate-bearing formations. Instrumented cells were designed for measuring the compressional (P) and shear (S) velocities of sand, silts, and clay with and without hydrate and subject to vertical effective stresses of 0.01 to 2 MPa. Tetrahydrofuran (THF), which is fully miscible in water, was used as the hydrate former to permit close control over the hydrate saturation Shyd and to produce hydrate from dissolved phase, as methane hydrate forms in most natural marine settings. The results demonstrate that laboratory hydrate formation technique controls the pattern of P and S velocity changes with increasing Shyd and that the small-strain properties of hydrate-bearing sediments are governed by effective stress, δ'v and sediment specific surface. The S velocity increases with hydrate saturation owing to an increase in skeletal shear stiffness, particularly when hydrate saturation exceeds Shyd≈ 0.4. At very high hydrate saturations, the small strain shear stiffness is determined by the presence of hydrates and becomes insensitive to changes in effective stress. The P velocity increases with hydrate saturation due to the increases in both the shear modulus of the skeleton and the bulk modulus of pore-filling phases during fluid-to-hydrate conversion. Small-strain Poisson's ratio varies from 0.5 in soft sediments lacking hydrates to 0.25 in stiff sediments (i.e., subject to high vertical effective stress or having high Shyd). At Shyd ≥ 0.5, hydrate hinders expansion and the loss of sediment stiffness during reduction of vertical effective stress, meaning that hydrate-rich natural sediments obtained through pressure coring should retain their in situ fabric for some time after core retrieval if the cores are maintained within the hydrate stability field.

Effects of hydration on mitral valve prolapse.

PubMed

Lax, D; Eicher, M; Goldberg, S J

1993-08-01

We investigated the effect of hydration on mitral valve prolapse (MVP). Ten subjects with documented diagnosis of MVP were studied before and after oral hydration with 1 L of fluid. Increased weight and cardiac output were present after hydration. Results showed that all 10 subjects with diagnosis of MVP before hydration continued to have MVP after hydration; however, subtle changes were detected, especially on auscultation. Seven of 9 subjects (with cardiac examination recorded before and after hydration) had auscultatory findings of MVP before hydration. No detectable auscultatory change after hydration was present in one subject; in six subjects a loss of either a click or a murmur was detected after hydration. All subjects had echocardiographically detected MVP before hydration; evidence of MVP on two-dimensional or M-mode examination persisted after hydration in all 10 subjects. Minor changes in the echocardiographic examination (M-mode n = 2, Doppler n = 1) were detected in three subjects. Thus we found that hydration of subjects with MVP did not alter the overall diagnosis; however, changes occurred, especially on auscultation. This suggests that alterations in hydration may affect auscultatory expression of MVP and could explain, in part, the variable auscultatory findings in patients with MVP.

Comparison of stromal hydration techniques for clear corneal cataract incisions: conventional hydration versus anterior stromal pocket hydration.

PubMed

Mifflin, Mark D; Kinard, Krista; Neuffer, Marcus C

2012-06-01

Anterior stromal pocket hydration was compared with conventional hydration for preventing wound leak after 2.8 mm uniplanar clear corneal incisions (CCIs) in patients having routine cataract surgery. Conventional hydration involves hydration of the lateral walls of the main incision with visible whitening of the stroma. The anterior stromal pocket hydration technique involves creation of an additional supraincisional stromal pocket overlying the main incision, which is then hydrated instead of the main incision. Sixty-six eyes of 48 patients were included in the data analysis with 33 assigned to each study group. The anterior stromal pocket hydration technique was significantly better than conventional hydration in preventing wound leak due to direct pressure on the posterior lip of the incision. Copyright © 2012 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

Development of a non-cryogenic nitrogen/oxygen supply system. [for spacecraft environments

NASA Technical Reports Server (NTRS)

1977-01-01

Modular components were refined or replaced to improve the performance of the electrolysis module in a system which generates both oxygen and hydrogen from hydrazine hydrate. Significant mechanical and electrical performance improvements were achieved in the cathode. Improvements were also made in the phase separation area but at considerable cost in time and money and to the detriment of other investigative areas. Only the pump/bubble separator failed in a manner necessitating redesign. Its failure was, however, due to its being operated above the temperature range for which it was designed. The basic electrolysis cell design was not changed.

Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition.

PubMed

Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A

2005-10-22

Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.

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

3D pore-type digital rock modeling of natural gas hydrate for permafrost and numerical simulation of electrical properties

NASA Astrophysics Data System (ADS)

Dong, Huaimin; Sun, Jianmeng; Lin, Zhenzhou; Fang, Hui; Li, Yafen; Cui, Likai; Yan, Weichao

2018-02-01

Natural gas hydrate is being considered as an alternative energy source for sustainable development and has become a focus of research throughout the world. In this paper, based on CT scanning images of hydrate reservoir rocks, combined with the microscopic distribution of hydrate, a diffusion limited aggregation (DLA) model was used to construct 3D hydrate digital rocks of different distribution types, and the finite-element method was used to simulate their electrical characteristics in order to study the influence of different hydrate distribution types, hydrate saturation and formation of water salinity on electrical properties. The results show that the hydrate digital rocks constructed using the DLA model can be used to characterize the microscopic distribution of different types of hydrates. Under the same conditions, the resistivity of the adhesive hydrate digital rock is higher than the cemented and scattered type digital rocks, and the resistivity of the scattered hydrate digital rock is the smallest among the three types. Besides, the difference in the resistivity of the different types of hydrate digital rocks increases with an increase in hydrate saturation, especially when the saturation is larger than 55%, and the rate of increase of each of the hydrate types is quite different. Similarly, the resistivity of the three hydrate types decreases with an increase in the formation of water salinity. The single distribution hydrate digital rock constructed, combined with the law of microscopic distribution and influence of saturation on the electrical properties, can effectively improve the accuracy of logging identification of hydrate reservoirs and is of great significance for the estimation of hydrate reserves.

Fluorescence properties of Yb3+-Er3+ co-doped phosphate glasses containing silver nanoparticles

NASA Astrophysics Data System (ADS)

Martínez Gámez, Ma A.; Vallejo H, Miguel A.; Kiryanov, A. V.; Licea-Jiménez, L.; Lucio M, J. L.; Pérez-García, S. A.

2018-04-01

Er3+-Yb3+ co-doped phosphate glasses containing silver nitrate (SN), were fabricated. Transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) analyses were used to evidence the nucleation and presence of silver nanoparticles (SNP). The basic parameters of the glasses were inspected by means of absorption and fluorescence spectra, and fluorescence lifetimes under excitation at 916 nm (in-band of Yb3+), and at 406 nm (in-band of surface plasmon resonance given by the presence of SNP). The spectra as well as estimates for the basic parameters defining the lasing/amplifying potential of the glasses were studied as a function of SN concentration. The experimental results indicate that by increasing the SN content an enhancement of Er3+/Yb3+ fluorescence takes place.

Seismic wave velocity of hydrate-bearing fine-grained sediments sampled from the Ulleung basin in East Sea, Korea

NASA Astrophysics Data System (ADS)

Kim, H.; Kwon, T.; Cho, G.

2012-12-01

Synthesizing gas hydrate in a fine-grained natural seabed sediment sample, mainly composed of silty-to-clayey soils, has been hardly attempted due to the low permeability. It has been known that hydrate loci in pore spaces and heterogeneity of hydrate growth in core-scale play a critical role in determining physical properties of hydrate-bearing sediments. In the presented study, we attempted to identify the effect of hydrate growth morphology on seismic velocities in natural fine-grained sediments sampled from the Ulleung Basin in East Sea. We synthesized CO2 hydrate in clayey silt sediments in an instrumented oedometric cell and measured seismic velocities during hydrate formation and loading processes. Herein, we present the experiment results on P-wave and S-wave velocities of gas hydrate-bearing fine-grained sediments. It is found that the geophysical properties of gas hydrate-bearing sediments are governed by hydrate saturation and effective stress as well as morphological feature of hydrate formation in sediments.

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.

Controls on the physical properties of gas-hydrate-bearing sediments because of the interaction between gas hydrate and porous media

USGS Publications Warehouse

Lee, Myung W.; Collett, Timothy S.

2005-01-01

Physical properties of gas-hydrate-bearing sediments depend on the pore-scale interaction between gas hydrate and porous media as well as the amount of gas hydrate present. Well log measurements such as proton nuclear magnetic resonance (NMR) relaxation and electromagnetic propagation tool (EPT) techniques depend primarily on the bulk volume of gas hydrate in the pore space irrespective of the pore-scale interaction. However, elastic velocities or permeability depend on how gas hydrate is distributed in the pore space as well as the amount of gas hydrate. Gas-hydrate saturations estimated from NMR and EPT measurements are free of adjustable parameters; thus, the estimations are unbiased estimates of gas hydrate if the measurement is accurate. However, the amount of gas hydrate estimated from elastic velocities or electrical resistivities depends on many adjustable parameters and models related to the interaction of gas hydrate and porous media, so these estimates are model dependent and biased. NMR, EPT, elastic-wave velocity, electrical resistivity, and permeability measurements acquired in the Mallik 5L-38 well in the Mackenzie Delta, Canada, show that all of the well log evaluation techniques considered provide comparable gas-hydrate saturations in clean (low shale content) sandstone intervals with high gas-hydrate saturations. However, in shaly intervals, estimates from log measurement depending on the pore-scale interaction between gas hydrate and host sediments are higher than those estimates from measurements depending on the bulk volume of gas hydrate.

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.

Methane hydrate formation in partially water-saturated Ottawa sand

USGS Publications Warehouse

Waite, W.F.; Winters, W.J.; Mason, D.H.

2004-01-01

Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

Hydrate-Bearing Clayey Sediments: Morphology, Physical Properties, Production and Engineering/Geological Implications

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

Dai, Sheng; Santamarina, J. Carlos

Fine-grained sediments host more than 90 percent of global gas hydrate accumulation. However, hydrate formation in clay-dominated sediments is less understood and characterized than other types of hydrate occurrence. There is an inadequate understanding of hydrate formation mechanisms, segregation structures, hydrate lens topology, system connectivity, and physical macro-scale properties of clay-dominated hydrate-bearing sediments. This situation hinders further analyses of the global carbon budget as well as engineering challenges/solutions related to hydrate instability and production. This project studies hydrate-bearing clay-dominated sediments with emphasis on the enhanced fundamental understanding of hydrate formation and resulting morphology, the development laboratory techniques to emulate naturalmore » hydrate formations, the assessment of analytical tools to predict physical properties, the evaluation of engineering and geological implications, and the advanced understanding of gas production potential from finegrained sediments.« less

Syncope among U.S. Air Force basic military trainees, August 2012-July 2013.

PubMed

Webber, Bryant J; Cropper, Thomas L; Federinko, Susan P

2013-11-01

Syncope is a common event with many possible etiologies, ranging from benign to severe. Syncopal episodes of any origin, however, may result in traumatic injury due to postural collapse. Based on the prevalence of internal and external stressors during training, basic military trainees may be at increased risk for syncope. Between 1 August 2012 and 31 July 2013, there were 112 unique individuals who experienced syncopal or pre-syncopal events among basic military trainees at Joint Base San Antonio-Lackland, Texas, the only basic training site in the U.S. Air Force. The overall rate was 19.6 cases per 1,000 person-years (18.4 and 36.1 per 1,000 person-years in males and females, respectively). Based upon the findings of electronic chart review of the 112 cases, a majority of events occurred either during or immediately after exercise (n=38) or during a blood draw, immunization, or laceration repair (n=22). The most common etiologies were judged to be neurocardiogenic (n=54) and orthostatic hypotension (n=40), and two cases were attributed to cardiovascular disease. These findings support current preventive measures, including anemia screening during medical in-processing, an emphasis on hydration throughout training, and a padded floor in the trainee vaccination bay.

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.

Ab initio investigation of the first hydration shell of protonated glycine

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

Wei, Zhichao; Chen, Dong, E-mail: dongchen@henu.edu.cn, E-mail: boliu@henu.edu.cn; Zhao, Huiling

2014-02-28

The first hydration shell of the protonated glycine is built up using Monte Carlo multiple minimum conformational search analysis with the MMFFs force field. The potential energy surfaces of the protonated glycine and its hydration complexes with up to eight water molecules have been scanned and the energy-minimized structures are predicted using the ab initio calculations. First, three favorable structures of protonated glycine were determined, and the micro-hydration processes showed that water can significantly stabilize the unstable conformers, and then their first hydration shells were established. Finally, we found that seven water molecules are required to fully hydrate the firstmore » hydration shell for the most stable conformer of protonated glycine. In order to analyse the hydration process, the dominant hydration sites located around the ammonium and carboxyl groups are studied carefully and systemically. The results indicate that, water molecules hydrate the protonated glycine in an alternative dynamic hydration process which is driven by the competition between different hydration sites. The first three water molecules are strongly attached by the ammonium group, while only the fourth water molecule is attached by the carboxyl group in the ultimate first hydration shell of the protonated glycine. In addition, the first hydration shell model has predicted most identical structures and a reasonable accord in hydration energy and vibrational frequencies of the most stable conformer with the conductor-like polarizable continuum model.« less

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.

Thermodynamic properties of methane hydrate in quartz powder.

PubMed

Voronov, Vitaly P; Gorodetskii, Evgeny E; Safonov, Sergey S

2007-10-04

Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.

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.

Basic Study on Production Well Integrity for Methane Hydrate Development

NASA Astrophysics Data System (ADS)

Kakumoto, M.; Yoneda, J.; Katagiri, J.; Tenma, N.; Aoki, K.

2014-12-01

Methane Hydrate (MH) exist as an ice-like crystal under low-temperature and high-pressure condition, and it has gathering attention as a non-conventional natural gas resource. Depressurization method is a method to reduce the bottom hole pressure by submersible pump lowering water level in the production well, and gas and water is recovered by MH dissociation at the in situ. During the depressurization operation, consolidation and deformation of sediment occurs because of increase of effective stress by depressurization and changes in the soil structure by MH dissociation. Then consolidation and deformation of sediment makes negative friction between the production well and sediment, and large stress is occur in casing. Therefore there is concern that it may cause compression failure and shear failure of the production well. For safe MH development, it is necessary to grasp the deformation and stress vicinity of the production well. At first, we conducted push-out test to get friction strength between the different materials simulated the well and sediment. And we have done numerical analysis for integrity using by these data. The results of numerical analysis showed that the large deformation of sediment occur around the depressurization zone, and for the well, the large tensile stress in the vertical direction occur the upper vicinity of the depressurization zone.This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by Ministry of Economy, Trade and Industry (METI). The authors thank the entire personnel related to MH21 Research Consortium.

Nuclear quantum effects in water exchange around lithium and fluoride ions

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

Wilkins, David M.; Manolopoulos, David; Dang, Liem X.

2015-02-14

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain reasonably good agreement with experimental data for solutions of lithium by augmenting the Coulombic interactions between the ion and the water molecules with a standard Lennard-Jones ion-oxygen potential, the same is not true for solutions of fluoride, for which we find that a potential with a softer repulsive wall gives much better agreement. A small degree of destabilization of the first hydration shell ismore » found in quantum simulations of both ions when compared with classical simulations, with the shell becoming less sharply defined and the mean residence time of the water molecules in the shell decreasing. In line with these modest differences, we find that the mechanisms of the water exchange reactions are unaffected by quantization, so a classical description of these reactions gives qualitatively correct and quantitatively reasonable results. We also find that the quantum effects in solutions of lithium are larger than in solutions of fluoride. This is partly due to the stronger interaction of lithium with water molecules, partly due to the lighter mass of lithium, and partly due to competing quantum effects in the hydration of fluoride, which are absent in the hydration of lithium. LXD was supported by US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Treatment of Xerosis with a Topical Formulation Containing Glyceryl Glucoside, Natural Moisturizing Factors, and Ceramide

PubMed Central

Kausch, Martina; Rippke, Frank; Schoelermann, Andrea M.; Filbry, Alexander W.

2012-01-01

Objective: To assess the effects of Light Formulation, an oil-in-water emulsion, and Rich Formulation, a water-in-oil emulsion, for the treatment of xerosis. Design: Two double-blind, vehicle-controlled trials (both formulations); a double-blind, randomized regression study (Rich Formulation); and a single-blind tolerability study (Light Formulation). The two formulations were applied twice daily for two weeks, for five days in the regression study, and twice daily for two weeks in the tolerability study. Setting: Studies were conducted during winter in Hamburg, Germany. Participants: A total of 169 subjects were enrolled and 154 completed the studies. The majority were between 50 and 80 years of age, women, all with very dry skin. One withdrew because of an incompatibility reaction that reoccurred with the subject's own body lotion after sun exposure. Measurements: Skin hydration and skin barrier function with both formulations over two weeks, long-term moisturization effect after discontinuation of Rich Formulation, and symptom improvement and skin tolerability with Light Formulation. Results: Vehicle-controlled studies of Light and Rich Formulations demonstrated significantly improved hydration at Weeks 1 and 2 versus the untreated site and vehicles, and significantly reduced transepidermal water loss versus untreated site and basic vehicle. Both products significantly decreased visible dryness and tactile roughness. In the regression study, Rich Formulation maintained significant moisturization six days after treatment discontinuation. Light Formulation reduced symptoms of itching, burning, tightness, tingling, and feeling of dryness. Conclusion: These formulations represent a new approach for the treatment of xerosis by addressing multiple key deficiencies in skin hydration. PMID:22916312

Development of hydrate risk quantification in oil and gas production

NASA Astrophysics Data System (ADS)

Chaudhari, Piyush N.

Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in order to reduce the parametric study that may require a long duration of time using The Colorado School of Mines Hydrate Kinetic Model (CSMHyK). The evolution of the hydrate plugging risk along flowline-riser systems is modeled for steady state and transient operations considering the effect of several critical parameters such as oil-hydrate slip, duration of shut-in, and water droplet size on a subsea tieback system. This research presents a novel platform for quantification of the hydrate plugging risk, which in-turn will play an important role in improving and optimizing current hydrate management strategies. The predictive strength of the hydrate risk quantification and hydrate prediction models will have a significant impact on flow assurance engineering and design with respect to building safe and efficient hydrate management techniques for future deep-water developments.

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.

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.

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.

Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

USGS Publications Warehouse

Lorenson, T.D.

1999-01-01

Molecular and isotopic composition of gases from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well demonstrate that the in situ gases can be divided into three zones composed of mixtures of microbial and thermogenic gases. Sediments penetrated by the well are thermally immature; thus the sediments are probably not a source of thermogenic gas. Thermogenic gas likely migrated from depths below 5000 m. Higher concentrations of gas within and beneath the gas hydrate zone suggest that gas hydrate is a partial barrier to gas migration. Gas hydrate accumulations occur wholly within zone 3, below the base of permafrost. The gas in gas hydrate resembles, in part, the thermogenic gas in surrounding sediments and gas desorbed from lignite. Gas hydrate composition implies that the primary gas hydrate form is Structure I. However, Structure II stabilizing gases are more concentrated and isotopically partitioned in gas hydrate relative to the sediment hosting the gas hydrate, implying that Structure II gas hydrate may be present in small quantities.

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

NASA Astrophysics Data System (ADS)

Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

2007-07-01

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

Economic geology of natural gas hydrate

USGS Publications Warehouse

Max, M.D.; Johnson, A.H.; Dillon, William P.

2006-01-01

This is the first book that attempts to broadly integrate the most recent knowledge in the fields of hydrate nucleation and growth in permafrost regions and marine sediments. Gas hydrate reactant supply, growth models, and implications for pore fill by natural gas hydrate are discussed for both seawater precursors in marine sediments and for permafrost hydrate. These models for forming hydrate concentrations that will constitute targets for exploration are discussed, along with exploration methods. Thermodynamic models for the controlled conversion of hydrate to natural gas, which can be recovered using conventional industry practices, suggest that a number of different types of hydrate occurrence are likely to be practical sources of hydrate natural gas. Current progress in the various aspects of commercial development of hydrate gas deposits are discussed, along with the principal extractive issues that have yet to be resolved.

Energy resource potential of natural gas hydrates

USGS Publications Warehouse

Collett, T.S.

2002-01-01

The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

Location of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

Locations of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg-white lysozyme from salt solutions. Previous studies employing X-ray crystallography have found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystals grown in bromide and chloride solutions. Five possible anion-binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four further sites were found which corresponded to the four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion-binding sites in lysozyme remain unchanged even when different anions and different crystal forms of lysozyme are employed.

Mesophilic, Circumneutral Anaerobic Iron Oxidation as a Remediation Mechanism for Radionuclides, Nitrate and Perchlorate

NASA Astrophysics Data System (ADS)

Bose, S.; Thrash, J. C.; Coates, J. D.

2008-12-01

Iron oxidation is a novel anaerobic metabolism where microorganisms obtain reducing equivalents from the oxidization of Fe(II) and assimilate carbon from organic carbon compounds or CO2. Recent evidence indicates that in combination with the activity of dissimilatory Fe(III)-reducing bacteria, anaerobic microbial Fe(II) oxidation can also contribute to the global iron redox cycle. Studies have also proved that Fe(II)- oxidation is ubiquitous in diverse environments and produce a broad range of insoluble iron forms as end products. These biogenic Fe(III)-oxides and mixed valence Fe minerals have a very high adsorption capacity of heavy metals and radionuclides. Adsorption and immobilization by these biogenic Fe phases produced at circumneutral pH, is now considered a very effective mode of remediation of radionuclides like Uranium, especially under variable redox conditions. By coupling soluble and insoluble Fe(II) oxidation with nitrate and perchlorate as terminal electron acceptors in-situ, anaerobic Fe-oxidation can also be used for environmental cleanup of Fe through Fe-mineral precipitation, as well as nitrate and perchlorate through reduction. Coupling of Fe as the sole electron and energy source to the reduction of perchlorate or nitrate boosts the metabolism without building up biomass hence also taking care of biofouling. To understand the mechanisms by which microorganisms can grow at circumneutral pH by mesophilic, anaerobic iron oxidation and the ability of microorganisms to reduce nitrate and perchlorate coupled to iron oxidation recent work in our lab involved the physiological characterization of Dechlorospirillum strain VDY which was capable of anaerobic iron-oxidation with either nitrate or perchlorate serving as terminal electron acceptor. Under non-growth conditions, VDY oxidized 3mM Fe(II) coupled to nitrate reduction, and 2mM Fe(II) coupled to perchlorate reduction, in 24 hours. It contained a copy of the RuBisCO cbbM subunit gene which was differentially regulated. With perchlorate as the sole terminal electron acceptor, cbbM was expressed under autotrophic growth with hydrogen as the electron donor but not during heterotrophic growth on acetate, indicating a putative carbon-fixation pathway. Similarly, Ferrutens uranioxidens strain 2002 was also capable of autotrophic growth during nitrate-dependent iron oxidation, although the carbon fixation pathway has yet to be identified. Anoxic XPRD analysis of the biogenic end products of nitrate-dependent Fe(II) oxidation by Diaphorobacter sp. strain TPSY and strain 2002 indicated the gradual appearance of green rust (GR II) with cacoxenite and lepidocrocite from the precursor vivianite over 81 days. SEM and TEM showed the presence of hexagonal plate like crystals surrounding the bacterial cells whose morphology closely resembled GR II, indicating a very low redox potential and a weakly acidic to weakly basic pH. Mixotrophic growth incubations of strain TPSY with 1, 5 and 10 mM Fe(II) showed markedly different end products. The identity of the mineral phases and the reason behind this difference is currently under investigation.

The effect of inorganic precursors on disinfection byproduct formation during UV-chlorine/chloramine drinking water treatment.

PubMed

Lyon, Bonnie A; Dotson, Aaron D; Linden, Karl G; Weinberg, Howard S

2012-10-01

Ultraviolet (UV) disinfection is being increasingly used in drinking water treatment. It is important to understand how its application to different types of water may influence finished water quality, particularly as anthropogenic activity continues to impact the quality of source waters. The objective of this study was to evaluate the effect of inorganic precursors on the formation of regulated and unregulated disinfection byproducts (DBPs) during UV irradiation of surface waters when combined with chlorination or chloramination. Samples were collected from three drinking water utilities supplied by source waters with varying organic and inorganic precursor content. The filtered samples were treated in the laboratory with a range of UV doses delivered from low pressure (LP, UV output at 253.7 nm) and medium pressure (MP, polychromatic UV output 200-400 nm) mercury lamps followed by chlorination or chloramination, in the presence and absence of additional bromide and nitrate. The regulated trihalomethanes and haloacetic acids were not affected by UV pretreatment at disinfection doses (40-186 mJ/cm²). With higher doses (1000 mJ/cm²), trihalomethane formation was increased 30-40%. While most effects on DBPs were only observed with doses much higher than typically used for UV disinfection, there were some effects on unregulated DBPs at lower doses. In nitrate-spiked samples (1-10 mg N/L), chloropicrin formation doubled and increased three- to six-fold with 40 mJ/cm² MP UV followed by chloramination and chlorination, respectively. Bromopicrin formation was increased in samples containing bromide (0.5-1 mg/L) and nitrate (1-10 mg N/L) when pretreated with LP or MP UV (30-60% with 40 mJ/cm² LP UV and four- to ten-fold increase with 40 mJ/cm² MP UV, after subsequent chlorination). The formation of cyanogen chloride doubled and increased three-fold with MP UV doses of 186 and 1000 mJ/cm², respectively, when followed by chloramination in nitrate-spiked samples but remained below the World Health Organization guideline value of 70 μg/L in all cases. MP UV and high LP UV doses (1000 mJ/cm²) increased chloral hydrate formation after subsequent chlorination (20-40% increase for 40 mJ/cm² MP UV). These results indicate the importance of bench-testing DBP implications of UV applications in combination with post-disinfectants as part of the engineering assessment of a UV-chlorine/chloramine multi-barrier disinfection design for drinking water treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

Methane hydrates in nature - Current knowledge and challenges

USGS Publications Warehouse

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance our understanding of methane hydrates in nature. COL assembled a Methane Hydrate Project Science Team with members from academia, industry, and government. This Science Team worked with COL and DOE to develop and host the Methane Hydrate Community Workshop, which surveyed a substantial cross section of the methane hydrate research community for input on the most important research developments in our understanding of methane hydrates in nature and their potential role as an energy resource, a geohazard, and/or as an agent of global climate change. Our understanding of how methane hydrates occur in nature is still growing and evolving, and it is known with certainty that field, laboratory, and modeling studies have contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information needed to advance our understanding of methane hydrates.

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.

The transformation of nitrogen in soil under Robinia Pseudacacia shelterbelt and in adjoining cultivated field

NASA Astrophysics Data System (ADS)

Szajdak, L.; Gaca, W.

2009-04-01

The shelterbelts perform more than twenty different functions favorable to the environment, human economy, health and culture. The most important for agricultural landscape is increase of water retention, purification of ground waters and prevent of pollution spread in the landscape, restriction of wind and water erosion effects, isolation of polluting elements in the landscape, preservation of biological diversity in agricultural areas and mitigation of effects of unfavorable climatic phenomena. Denitrification is defined as the reduction of nitrate or nitrite coupled to electron transport phosphorylation resulting in gaseous N either as molecular N2 or as an oxide of N. High content of moisture, low oxygen, neutral and basic pH favour the denitrification. Nitrate reductase is an important enzyme involved in the process of denitrification. The reduction of nitrate to nitrite is catalyzed by nitrate reductase. Nitrite reductase is catalyzed reduction nitrite to nitrous oxide. The conversion of N2O to N2 is catalyzed by nitrous oxide reductase. This process leads to the lost of nitrogen in soil mainly in the form of N2 and N2O. Nitrous oxide is a greenhouse gas which cause significant depletion of the Earth's stratospheric ozone layer. The investigations were carried out in Dezydery Chlapowski Agroecological Landscape Park in Turew (40 km South-West of Poznań, West Polish Lowland). Our investigations were focused on the soils under Robinia pseudacacia shelterbelt and in adjoining cultivated field. The afforestation was created 200 years ago and it is consist of mainly Robinia pseudacacia with admixture of Quercus petraea and Quercus robur. This shelterbelt and adjoining cultivated field are located on grey-brown podzolic soil. The aim of this study is to present information on the changes of nitrate reductase activity in soil with admixture urea (organic form of nitrogen) in two different concentrations 0,25% N and 0,5% N. Our results have shown that this process runs according to the equation rate of first-order kinetic reaction model. Activity of nitrate reductase increases with an addition of urea under Robinia pseudacacia shelterbelt and in adjoining cultivated fields. However the activity of nitrate reductase decreases during a long term of experiment. First-order rate constant was calculated for the changes of activity of nitrate reductase. Admixture of urea influenced on reaction rate constant. It was observed similar contents at addition 0,25% N and 0,5% N. In adjoining cultivated field to Robinia pseudacacia shelterbelt first order rate constant was higher at addition 0,25% N than 0,5% N. This work was supported by a grant No. N N305 121934 founded by Polish Ministry of Education.

Diversity of microbial communities correlated to physiochemical parameters in a digestion basin of a zero-discharge mariculture system.

PubMed

Cytryn, Eddie; Gelfand, Ilya; Barak, Yoram; van Rijn, Jaap; Minz, Dror

2003-01-01

Bacterial community structure and physiochemical parameters were examined in a sedimentation basin of a zero-discharge mariculture system. The system consisted of an intensively stocked fish basin from which water was recirculated through two separate treatment loops. Surface water from the basin was pumped over a trickling filter in one loop while bottom-water was recirculated through a sedimentation basin followed by a fluidized bed reactor in the other. Ammonia oxidation to nitrate in the trickling filter and organic matter digestion together with nitrate reduction in the sedimentation basin and fluidized bed reactor, allowed zero-discharge operation of the system. Relatively high concentrations of oxygen, nitrate, sulphate and organic matter detected simultaneously in the digestion basin suggested the potential for a wide range of microbially-mediated transformation processes. In this study, physiochemical parameters were correlated to bacterial diversity and distribution in horizontal and vertical profiles within this basin in an effort to obtain a basic understanding of the chemical and microbial processes in this system. Chemical activity and microbial diversity, the latter measured by denaturing gradient gel electrophoresis (DGGE) analysis of polymerase chain reaction (PCR) amplified 16S rDNA fragments, were higher in the sludge layer than in the overlying aqueous layer of the basin. Chemical parameters in sludge samples close to the basin inlet suggested enhanced microbial activity relative to other sampling areas with evidence of both nitrate and sulphate reduction. Four of the nine DGGE bands identified in this zone were affiliated with the Bacteroidetes phylum. Detected sequences closely related to sequences of organisms involved in the sulphur cycle included Desulfovibrio, Dethiosulfovibrio and apparent sulphur oxidizers from the gamma-proteobacteria. In addition, a number of sequences from the beta and alpha-proteobacteria were identified.

The effects of agriculture on the volcanic aquifers of the canary islands

NASA Astrophysics Data System (ADS)

Custodio, E.; Guerra, J. A.; Jiménez, J.; Medina, J. A.; Soler, C.

1983-12-01

Agriculture is a basic economic activity in the Canary Islands, a Spanish region in the Atlantic Ocean, facing the Sahara. The main crops are bananas, tomatoes, and other special ones suitable for exportation. Fertilizers are applied in high quantities on the scarce land available. The relatively good vertical permeability of the soils favors the deep infiltration of irrigation return flows. Water is obtained by an extraordinary net of shaft wells and water galleries, supplemented when possible by surface reservoirs in the deep gullies. Water is distributed by an extensive network of pipes and canals, allowing the transportation of water to virtually any point from any water source. Water quality is widely variable, from almost rain water to brackish, with a high frequency of sodium bicarbonate types. Return flows, especially when water is applied with good irrigation techniques and the original quality is poor, are saline and contain chemicals leached from the fertilizers. On Tenerife Island, most of the return flows go to coastal aquifers, while most of the water comes from high-altitude water galleries. Agricultural pollution is not generally appraised, but it exists. It can be masked by the frequent, high natural nitrate content in groundwater. On Gran Canaria Island, since water comes mainly from deep shaft wells near the irrigated areas, the nitrate pollution is much more clear. On La Palma Island, besides the nitrate pollution, a potassium pollution of agricultural origin has been mentioned. Other situations on the remaining islands are also discussed. It can be concluded that agriculture is a big concern for the water quality in many areas and impairs its suitability for other uses. Because of the great depth of the water table, the nitrate pollution may not become obvious for many years, especially for the deep-water galleries.

Using polarizable POSSIM force field and fuzzy-border continuum solvent model to calculate pK(a) shifts of protein residues.

PubMed

Sharma, Ity; Kaminski, George A

2017-01-15

Our Fuzzy-Border (FB) continuum solvent model has been extended and modified to produce hydration parameters for small molecules using POlarizable Simulations Second-order Interaction Model (POSSIM) framework with an average error of 0.136 kcal/mol. It was then used to compute pK a shifts for carboxylic and basic residues of the turkey ovomucoid third domain (OMTKY3) protein. The average unsigned errors in the acid and base pK a values were 0.37 and 0.4 pH units, respectively, versus 0.58 and 0.7 pH units as calculated with a previous version of polarizable protein force field and Poisson Boltzmann continuum solvent. This POSSIM/FB result is produced with explicit refitting of the hydration parameters to the pK a values of the carboxylic and basic residues of the OMTKY3 protein; thus, the values of the acidity constants can be viewed as additional fitting target data. In addition to calculating pK a shifts for the OMTKY3 residues, we have studied aspartic acid residues of Rnase Sa. This was done without any further refitting of the parameters and agreement with the experimental pK a values is within an average unsigned error of 0.65 pH units. This result included the Asp79 residue that is buried and thus has a high experimental pK a value of 7.37 units. Thus, the presented model is capable or reproducing pK a results for residues in an environment that is significantly different from the solvated protein surface used in the fitting. Therefore, the POSSIM force field and the FB continuum solvent parameters have been demonstrated to be sufficiently robust and transferable. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Molecular insights into the enhanced rate of CO2 absorption to produce bicarbonate in aqueous 2-amino-2-methyl-1-propanol.

PubMed

Stowe, Haley M; Hwang, Gyeong S

2017-12-06

2-Amino-2-methyl-1-propanol (AMP), a sterically hindered amine, exhibits a much higher CO 2 absorption rate relative to tertiary amine diethylethanolamine (DEEA), while both yield bicarbonate as a major product in aqueous solution, despite their similar basicity. We present molecular mechanisms underlying the significant difference of CO 2 absorption rate based on ab initio molecular dynamics simulations combined with metadynamics. Our calculations predict the free energy barrier for base-catalyzed CO 2 hydration to be lower in aqueous AMP compared to DEEA. Further molecular analysis suggests that the difference in free energy barrier is largely attributed to entropic effects associated with reorganization of H 2 O molecules adjacent to the basic N site. Stronger hydrogen bonding of H 2 O with N of DEEA than AMP, in addition to the presence of bulky ethyl groups, suppresses the thermal rearrangement of adjacent H 2 O molecules, thereby leading to lower stability of the transition state involving OH - creation and CO 2 polarization. Moreover, the hindered reorganization of adjacent H 2 O molecules is found to facilitate migration of OH - (created via proton abstraction by DEEA) away from the N site while suppressing CO 2 approach. This leads us to speculate that catalyzed CO 2 hydration in aqueous DEEA may involve OH - migration through multiple hydrogen-bonded H 2 O molecules prior to reaction with CO 2 , whereas in aqueous AMP it seems to preferentially follow the one H 2 O-mediated mechanism. This study highlights the importance of entropic effects in determining both mechanisms and rates of CO 2 absorption into aqueous sterically hindered amines.

Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions

NASA Astrophysics Data System (ADS)

Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

2017-07-01

Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)- complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)]- and [MAII-H+(HNO3)]- ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n]3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins.

Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions.

PubMed

Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

2017-07-01

Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO 3 ) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO 3 -nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO 3 ) was produced in the flame. The HNO 3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO 3 showed the strongest affinity to histidine and formed (M histidine -H+HNO 3 ) - complex ions, whereas some amino acids did not react with HNO 3 at all. Reactions between HNO 3 and histidine residues in AI and AII resulted in the formation of dominant [M AI -H+(HNO 3 )] - and [M AII -H+(HNO 3 )] - ions. Results from analyses of AAs and insulin indicated that HNO 3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO 3 ) n ] 3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins. Graphical Abstract ᅟ.

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need to match the arrangements of silanols to form more hydrogen bonds. At the end of the simulation, the hydrate solid is separated from the silica surface by liquid water, with only several cages forming hydrogen bonds with the silica surface, mainly due to the low CH 4 aqueous concentrations near the surface. To further explore hydrate formation between graphite surfaces, CH 4 /water homogeneous solution systems are also simulated. CH 4 molecules in the solution are adsorbed onto graphite and hydrate nucleation occurs in the bulk region. During hydrate growth, the adsorbed CH 4 molecules are gradually converted into hydrate solid. It is found that the hydrate-like ordering of interfacial water induced by graphite promotes the contact between hydrate solid and graphite. We reveal that the ability of silanol groups on silica to form strong hydrogen bonds to stabilize incipient hydrate solid, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

Molecular Dynamics Simulation of the Crystal Nucleation and Growth Behavior of Methane Hydrate in the Presence of the Surface and Nanopores of Porous Sediment.

PubMed

Yan, Ke-Feng; Li, Xiao-Sen; Chen, Zhao-Yang; Xia, Zhi-Ming; Xu, Chun-Gang; Zhang, Zhiqiang

2016-08-09

The behavior of hydrate formation in porous sediment has been widely studied because of its importance in the investigation of reservoirs and in the drilling of natural gas hydrate. However, it is difficult to understand the hydrate nucleation and growth mechanism on the surface and in the nanopores of porous media by experimental and numerical simulation methods. In this work, molecular dynamics simulations of the nucleation and growth of CH4 hydrate in the presence of the surface and nanopores of clay are carried out. The molecular configurations and microstructure properties are analyzed for systems containing one H2O hydrate layer (System A), three H2O hydrate layers (System B), and six H2O hydrate layers (System C) in both clay and the bulk solution. It is found that hydrate formation is more complex in porous media than in the pure bulk solution and that there is cooperativity between hydrate growth and molecular diffusion in clay nanopores. The hydroxylated edge sites of the clay surface could serve as a source of CH4 molecules to facilitate hydrate nucleation. The diffusion velocity of molecules is influenced by the growth of the hydrate that forms a block in the throats of the clay nanopore. Comparing hydrate growth in different clay pore sizes reveals that the pore size plays an important role in hydrate growth and molecular diffusion in clay. This simulation study provides the microscopic mechanism of hydrate nucleation and growth in porous media, which can be favorable for the investigation of the formation of natural gas hydrate in sediments.

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.

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.

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.

Dielectric method of high-resolution gas hydrate estimation

NASA Astrophysics Data System (ADS)

Sun, Y. F.; Goldberg, D.

2005-02-01

In-situ dielectric properties of natural gas hydrate are measured for the first time in the Mallik 5L-38 Well in the Mackenzie Delta, Canada. The average dielectric constant of the hydrate zones is 9, ranging from 5 to 20. The average resistivity is >5 ohm.m in the hydrate zones, ranging from 2 to 10 ohm.m at a 1.1 GHz dielectric tool frequency. The dielectric logs show similar trends with sonic and induction resistivity logs, but exhibits inherently higher vertical resolution (<5 cm). The average in-situ hydrate saturation in the well is about 70%, ranging from 20% to 95%. The dielectric estimates are overall in agreement with induction estimates but the induction log tends to overestimate hydrate content up to 15%. Dielectric estimates could be used as a better proxy of in-situ hydrate saturation in modeling hydrate dynamics. The fine-scale structure in hydrate zones could help reveal hydrate formation history.

Properties of samples containing natural gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, determined using Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI)

USGS Publications Warehouse

Winters, W.J.

1999-01-01

As part of an ongoing laboratory study, preliminary acoustic, strength, and hydraulic conductivity results are presented from a suite of tests conducted on four natural-gas-hydrate-containing samples from the Mackenzie Delta JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The gas hydrate samples were preserved in pressure vessels during transport from the Northwest Territories to Woods Hole, Massachusetts, where multistep tests were performed using GHASTLI (Gas Hydrate And Sediment Test Laboratory Instrument), which recreates pressure and temperature conditions that are stable for gas hydrate. Properties and changes in sediment behaviour were measured before, during, and after controlled gas hydrate dissociation. Significant amounts of gas hydrate occupied the sample pores and substantially increased acoustic velocity and shear strength.

Surfactant process for promoting gas hydrate formation and application of the same

DOEpatents

Rogers, Rudy E.; Zhong, Yu

2002-01-01

This invention relates to a method of storing gas using gas hydrates comprising forming gas hydrates in the presence of a water-surfactant solution that comprises water and surfactant. The addition of minor amounts of surfactant increases the gas hydrate formation rate, increases packing density of the solid hydrate mass and simplifies the formation-storage-decomposition process of gas hydrates. The minor amounts of surfactant also enhance the potential of gas hydrates for industrial storage applications.

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.

Probing methane hydrate nucleation through the forward flux sampling method.

PubMed

Bi, Yuanfei; Li, Tianshu

2014-11-26

Understanding the nucleation of hydrate is the key to developing effective strategies for controlling methane hydrate formation. Here we present a computational study of methane hydrate nucleation, by combining the forward flux sampling (FFS) method and the coarse-grained water model mW. To facilitate the application of FFS in studying the formation of methane hydrate, we developed an effective order parameter λ on the basis of the topological analysis of the tetrahedral network. The order parameter capitalizes the signature of hydrate structure, i.e., polyhedral cages, and is capable of efficiently distinguishing hydrate from ice and liquid water while allowing the formation of different hydrate phases, i.e., sI, sII, and amorphous. Integration of the order parameter λ with FFS allows explicitly computing hydrate nucleation rates and obtaining an ensemble of nucleation trajectories under conditions where spontaneous hydrate nucleation becomes too slow to occur in direct simulation. The convergence of the obtained hydrate nucleation rate was found to depend crucially on the convergence of the spatial distribution for the spontaneously formed hydrate seeds obtained from the initial sampling of FFS. The validity of the approach is also verified by the agreement between the calculated nucleation rate and that inferred from the direct simulation. Analyzing the obtained large ensemble of hydrate nucleation trajectories, we show hydrate formation at 220 K and 500 bar is initiated by the nucleation events occurring in the vicinity of water-methane interface, and facilitated by a gradual transition from amorphous to crystalline structure. The latter provides the direct support to the proposed two-step nucleation mechanism of methane hydrate.

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

PubMed

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

2006-04-28

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

CO2 hydrate formation and dissociation in cooled porous media: a potential technology for CO2 capture and storage.

PubMed

Yang, Mingjun; Song, Yongchen; Jiang, Lanlan; Zhu, Ningjun; Liu, Yu; Zhao, Yuechao; Dou, Binlin; Li, Qingping

2013-09-03

The purpose of this study was to investigate the hydrate formation and dissociation with CO2 flowing through cooled porous media at different flow rates, pressures, temperatures, and flow directions. CO2 hydrate saturation was quantified using the mean intensity of water. The experimental results showed that the hydrate block appeared frequently, and it could be avoided by stopping CO2 flooding early. Hydrate formed rapidly as the temperature was set to 274.15 or 275.15 K, but the hydrate formation delayed when it was 276.15 K. The flow rate was an important parameter for hydrate formation; a too high or too low rate was not suitable for CO2 hydration formation. A low operating pressure was also unacceptable. The gravity made hydrate form easily in the vertically upward flow direction. The pore water of the second cycle converted to hydrate more completely than that of the first cycle, which was a proof of the hydrate "memory effect". When the pressure was equal to atmospheric pressure, hydrate did not dissociate rapidly and abundantly, and a long time or reduplicate depressurization should be used in industrial application.

Thermodynamic properties of hydrate phases immersed in ice phase

NASA Astrophysics Data System (ADS)

Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

2006-01-01

Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

Numerical analysis of wellbore instability in gas hydrate formation during deep-water drilling

NASA Astrophysics Data System (ADS)

Zhang, Huaiwen; Cheng, Yuanfang; Li, Qingchao; Yan, Chuanliang; Han, Xiuting

2018-02-01

Gas hydrate formation may be encountered during deep-water drilling because of the large amount and wide distribution of gas hydrates under the shallow seabed of the South China Sea. Hydrates are extremely sensitive to temperature and pressure changes, and drilling through gas hydrate formation may cause dissociation of hydrates, accompanied by changes in wellbore temperatures, pore pressures, and stress states, thereby leading to wellbore plastic yield and wellbore instability. Considering the coupling effect of seepage of drilling fluid into gas hydrate formation, heat conduction between drilling fluid and formation, hydrate dissociation, and transformation of the formation framework, this study established a multi-field coupling mathematical model of the wellbore in the hydrate formation. Furthermore, the influences of drilling fluid temperatures, densities, and soaking time on the instability of hydrate formation were calculated and analyzed. Results show that the greater the temperature difference between the drilling fluid and hydrate formation is, the faster the hydrate dissociates, the wider the plastic dissociation range is, and the greater the failure width becomes. When the temperature difference is greater than 7°C, the maximum rate of plastic deformation around the wellbore is more than 10%, which is along the direction of the minimum horizontal in-situ stress and associated with instability and damage on the surrounding rock. The hydrate dissociation is insensitive to the variation of drilling fluid density, thereby implying that the change of the density of drilling fluids has a minimal effect on the hydrate dissociation. Drilling fluids that are absorbed into the hydrate formation result in fast dissociation at the initial stage. As time elapses, the hydrate dissociation slows down, but the risk of wellbore instability is aggravated due to the prolonged submersion in drilling fluids. For the sake of the stability of the wellbore in deep-water drilling through hydrate formation, the drilling fluid with low temperatures should be given priority. The drilling process should be kept under balanced pressures, and the drilling time should be shortened.

Effect of Sodium Dodecyl Sulfate Surfactant on Methane Hydrate Formation: A Molecular Dynamics Study.

PubMed

Choudhary, Nilesh; Hande, Vrushali R; Roy, Sudip; Chakrabarty, Suman; Kumar, Rajnish

2018-06-28

In experimental studies, it has been observed that the presence of sodium dodecyl sulfate (SDS) significantly increases the kinetics of hydrate formation and the final water-to-hydrate conversion ratio. In this study, we intend to understand the molecular mechanism behind the effect of SDS on the formation of methane hydrate through molecular dynamics simulation. Hydrate formation conditions similar to that of laboratory experiments were chosen to study hydrate growth kinetics in 1 wt % SDS solution. We also investigate the effect of interactions with isolated SDS molecules on methane hydrate growth. It was observed that the hydrophobic tail part of the SDS molecule favorably interacts with the growing hydrate surface and may occupy the partial hydrate cages while the head groups remain exposed to water.

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.

Equilibrium, Kinetics, and Spectroscopic Studies of SF6 Hydrate in NaCl Electrolyte Solution.

PubMed

Seo, Youngrok; Moon, Donghyun; Lee, Changho; Park, Jeong-Woo; Kim, Byeong-Soo; Lee, Gang-Woo; Dotel, Pratik; Lee, Jong-Won; Cha, Minjun; Yoon, Ji-Ho

2015-05-19

Many studies have focused on desalination via hydrate formation; however, for their potential application, knowledge pertaining to thermodynamic stability, formation kinetics, and guest occupation behavior in clathrate hydrates needs to be determined. Herein, the phase equilibria of SF6 hydrates in the presence of NaCl solutions (0, 2, 4, and 10 wt %) were monitored in the temperature range of 277-286 K and under pressures of up to 1.4 MPa. The formation kinetics of SF6 hydrates in the presence of NaCl solutions (0, 2, and 4 wt %) was also investigated. Gas consumption curves of SF6 hydrates showed that a pure SF6 hydrate system allowed fast hydrate growth as well as high conversion yield, whereas SF6 hydrate in the presence of NaCl solutions showed retarded hydrate growth rate as well as low conversion yield. In addition, structural identification of SF6 hydrates with and without NaCl solutions was performed using spectroscopic tools such as Raman spectroscopy and X-ray diffraction. The Raman spectrometer was also used to evaluate the temperature-dependent release behavior of guest molecules in SF6 and SF6 + 4 wt % NaCl hydrates. The results indicate that whereas SF6 hydrate starts to decompose at around 240 K, the escape of SF6 molecules in SF6 + 4 wt % NaCl hydrate is initiated rapidly at around 205 K. The results of this study can provide a better understanding of guest-host interaction in electrolyte-containing systems.

Micromechanical cohesion force between gas hydrate particles measured under high pressure and low temperature conditions.

PubMed

Lee, Bo Ram; Sum, Amadeu K

2015-04-07

To prevent hydrate plugging conditions in the transportation of oil/gas in multiphase flowlines, one of the key processes to control is the agglomeration/deposition of hydrate particles, which are determined by the cohesive/adhesive forces. Previous studies reporting measurements of the cohesive/adhesive force between hydrate particles used cyclopentane hydrate particles in a low-pressure micromechanical force apparatus. In this study, we report the cohesive forces of particles measured in a new high-pressure micromechanical force (MMF) apparatus for ice particles, mixed (methane/ethane, 74.7:25.3) hydrate particles (Structure II), and carbon dioxide hydrate particles (Structure I). The cohesive forces are measured as a function of the contact time, contact force, temperature, and pressure, and determined from pull-off measurements. For the measurements performed of the gas hydrate particles in the gas phase, the determined cohesive force is about 30-35 mN/m, about 8 times higher than the cohesive force of CyC5 hydrates in the liquid CyC5, which is about 4.3 mN/m. We show from our results that the hydrate structure (sI with CO2 hydrates and sII with CH4/C2H6 hydrates) has no influence on the cohesive force. These results are important in the deposition of a gas-dominated system, where the hydrate particles formed in the liquid phase can then stick to the hydrate deposited in the wall exposed to the gas phase.

The water retention curve and relative permeability for gas production from hydrate-bearing sediments: pore-network model simulation

NASA Astrophysics Data System (ADS)

Mahabadi, Nariman; Dai, Sheng; Seol, Yongkoo; Sup Yun, Tae; Jang, Jaewon

2016-08-01

The water retention curve and relative permeability are critical to predict gas and water production from hydrate-bearing sediments. However, values for key parameters that characterize gas and water flows during hydrate dissociation have not been identified due to experimental challenges. This study utilizes the combined techniques of micro-focus X-ray computed tomography (CT) and pore-network model simulation to identify proper values for those key parameters, such as gas entry pressure, residual water saturation, and curve fitting values. Hydrates with various saturation and morphology are realized in the pore-network that was extracted from micron-resolution CT images of sediments recovered from the hydrate deposit at the Mallik site, and then the processes of gas invasion, hydrate dissociation, gas expansion, and gas and water permeability are simulated. Results show that greater hydrate saturation in sediments lead to higher gas entry pressure, higher residual water saturation, and steeper water retention curve. An increase in hydrate saturation decreases gas permeability but has marginal effects on water permeability in sediments with uniformly distributed hydrate. Hydrate morphology has more significant impacts than hydrate saturation on relative permeability. Sediments with heterogeneously distributed hydrate tend to result in lower residual water saturation and higher gas and water permeability. In this sense, the Brooks-Corey model that uses two fitting parameters individually for gas and water permeability properly capture the effect of hydrate saturation and morphology on gas and water flows in hydrate-bearing sediments.

Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

NASA Astrophysics Data System (ADS)

Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

2014-05-01

The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase. Hence, it is possible to detect areas in the sediment sample where free gas is released due to hydrate dissociation and displaces the liquid phase. Combined with measurements and numerical simulation of the total two-phase fluxes from the sediment sample (see abstract Abendroth et al., this volume), the LARS experiments allow for detailed information on the dissociation process during hydrate production. Here we present the workflow and first results estimating local hydrate saturations and permeabilities during hydrate formation and the movement of liquid and gas phases during hydrate dissociation, respectively.

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.

Effect of Electric Field on Gas Hydrate Nucleation Kinetics: Evidence for the Enhanced Kinetics of Hydrate Nucleation by Negatively Charged Clay Surfaces.

PubMed

Park, Taehyung; Kwon, Tae-Hyuk

2018-03-06

Natural gas hydrates are found widely in oceanic clay-rich sediments, where clay-water interactions have a profound effect on the formation behavior of gas hydrates. However, it remains unclear why and how natural gas hydrates are formed in clay-rich sediments in spite of factors that limit gas hydrate formation, such as small pore size and high salinity. Herein, we show that polarized water molecules on clay surfaces clearly promote gas hydrate nucleation kinetics. When water molecules were polarized with an electric field of 10 4 V/m, gas hydrate nucleation occurred significantly faster with an induction time reduced by 5.8 times. Further, the presence of strongly polarized water layers at the water-gas interface hindered gas uptake and thus hydrate formation, when the electric field was applied prior to gas dissolution. Our findings expand our understanding of the formation habits of naturally occurring gas hydrates in clay-rich sedimentary deposits and provide insights into gas production from natural hydrate deposits.

In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

PubMed

Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

2013-01-02

We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

Historical methane hydrate project review

USGS Publications Warehouse

Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

2013-01-01

In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated effort, the U.S. Congress enacted Public Law 106-­‐193, the Methane Hydrate Research and Development Act of 2000. This Act called for the Secretary of Energy to begin a methane hydrate research and development program in consultation with other U.S. federal agencies. At the same time a new methane hydrate research program had been launched in Japan by the Ministry of International Trade and Industry to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. Since this early start we have seen other countries including India, China, Canada, and the Republic of Korea establish large gas hydrate research and development programs. These national led efforts have also included the investment in a long list of important scientific research drilling expeditions and production test studies that have provided a wealth of information on the occurrence of methane hydrate in nature. The most notable expeditions and projects have including the following:-­‐Ocean Drilling Program Leg 164 (1995)-­‐Japan Nankai Trough Project (1999-­‐2000)-­‐Ocean Drilling Program Leg 204 (2004)-­‐Japan Tokai-­‐oki to Kumano-­‐nada Project (2004)-­‐Gulf of Mexico JIP Leg I (2005)-­‐Integrated Ocean Drilling Program Expedition 311 (2005)-­‐Malaysia Gumusut-­‐Kakap Project (2006)-­‐India NGHP Expedition 01 (2006)-­‐China GMGS Expedition 01 (2007)-­‐Republic of Korea UBGH Expedition 01 (2007)-­‐Gulf of Mexico JIP Leg II (2009)-­‐Republic of Korea UBGH Expedition 02 (2010)-­‐MH-­‐21 Nankai Trough Pre-­‐Production Expedition (2012-­‐2013)-­‐Mallik Gas Hydrate Testing Projects (1998/2002/2007-­‐2008)-­‐Alaska Mount Elbert Stratigraphic Test Well (2007)-­‐Alaska Iġnik Sikumi Methane Hydrate Production Test Well (2011-­‐2012)Research coring and seismic programs carried out by the Ocean Drilling Program (ODP) and Integrated Ocean Drilling Program (IODP), starting with the ODP Leg 164 drilling of the Blake Ridge in the Atlantic Ocean in 1995, have also contributed greatly to our understanding of the geologic controls on the formation, occurrence, and stability of gas hydrates in marine environments. For the most part methane hydrate research expeditions carried out by the ODP and IODP provided the foundation for our scientific understanding of gas hydrates. The methane hydrate research efforts under ODP-­‐IODP have mostly dealt with the assessment of the geologic controls on the occurrence of gas hydrate, with a specific goal to study the role methane hydrates may play in the global carbon cycle.Over the last 10 years, national led methane hydrate research programs, along with industry interest have led to the development and execution of major methane hydrate production field test programs. Two of the most important production field testing programs have been conducted at the Mallik site in the Mackenzie River Delta of Canada and in the Eileen methane hydrate accumulation on the North Slope of Alaska. Most recently we have also seen the completion of the world’s first marine methane hydrate production test in the Nankai Trough in the offshore of Japan. Industry interest in gas hydrates has also included important projects that have dealt with the assessment of geologic hazards associated with the presence of hydrates.The scientific drilling and associated coring, logging, and borehole monitoring technologies developed in the long list of methane hydrate related field studies are one of the most important developments and contributions associated with methane hydrate research and development activities. Methane hydrate drilling has been conducted from advanced scientific drilling platforms like the JOIDES Resolution and the D/V Chikyu, which feature highly advanced integrated core laboratories and borehole logging capabilities. Hydrate research drilling has also included the use of a wide array of industry, geotechnical and multi-­‐service ships. All of which have been effectively used to collect invaluable geologic and engineering data on the occurrence of methane hydrates throughout the world. Technologies designed specifically for the collection and analysis of undisturbed methane hydrate samples have included the development of a host of pressure core systems and associated specialty laboratory apparatus. The study and use of both wireline conveyed and logging-­‐while-­‐drilling technologies have also contributed greatly to our understanding of the in-­‐situ nature of hydrate-­‐bearing sediments. Recent developments in borehole instrumentation specifically designed to monitor changes associated with hydrates in nature through time or to evaluate the response of hydrate accumulations to production have also contributed greatly to our understanding of the complex nature and evolution of methane hydrate systems.Our understanding of how methane hydrates occur and behave in nature is still growing and evolving – we do not yet know if methane hydrates can be economically produced, nor do we know fully the role of hydrates as an agent of climate change or as a geologic hazard. But it is known for certain that scientific drilling has contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information to advance our understanding of methane hydrates.

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).

Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

2014-12-01

The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E, Haeckel M. Methane Production from Gas Hydrate Deposits through Injection of Supercritical CO2. Energies 2012:5(7): 2112-2140.

The impact of permafrost-associated microorganisms on hydrate formation kinetics

NASA Astrophysics Data System (ADS)

Luzi-Helbing, Manja; Liebner, Susanne; Spangenberg, Erik; Wagner, Dirk; Schicks, Judith M.

2016-04-01

The relationship between gas hydrates, microorganisms and the surrounding sediment is extremely complex: On the one hand, microorganisms producing methane provide the prerequisite for gas hydrate formation. As it is known most of the gas incorporated into natural gas hydrates originates from biogenic sources. On the other hand, as a result of microbial activity gas hydrates are surrounded by a great variety of organic compounds which are not incorporated into the hydrate structure but may influence the formation or degradation process. For gas hydrate samples from marine environments such as the Gulf of Mexico a direct association between microbes and gas hydrates was shown by Lanoil et al. 2001. It is further assumed that microorganisms living within the gas hydrate stability zone produce biosurfactants which were found to enhance the hydrate formation process significantly and act as nucleation centres (Roger et al. 2007). Another source of organic compounds is sediment organic matter (SOM) originating from plant material or animal remains which may also enhance hydrate growth. So far, the studies regarding this relationship were focused on a marine environment. The scope of this work is to extend the investigations to microbes originating from permafrost areas. To understand the influence of microbial activity in a permafrost environment on the methane hydrate formation process and the stability conditions of the resulting hydrate phase we will perform laboratory studies. Thereby, we mimic gas hydrate formation in the presence and absence of methanogenic archaea (e.g. Methanosarcina soligelidi) and other psychrophilic bacteria isolated from permafrost environments of the Arctic and Antarctic to investigate their impact on hydrate induction time and formation rates. Our results may contribute to understand and predict the occurrences and behaviour of potential gas hydrates within or adjacent to the permafrost. Lanoil BD, Sassen R, La Duc MT, Sweet ST, Nealson KH (2001). Bacteria and Archaea Physically Associated with Gulf of Mexico Gas Hydrates. Appl Environ Microbiol 67: 5143-5153. Rogers R, Zhang G, Dearman J, Woods C (2007). Investigations into surfactant/gas hydrate relationship. J Petrol Sci Eng 56: 82-88.

Gas hydrate hunting in China seas

NASA Astrophysics Data System (ADS)

Yang, J.; Zhang, X.; Chen, J.; Xiang, Q.; Ye, Y.; Gong, J.

2003-04-01

Gas hydrate research is a hotspot now in geosciences. Many countries have carried on gas hydrate survey and research for many years. China, as a country with large sea areas unfolded gas hydrate research work in its marine areas in 1999 and tries to keep pace with the advanced countries on gas hydrate study. Substantial funds were launched by various governmental and non-governmental funding agencies to support gas hydrate research. Many institutions on marine geosciences are involved in. China Geological Survey (CGS) has launched several research projects in the sea. So far, some fieldwork such as seismic survey, sampling, profiling, underwater video imaging have been done in South China Sea and East China Sea areas. Some preliminary results have been achieved. BSRs are found in many seismic profiles. Some potential gas hydrate bearing areas are marked and potential amount of gas hydrate resources is calculated. At the same time, gas hydrate laboratory was founded and successful experiments have been carried out to model the gas hydrate synthesis in accordance with the geological condition of the China seas. Now, gas hydrate detecting techniques such as sampling equipment (PCS), seismic data processing, interpretation and the formation mechanism study as well as environmental effect research are undergoing. Though China's gas hydrate research work is still at its initial stage, China is willing to be an active member in the international society of gas hydrate study and hopes to contribute its effort.

Natural gas hydrate in oceanic and permafrost environments

USGS Publications Warehouse

Max, Michael D.

2003-01-01

THE BEGINNINGS OF HYDRATE RESEARCH Until very recently, our understanding of hydrate in the natural environment and its impact on seafloor stability, its importance as a sequester of methane, and its potential as an important mechanism in the Earth's climate change system, was masked by our lack of appreciation of the vastness of the hydrate resource. Only a few publications on naturally occurring hydrate existed prior to 1975. The first published reference to oceanic gas hydrate (Bryan and Markl, 1966) and the first publication in the scientific literature (Stoll, et a1., 1971) show how recently it has been since the topic of naturally occurring hydrate has been raised. Recently, however, the number of hydrate publications has increased substantially, reflecting increased research into hydrate topics and the initiation of funding to support the researchers. Awareness of the existence of naturally occurring gas hydrate now has spread beyond the few scientific enthusiasts who pursued knowledge about the elusive hydrate because of simple interest and lurking suspicions that hydrate would prove to be an important topic. The first national conference on gas hydrate in the U.S. was held as recently as April, 1991 at the U.S. National Center of the U.s. Geological Survey in Reston Virginia (Max et al., 1991). The meeting was co-hosted by the U.s. Geological Survey, the Naval Research Laboratory, and the U.S.

Complex admixtures of clathrate hydrates in a water desalination method

DOEpatents

Simmons, Blake A [San Francisco, CA; Bradshaw, Robert W [Livermore, CA; Dedrick, Daniel E [Berkeley, CA; Anderson, David W [Riverbank, CA

2009-07-14

Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

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.

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.

Modeling dynamic accumulation of gas hydrates in Shenhu area, northern South China Sea

NASA Astrophysics Data System (ADS)

Su, Z.; Cao, Y.; Wu, N.

2013-12-01

The accumulation of the hydrates in Shenhu area on northern continental slope of the South China Sea (SCS) could not be well quantified by the numerical models. The formation mechanism of the hydrate deposits remains an open question. Here, a conceptual model was applied for illustrating the formation pattern of hydrate accumulation in Shenhu area based on the studies of sedimentary and tectonic geologies. Our results indicated that the present hydrate deposits were a development of 'ancient hydrates' in the faulted sediment. The dynamic accumulation of the hydrates was further quantified by using a numerical model with two controlling parameters of seafloor sedimentation rate and water flow rate. The model results were testified with the hydrate saturations derived from the chloride abnormalities at site SH2 in Shenhu area. It suggested that the hydrate accumulation in Shenhu area had experienced two typical stages. In the first stage, the gas hydrates grew in the fractured sediment ~1.5 Ma. High permeability of the fractured sediment permitted rapid water flow that carrying methane gas toward the seafloor. Massive gas transformed to gas hydrate in the gas hydrate stability zone (GHSZ) at water flow rate of 50m/kyr within 40kyrs. The 'ancient hydrate' filled 20% volume of the sediment pores in the stage. The second stage was initiated after ending of the last faulting activity. The water flow rate dropped to 0.7m/kyr due to quick burial of fine-grained sediments. Inadequate gas supply could merely sustain hydrate growth slowly at the base of GHSZ, and ultimately yielded the current hydrate deposits in Shenhu area after a subsequent evolution of 1.5 Myrs.

Regional Mapping and Resource Assessment of Shallow Gas Hydrates of Japan Sea - METI Launched 3 Years Project in 2013.

NASA Astrophysics Data System (ADS)

Matsumoto, R.

2014-12-01

Agency of Natural Resources and Energy of METI launched a 3 years shallow gas hydrate exploration project in 2013 to make a precise resource assessment of shallow gas hydrates in the eastern margin of Japan Sea and around Hokkaido. Shallow gas hydrates of Japan Sea occur in fine-grained muddy sediments of shallow subsurface of mounds and gas chimneys in the form of massive nodular to platy accumulation. Gas hydrate bearing mounds are often associated with active methane seeps, bacterial mats and carbonate concretions and pavements. Gases of gas hydrates are derived either from deep thermogenic, shallow microbial or from the mixed gases, contrasting with totally microbial deep-seated stratigraphically controlled hydrates. Shallow gas hydrates in Japan Sea have not been considered as energy resource due to its limited distribution in narrow Joetsu basin. However recently academic research surveys have demonstrated regional distribution of gas chimney and hydrate mound in a number of sedimentary basins along the eastern margin of Japan Sea. Regional mapping of gas chimney and hydrate mound by means of MBES and SBP surveys have confirmed that more than 200 gas chimneys exist in 100 km x 100 km area. ROV dives have identified dense accumulation of hydrates on the wall of half collapsed hydrate mound down to 30 mbsf. Sequential LWD and shallow coring campaign in the Summer of 2014, R/V Hakurei, which is equipped with Fugro Seacore R140 drilling rig, drilled through hydrate mounds and gas chimneys down to the BGHS (base of gas hydrate stability) level and successfully recovered massive gas hydrates bearing sediments from several horizons.

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

A molecular dynamics study of model SI clathrate hydrates: the effect of guest size and guest-water interaction on decomposition kinetics.

PubMed

Das, Subhadip; Baghel, Vikesh Singh; Roy, Sudip; Kumar, Rajnish

2015-04-14

One of the options suggested for methane recovery from natural gas hydrates is molecular replacement of methane by suitable guests like CO2 and N2. This approach has been found to be feasible through many experimental and molecular dynamics simulation studies. However, the long term stability of the resultant hydrate needs to be evaluated; the decomposition rate of these hydrates is expected to depend on the interaction between these guest and water molecules. In this work, molecular dynamics simulation has been performed to illustrate the effect of guest molecules with different sizes and interaction strengths with water on structure I (SI) hydrate decomposition and hence the stability. The van der Waals interaction between water of hydrate cages and guest molecules is defined by Lennard Jones potential parameters. A wide range of parameter spaces has been scanned by changing the guest molecules in the SI hydrate, which acts as a model gas for occupying the small and large cages of the SI hydrate. All atomistic simulation results show that the stability of the hydrate is sensitive to the size and interaction of the guest molecules with hydrate water. The increase in the interaction of guest molecules with water stabilizes the hydrate, which in turn shows a slower rate of hydrate decomposition. Similarly guest molecules with a reasonably small (similar to Helium) or large size increase the decomposition rate. The results were also analyzed by calculating the structural order parameter to understand the dynamics of crystal structure and correlated with the release rate of guest molecules from the solid hydrate phase. The results have been explained based on the calculation of potential energies felt by guest molecules in amorphous water, hydrate bulk and hydrate-water interface regions.

Well log characterization of natural gas hydrates

USGS Publications Warehouse

Collett, Timothy S.; Lee, Myung W.

2011-01-01

In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids (i.e., free-water along with clay and capillary bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate production schemes.

Unraveling Mixed Hydrate Formation: Microscopic Insights into Early Stage Behavior.

PubMed

Hall, Kyle Wm; Zhang, Zhengcai; Kusalik, Peter G

2016-12-29

The molecular-level details of mixed hydrate nucleation remain unclear despite the broad implications of this process for a variety of scientific domains. Through analysis of mixed hydrate nucleation in a prototypical CH 4 /H 2 S/H 2 O system, we demonstrate that high-level kinetic similarities between mixed hydrate systems and corresponding pure hydrate systems are not a reliable basis for estimating the composition of early stage mixed hydrate nuclei. Moreover, we show that solution compositions prior to and during nucleation are not necessarily effective proxies for the composition of early stage mixed hydrate nuclei. Rather, microscopic details, (e.g., guest-host interactions and previously neglected cage types) apparently play key roles in determining early stage behavior of mixed hydrates. This work thus provides key foundational concepts and insights for understanding mixed hydrate nucleation.

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

NASA Astrophysics Data System (ADS)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Numerical simulations of CO2 -assisted gas production from hydrate reservoirs

NASA Astrophysics Data System (ADS)

Sridhara, P.; Anderson, B. J.; Myshakin, E. M.

2015-12-01

A series of experimental studies over the last decade have reviewed the feasibility of using CO2 or CO2+N2 gas mixtures to recover CH4 gas from hydrates deposits. That technique would serve the dual purpose of CO2 sequestration and production of CH4 while maintaining the geo-mechanical stability of the reservoir. In order to analyze CH4 production process by means of CO2 or CO2+N2 injection into gas hydrate reservoirs, a new simulation tool, Mix3HydrateResSim (Mix3HRS)[1], was previously developed to account for the complex thermodynamics of multi-component hydrate phase and to predict the process of CH4 substitution by CO2 (and N2) in the hydrate lattice. In this work, Mix3HRS is used to simulate the CO2 injection into a Class 2 hydrate accumulation characterized by a mobile aqueous phase underneath a hydrate bearing sediment. That type of hydrate reservoir is broadly confirmed in permafrost and along seashore. The production technique implies a two-stage approach using a two-well design, one for an injector and one for a producer. First, the CO2 is injected into the mobile aqueous phase to convert it into immobile CO2 hydrate and to initiate CH4 release from gas hydrate across the hydrate-water boundary (generally designating the onset of a hydrate stability zone). Second, CH4 hydrate decomposition is induced by the depressurization method at a producer to estimate gas production potential over 30 years. The conversion of the free water phase into the CO2 hydrate significantly reduces competitive water production in the second stage, thereby improving the methane gas production. A base case using only the depressurization stage is conducted to compare with enhanced gas production predicted by the CO2-assisted technique. The approach also offers a possibility to permanently store carbon dioxide in the underground formation to greater extent comparing to a direct injection of CO2 into gas hydrate sediment. Numerical models are based on the hydrate formations at the Prudhoe Bay L-Pad region on the Alaska North Slope. References [1] N.Garapati, "Reservoir Simulation for Production of CH4 from Gas Hydrate Reservoirs Using CO2/CO2+N2 by HydrateResSim", Ph.D. thesis, West Virginia University, 2013.

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.

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.

Nasogastric hydration versus intravenous hydration for infants with bronchiolitis: a randomised trial.

PubMed

Oakley, Ed; Borland, Meredith; Neutze, Jocelyn; Acworth, Jason; Krieser, David; Dalziel, Stuart; Davidson, Andrew; Donath, Susan; Jachno, Kim; South, Mike; Theophilos, Theane; Babl, Franz E

2013-04-01

Bronchiolitis is the most common lower respiratory tract infection in infants and the leading cause of hospital admission. Hydration is a mainstay of treatment, but insufficient evidence exists to guide clinical practice. We aimed to assess whether intravenous hydration or nasogastric hydration is better for treatment of infants. In this multicentre, open, randomised trial, we enrolled infants aged 2-12 months admitted to hospitals in Australia and New Zealand with a clinical diagnosis of bronchiolitis during three bronchiolitis seasons (April 1-Oct 31, in 2009, 2010, and 2011). We randomly allocated infants to nasogastric hydration or intravenous hydration by use of a computer-generated sequence and opaque sealed envelopes, with three randomly assigned block sizes and stratified by hospital site and age group (2-<6 months vs 6-12 months). The primary outcome was length of hospital stay, assessed in all randomly assigned infants. Secondary outcomes included rates of intensive-care unit admission, adverse events, and success of insertion. This trial is registered with the Australian and New Zealand clinical trials registry, ACTRN12605000033640. Mean length of stay for 381 infants assigned nasogastric hydration was 86·6 h (SD 58·9) compared with 82·2 h (58·8) for 378 infants assigned intravenous hydration (absolute difference 4·5 h [95% CI -3·9 to 12·9]; p=0·30). Rates of admission to intensive-care units, need for ventilatory support, and adverse events did not differ between groups. At randomisation, seven infants assigned nasogastric hydration were switched to intravenous hydration and 56 infants assigned intravenous hydration were switched to nasogastric hydration because the study-assigned method was unable to be inserted. For those infants who had data available for successful insertion, 275 (85%) of 323 infants in the nasogastric hydration group and 165 (56%) of 294 infants in the intravenous hydration group required only one attempt for successful insertion. Intravenous hydration and nasogastric hydration are appropriate means to hydrate infants with bronchiolitis. Nasogastric insertion might require fewer attempts and have a higher success rate of insertion than intravenous hydration. Australian National Health and Medical Research Council, Samuel Nissen Charitable Foundation (Perpetual), Murdoch Children's Research Institute, Victorian Government. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching.

PubMed

Grim, R Gary; Kerkar, Prasad B; Sloan, E Dendy; Koh, Carolyn A; Sum, Amadeu K

2012-06-21

In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.

Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand

USGS Publications Warehouse

Waite, W.F.; deMartin, B.J.; Kirby, S.H.; Pinkston, J.; Ruppel, C.D.

2002-01-01

Using von Herzen and Maxwell's needle probe method, we measured thermal conductivity in four porous mixtures of quartz sand and methane gas hydrate, with hydrate composing 0, 33, 67 and 100% of the solid volume. Thermal conductivities were measured at a constant methane pore pressure of 24.8 MPa between -20 and +15??C, and at a constant temperature of -10??C between 3.5 and 27.6 MPa methane pore pressure. Thermal conductivity decreased with increasing temperature and increased with increasing methane pore pressure. Both dependencies weakened with increasing hydrate content. Despite the high thermal conductivity of quartz relative to methane hydrate, the largest thermal conductivity was measured in the mixture containing 33% hydrate rather than in hydrate-free sand. This suggests gas hydrate enhanced grain-to-grain heat transfer, perhaps due to intergranular contact growth during hydrate synthesis. These results for gas-filled porous mixtures can help constrain thermal conductivity estimates in porous, gas hydrate-bearing systems.

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

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

2016-12-01

Naturally occurring gas hydrates in marine or permafrost environments can trap methane and heavier hydrocarbons within its host lattice structure built up with hydrogen-bonded water molecules. Naturally occurring gas hydrates have been expected as new natural gas resources. It is important to reveal the distribution of guest hydrocarbons in host hydrate framework from viewpoint of assessment of gas capacity. In this study, we assessed cage occupancies of guest hydrocarbons in host hydrate framework of synthetic and natural gas hydrates using solid-state 13C NMR technique. As synthetic samples, gas hydrates formed from gas mixtures including C1 to C5 were investigated. As a natural sample, the pore-space gas hydrate sample recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation was studied. As a result, it revealed that all heavier hydrocarbons than ethane are preferentially incorporated into the larger cage cavities in hydrate frameworks. We performed this study as a part of a Japanese National hydrate research program (MH21, funded by METI).

The U.S. Geological Survey’s Gas Hydrates Project

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

The Gas Hydrates Project at the U.S. Geological Survey (USGS) focuses on the study of methane hydrates in natural environments. The project is a collaboration between the USGS Energy Resources and the USGS Coastal and Marine Geology Programs and works closely with other U.S. Federal agencies, some State governments, outside research organizations, and international partners. The USGS studies the formation and distribution of gas hydrates in nature, the potential of hydrates as an energy resource, and the interaction between methane hydrates and the environment. The USGS Gas Hydrates Project carries out field programs and participates in drilling expeditions to study marine and terrestrial gas hydrates. USGS scientists also acquire new geophysical data and sample sediments, the water column, and the atmosphere in areas where gas hydrates occur. In addition, project personnel analyze datasets provided by partners and manage unique laboratories that supply state-of-the-art analytical capabilities to advance national and international priorities related to gas hydrates.

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.

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.

Physical Properties of Gas Hydrates: A Review

DOE PAGES

Gabitto, Jorge F.; Tsouris, Costas

2010-01-01

Memore » thane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 10 16   m 3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.« less

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

Hydration behaviour of food grains and modelling their moisture pick up as per Peleg's equation: Part I. Cereals.

PubMed

Vasudeva, Singh; Vishwanathan, K H; Aswathanarayana, K N; Indhudhara Swamy, Y M

2010-01-01

Cereals and millets generally hydrate at a moderate rate and their hydration behaviour differs in native and in processed state. The study was on the hydration of paddy, milled rice, parboiled rice, wheat, millets and equilibrium moisture content (EMC) on soaking at room temperature. Paddy hydrated very slowly, hydration rate was slow in brown rice but fast in milled rice and highest in waxy rice. In most of the rice varieties, maximum absorption occurred at the end of 30 min. In wheat hydration rate was slow and its EMC was highest (43%). Maize grits of big size hydrated slowly compared to small grits. In coarse cereals EMC varied from 28 to 38%. Foxtail millet hydration was slow whereas that of finger millet was fast. The data were tested on the Peleg's equation, which gave a reasonable fit to experimental data. Peleg's constants k1 and k2 were calculated for the above grains and their hydration behaviour has been predicted. The model fitted very well to milled rice hydration data where the coefficient of variance ranged from 0.9982 to 0.9995. With exception in some millet the hydration data fitted well with the Peleg's equation. Generalized equations have been formulated for prediction of moisture content of cereals and millets.

Screening and Characterization of Hydrate Forms of T-3256336, a Novel Inhibitor of Apoptosis (IAP) Protein Antagonist.

PubMed

Takeuchi, Shoko; Kojima, Takashi; Hashimoto, Kentaro; Saito, Bunnai; Sumi, Hiroyuki; Ishikawa, Tomoyasu; Ikeda, Yukihiro

2015-01-01

Different crystal packing of hydrates from anhydrate crystals leads to different physical properties, such as solubility and stability. Investigation of the potential of varied hydrate formation, and understanding the stability in an anhydrous/hydrate system, are crucial to prevent an undesired transition during the manufacturing process and storage. Only one anhydrous form of T-3256336, a novel inhibitor of apoptosis (IAP) protein antagonist, was discovered during synthesis, and no hydrate form has been identified. In this study, we conducted hydrate screening such as dynamic water vapor sorption/desorption (DVS), and the slurry experiment, and characterized the solid-state properties of anhydrous/hydrate forms to determine the most desirable crystalline form for development. New hydrate forms, both mono-hydrate and hemi-hydrate forms, were discovered as a result of this hydrate screening. The characterization of two new hydrate forms was conducted, and the anhydrous form was determined to be the most desirable development form of T-3256336 in terms of solid-state stability. In addition, the stability of the anhydrous form was investigated using the water content and temperature controlled slurry experiment to obtain the desirable crystal form in the crystallization process. The water content regions of the stable phase of the desired form, the anhydrous form, were identified for the cooling crystallization process.

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.

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.

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

Development of Carbon Sequestration Options by Studying Carbon Dioxide-Methane Exchange in Hydrates

NASA Astrophysics Data System (ADS)

Horvat, Kristine Nicole

Gas hydrates form naturally at high pressures (>4 MPa) and low temperatures (<4 °C) when a set number of water molecules form a cage in which small gas molecules can be entrapped as guests. It is estimated that about 700,000 trillion cubic feet (tcf) of methane (CH4) exist naturally as hydrates in marine and permafrost environments, which is more than any other natural sources combined as CH4 hydrates contain about 14 wt% CH4. However, a vast amount of gas hydrates exist in marine environments, which makes gas extraction an environmental challenge, both for potential gas losses during extraction and the potential impact of CH4 extraction on seafloor stability. From the climate change point of view, a 100 ppm increase in atmospheric carbon dioxide (CO2) levels over the past century is of urgent concern. A potential solution to both of these issues is to simultaneously exchange CH4 with CO 2 in natural hydrate reserves by forming more stable CO2 hydrates. This approach would minimize disturbances to the host sediment matrix of the seafloor while sequestering CO2. Understanding hydrate growth over time is imperative to prepare for large scale CH4 extraction coupled with CO2 sequestration. In this study, we performed macroscale experiments in a 200 mL high-pressure Jerguson cell that mimicked the pressure-temperature conditions of the seafloor. A total of 13 runs were performed under varying conditions. These included the formation of CH4 hydrates, followed by a CO2 gas injection and CO2 hydrate formation followed by a CH4 gas injection. Results demonstrated that once gas hydrates formed, they show "memory effect" in subsequent charges, irrespective of the two gases injected. This was borne out by the induction time data for hydrate formation that reduced from 96 hours for CH4 and 24 hours for CO2 to instant hydrate formation in both cases upon injection of a secondary gas. During the study of CH4-CO2 exchange where CH4 hydrates were first formed and CO2 gas was injected into the system, gas chromatographic (GC) analysis of the cell indicated a pure CH4 gas phase, i.e., all injected CO2 gas entered the hydrate phase and remained trapped in hydrate cages for several hours, though over time some CO2 did enter the gas phase. Alternatively, during the CH 4-CO2 exchange study where CO2 hydrates were first formed, the injected CH4 initially entered the hydrate phase, but quickly gaseous CO2 exchanged with CH4 in hydrates to form more stable CO2 hydrates. These results are consistent with the better thermodynamic stability of CO2 hydrates, and this appears to be a promising method to sequester CO2 in natural CH4 hydrate matrices. The macroscale study described above was complemented by a microscale study to visualize hydrate growth. This first-of-its-kind in-situ study utilized the x-ray computed microtomography (CMT) technique to visualize microscale CO2, CH4, and mixed CH 4-CO2 hydrate growth phenomenon in salt solutions in the presence or absence of porous media. The data showed that under the experimental conditions used, pure CH4 formed CH4 hydrates as mostly spheres, while pure CO2 hydrates were more dendritic branches. Additionally, varying ratios of mixed CH4-CO2 hydrates were also formed that had needle-like growth. In porous media, CO2 hydrates grew, consistent with known growth models in which the solution was the sediment wetting phase. When glass beads and Ottawa sand were used as a host, the system exhibited pore-filling hydrate growth, while the presence of liquid CO2 and possible CO2 hydrates in Ottawa sand initially were pore-filling that over time transformed into a grain-displacing morphology. The data appears promising to develop a method that would supplant our energy supply by extracting CH4 from naturally occurring hydrates while CO2 is sequestered in the same formations.

Effectiveness of oral hydration in preventing contrast-induced acute kidney injury in patients undergoing coronary angiography or intervention: a pairwise and network meta-analysis.

PubMed

Zhang, Weidai; Zhang, Jiawei; Yang, Baojun; Wu, Kefei; Lin, Hanfei; Wang, Yanping; Zhou, Lihong; Wang, Huatao; Zeng, Chujuan; Chen, Xiao; Wang, Zhixing; Zhu, Junxing; Songming, Chen

2018-06-01

The effectiveness of oral hydration in preventing contrast-induced acute kidney injury (CI-AKI) in patients undergoing coronary angiography or intervention has not been well established. This study aims to evaluate the efficacy of oral hydration compared with intravenous hydration and other frequently used hydration strategies. PubMed, Embase, Web of Science, and the Cochrane central register of controlled trials were searched from inception to 8 October 2017. To be eligible for analysis, studies had to evaluate the relative efficacy of different prophylactic hydration strategies. We selected and assessed the studies that fulfilled the inclusion criteria and carried out a pairwise and network meta-analysis using RevMan5.2 and Aggregate Data Drug Information System 1.16.8 software. A total of four studies (538 participants) were included in our pairwise meta-analysis and 1754 participants from eight studies with four frequently used hydration strategies were included in a network meta-analysis. Pairwise meta-analysis indicated that oral hydration was as effective as intravenous hydration for the prevention of CI-AKI (5.88 vs. 8.43%; odds ratio: 0.73; 95% confidence interval: 0.36-1.47; P>0.05), with no significant heterogeneity between studies. Network meta-analysis showed that there was no significant difference in the prevention of CI-AKI. However, the rank probability plot suggested that oral plus intravenous hydration had a higher probability (51%) of being the best strategy, followed by diuretic plus intravenous hydration (39%) and oral hydration alone (10%). Intravenous hydration alone was the strategy with the highest probability (70%) of being the worst hydration strategy. Our study shows that oral hydration is not inferior to intravenous hydration for the prevention of CI-AKI in patients with normal or mild-to-moderate renal dysfunction undergoing coronary angiography or intervention.

Thermal properties of methane gas hydrates

USGS Publications Warehouse

Waite, William F.

2007-01-01

Gas hydrates are crystalline solids in which molecules of a “guest” species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0°C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply “gas hydrates,” are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, λ: if λ is high, heat travels easily through the material. - Thermal diffusivity, κ: if κ is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to raise the temperature of the material.

Mechanical and electromagnetic properties of northern Gulf of Mexico sediments with and without THF hydrates

USGS Publications Warehouse

Lee, J.Y.; Santamarina, J.C.; Ruppel, C.

2008-01-01

Using an oedometer cell instrumented to measure the evolution of electromagnetic properties, small strain stiffness, and temperature, we conducted consolidation tests on sediments recovered during drilling in the northern Gulf of Mexico at the Atwater Valley and Keathley Canyon sites as part of the 2005 Chevron Joint Industry Project on Methane Hydrates. The tested specimens include both unremolded specimens (as recovered from the original core liner) and remolded sediments both without gas hydrate and with pore fluid exchanged to attain 100% synthetic (tetrahydrofuran) hydrate saturation at any stage of loading. Test results demonstrate the extent to which the electromagnetic and mechanical properties of hydrate-bearing marine sediments are governed by the vertical effective stress, stress history, porosity, hydrate saturation, fabric, ionic concentration of the pore fluid, and temperature. We also show how permittivity and electrical conductivity data can be used to estimate the evolution of hydrate volume fraction during formation. The gradual evolution of geophysical properties during hydrate formation probably reflects the slow increase in ionic concentration in the pore fluid due to ion exclusion in closed systems and the gradual decrease in average pore size in which the hydrate forms. During hydrate formation, the increase in S-wave velocity is delayed with respect to the decrease in permittivity, consistent with hydrate formation on mineral surfaces and subsequent crystal growth toward the pore space. No significant decementation/debonding occurred in 100% THF hydrate-saturated sediments during unloading, hence the probability of sampling hydrate-bearing sediments without disturbing the original sediment fabric is greatest for samples in which the gas hydrate is primarily responsible for maintaining the sediment fabric and for which the time between core retrieval and restoration of in situ effective stress in the laboratory is minimized. In evaluating the impact of core retrieval on specimen properties, it is also important to consider how far removed hydrate-bearing samples are from hydrate stability conditions. ?? 2008 Elsevier Ltd.

Well log characterization of natural gas-hydrates

USGS Publications Warehouse

Collett, Timothy S.; Lee, Myung W.

2012-01-01

In the last 25 years there have been significant advancements in the use of well-logging tools to acquire detailed information on the occurrence of gas hydrates in nature: whereas wireline electrical resistivity and acoustic logs were formerly used to identify gas-hydrate occurrences in wells drilled in Arctic permafrost environments, more advanced wireline and logging-while-drilling (LWD) tools are now routinely used to examine the petrophysical nature of gas-hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Resistivity- and acoustic-logging tools are the most widely used for estimating the gas-hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. Recent integrated sediment coring and well-log studies have confirmed that electrical-resistivity and acoustic-velocity data can yield accurate gas-hydrate saturations in sediment grain-supported (isotropic) systems such as sand reservoirs, but more advanced log-analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. New well-logging tools designed to make directionally oriented acoustic and propagation-resistivity log measurements provide the data needed to analyze the acoustic and electrical anisotropic properties of both highly interbedded and fracture-dominated gas-hydrate reservoirs. Advancements in nuclear magnetic resonance (NMR) logging and wireline formation testing (WFT) also allow for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids(i.e., free water along with clay- and capillary-bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas-hydrate reservoir properties (i.e., porosities and permeabilities) needed to accurately predict gas production rates for various gas-hydrate production schemes.

Complex Resistivity experiment of Methane Hydrate in Porous Media

NASA Astrophysics Data System (ADS)

Chen, Q.; Wang, C.

2017-12-01

Electric logging plays an important role in gas hydrate exploration and saturation estimation. However, due to the lack of specialized model, some classical models of petroleum industry were used to calculate the hydrate reserves such as Archie's law. But the widely used resistivity model is unable to characterize the electrical properties of hydrate bearing sediments comprehensively, while the complex resistivity method can reveal more details about the electric properties of gas hydrate porous media. In this paper, a series of electrochemical impedance spectroscope tests were carried out during methane hydrate formation and dissociation process in porous media with 3.5% brine. The hydrate saturation was controlled by decrease the pressure at certain temperature. At each saturation, complex resistivities with frequency of 0.1 Hz 1 MHz were acquired and the frequency dispersion characteristics were analyzed. Conclusion as below: 1. It exhibited remarkable frequency dispersion characteristics in hydrate porous media, especially when the frequency was below 10Hz. At certain hydrate saturation, the resistivity amplitude/real part/imaginary part decreased with frequency, but the resistivity variation trends were complicated with frequency: between 0.1- 2.3Hz, the resistivity amplitude and real part were decreased as hydrate saturation increasing; however when the frequency become higher, the resistivity were increased with hydrate saturation. 2. In the hydrate porous media test, the resistivity amplitude/real part/imaginary part didn't show a linear variation with hydrate saturation in the double logarithmic coordinate, so the Archie's law cannot get constant a, m parameters. Moreover, different frequency lead to different resistivity value at certain saturation, Archie's law parameters must be readjusted to certain logging method. 3. In this study the impedance spectroscopy of porous medium containing hydrate can be fitted through an equivalent circuit model with a resistor and capacitor in series, and the resultant complex resistivity model can be used to calculate the gas hydrate saturation which may provide a new way to predict hydrate reserves.

Structure and stability of complexes of agmatine with some functional receptor residues of proteins

NASA Astrophysics Data System (ADS)

Remko, Milan; Broer, Ria; Remková, Anna; Van Duijnen, Piet Th.

2017-04-01

The paper reports the results of a theoretical study of the conformational behavior and basicity of biogenic amine agmatine. The complexes modelling of agmatine - protein interaction are also under scrutiny of our investigation using the Becke3LYP and B97D levels of the density functional theory. The relative stabilities (Gibbs energies) of individual complexes are by both DFT methods described equally. Hydration has a dramatic effect on the hydrogen bonded complexes studied. The pairing acidic carboxylate group with different agmatine species resulted in charged hydrogen bond complexes containing negatively charged acetate species acting as proton acceptors.

The Use of Chromium(III) to Supercharge Peptides by Protonation at Low Basicity Sites

NASA Astrophysics Data System (ADS)

Feng, Changgeng; Commodore, Juliette J.; Cassady, Carolyn J.

2015-02-01

The addition of chromium(III) nitrate to solutions of peptides with seven or more residues greatly increases the formation of doubly protonated peptides, [M + 2H]2+, by electrospray ionization. The test compound heptaalanine has only one highly basic site (the N-terminal amino group) and undergoes almost exclusive single protonation using standard solvents. When Cr(III) is added to the solution, abundant [M + 2H]2+ forms, which involves protonation of the peptide backbone or the C-terminus. Salts of Al(III), Mn(II), Fe(III), Fe(II), Cu(II), Zn (II), Rh(III), La(III), Ce(IV), and Eu(III) were also studied. Although several metal ions slightly enhance protonation, Cr(III) has by far the greatest ability to generate [M + 2H]2+. Cr(III) does not supercharge peptide methyl esters, which suggests that the mechanism involves interaction of Cr(III) with a carboxylic acid group. Other factors may include the high acidity of hexa-aquochromium(III) and the resistance of Cr(III) to reduction. Nitrate salts enhance protonation more than chloride salts and a molar ratio of 10:1 Cr(III):peptide produces the most intense [M + 2H]2+. Cr(III) also supercharges numerous other small peptides, including highly acidic species. For basic peptides, Cr(III) increases the charge state (2+ versus 1+) and causes the number of peptide molecules being protonated to double or triple. Chromium(III) does not supercharge the proteins cytochrome c and myoglobin. The ability of Cr(III) to enhance [M + 2H]2+ intensity may prove useful in tandem mass spectrometry because of the resulting overall increase in signal-to-noise ratio, the fact that [M + 2H]2+ generally dissociate more readily than [M + H]+, and the ability to produce [M + 2H]2+ precursors for electron-based dissociation techniques.

Indian National Gas Hydrate Program Expedition 01 report

USGS Publications Warehouse

Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.V.; ,

2015-01-01

The Indian National Gas Hydrate Program Expedition 01 was designed to study the gas-hydrate occurrences off the Indian Peninsula and along the Andaman convergent margin with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. During Indian National Gas Hydrate Program Expedition 01, dedicated gas-hydrate coring, drilling, and downhole logging operations were conducted from 28 April 2006 to 19 August 2006.

Physical properties of sediment containing methane gas hydrate

USGS Publications Warehouse

Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.

2005-01-01

A study conducted by the US Geological Survey (USGS) on the formation, behavior, and properties of mixtures of gas hydrate and sediment is presented. The results show that the properties of host material influence the type and quantity of hydrates formed. The presence of hydrate during mechanical shear tests affects the measured sediment pore pressure. Sediment shear strength may be increased more than 500 percent by intact hydrate, but greatly weakened if the hydrate dissociates.

Anisotropic Velocities of Gas Hydrate-Bearing Sediments in Fractured Reservoirs

USGS Publications Warehouse

Lee, Myung W.

2009-01-01

During the Indian National Gas Hydrate Program Expedition 01 (NGHP-01), one of the richest marine gas hydrate accumulations was discovered at drill site NGHP-01-10 in the Krishna-Godavari Basin, offshore of southeast India. The occurrence of concentrated gas hydrate at this site is primarily controlled by the presence of fractures. Gas hydrate saturations estimated from P- and S-wave velocities, assuming that gas hydrate-bearing sediments (GHBS) are isotropic, are much higher than those estimated from the pressure cores. To reconcile this difference, an anisotropic GHBS model is developed and applied to estimate gas hydrate saturations. Gas hydrate saturations estimated from the P-wave velocities, assuming high-angle fractures, agree well with saturations estimated from the cores. An anisotropic GHBS model assuming two-component laminated media - one component is fracture filled with 100-percent gas hydrate, and the other component is the isotropic water-saturated sediment - adequately predicts anisotropic velocities at the research site.

Hydration and Hot Yoga: Encouragement, Behaviors, and Outcomes.

PubMed

Mace Firebaugh, Casey J; Eggleston, Brandon

2017-01-01

Currently, the literature on hot yoga is lacking, and there is still much to understand regarding the safety of these practices. However, one point of safety often emphasized is hydration during the practice of hot yoga. The aim of this study was to examine hydration encouragement by hot yoga instructors and hydration behaviors and related outcomes by hot yoga participants. A cross-sectional study ( n = 700) collected self-report data on demographics, types and frequency of yoga practiced, hydration behaviors, and self-report measures of adverse outcomes experienced by participants during hot yoga. Associations between hydration encouragement, protective behaviors, and adverse outcomes were analyzed through Chi-square tests. Every protective hydration behavior was significantly associated with instructor encouragement ( P < 0.05). Hydration before or during hot yoga participation was associated with a lower occurrence of dehydration symptoms ( P < 0.05). Hot yoga instructors hold a key role in encouraging hydration and student safety outcomes.

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Ductile flow of methane hydrate

USGS Publications Warehouse

Durham, W.B.; Stern, L.A.; Kirby, S.H.

2003-01-01

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

Water permeability in hydrate-bearing sediments: A pore-scale study

NASA Astrophysics Data System (ADS)

Dai, Sheng; Seol, Yongkoo

2014-06-01

Permeability is a critical parameter governing methane flux and fluid flow in hydrate-bearing sediments; however, limited valid data are available due to experimental challenges. Here we investigate the relationship between apparent water permeability (k') and hydrate saturation (Sh), accounting for hydrate pore-scale growth habit and meso-scale heterogeneity. Results from capillary tube models rely on cross-sectional tube shapes and hydrate pore habits, thus are appropriate only for sediments with uniform hydrate distribution and known hydrate pore character. Given our pore network modeling results showing that accumulating hydrate in sediments decreases sediment porosity and increases hydraulic tortuosity, we propose a modified Kozeny-Carman model to characterize water permeability in hydrate-bearing sediments. This model agrees well with experimental results and can be easily implemented in reservoir simulators with no empirical variables other than Sh. Results are also relevant to flow through other natural sediments that undergo diagenesis, salt precipitation, or bio-clogging.

X-Ray Micro-CT Observations of Hydrate Pore Habit and Lattice Boltzmann Simulations on Permeability Evolution in Hydrate Bearing Sediments (HBS)

NASA Astrophysics Data System (ADS)

Chen, X.; Espinoza, N.; Verma, R.; Prodanovic, M.

2017-12-01

We use X-ray micro-computed tomography (μCT) to observe xenon hydrate growth. During xenon hydrate formation in a single pore and a sandpack, we observe heterogeneous (patchy) hydrate distribution at both pore (10 μm) and core scales (10 cm). These results present similarities with earlier observations on naturally occurring and synthetic hydrate-bearing sediment (HBS). Based on image analyses of xenon hydrate in the single pore, we find that, under the quasi-isothermal condition, the xenon volumetric growth rate versus overpressurization curve fits an Arrhenius type equation. Using the μCT images of HBS, we are able to calculate the permeability of HBS using a lattice Boltzmann method. We find the reduced permeability versus hydrate saturation curve fits a simple Corey-type model as suggested by earlier studies. However, patchy distribution of hydrate does not permit a straightforward interpretation of the saturation exponent. This work provides fundamental observations of hydrate growth and pore habit in sediments and how hydrate habit affects the hydraulic conductivity of HBS. Further implications can be extended to the strength, seismic velocities and electrical properties of HBS.

Delineating the anti-cytotoxic and anti-genotoxic potentials of catechin hydrate against cadmium toxicity in human peripheral blood lymphocytes.

PubMed

Alshatwi, Ali A; Hasan, Tarique N; Alqahtani, Ali M; Syed, Naveed A; Shafi, Gowhar; Al-Assaf, Abdullah H; Al-Khalifa, Abdulrahmann S

2014-09-01

Catechins (flavan-3-ol) are a type of natural phenol and well-studied antioxidants. Catechin hydrate, also known as taxifolin; is non-mutagenic, low in toxicity compared to other immunomodulator antioxidants. We aimed to determine the potential of catechin hydrate to prevent the cyto-genotoxic effects of cadmium in lymphocytes; demonstrate the immuno-protective activity of catechin hydrate. Our previous study indicated that cadmium is apoptogenic. Lymphocytes were treated with catechin hydrate or cadmium and catechine hydrate combinations (range 0.1-100μM) to determine their effects on cell viability. Lymphocytes treated with 100μM catechin hydrate and 100μM cadmium showed cell viability 70.65±6.92% and 5.69±2.27%, respectively. In our previous study cadmium (10 and 20μM) induced apoptosis in 31.8% and 44.4% of lymphocytes, respectively. However, the percentage of apoptotic cells after treatment with the combination of cadmium and catechin hydrate was not significantly different from that of catechin hydrate (P>0.05). Only 7.3% and 10.5% of the lymphocytes were apoptotic after treatment with 10μM cadmium+10μM catechin hydrate and 20μM cadmium+20μM catechin hydrate, respectively. The anti-geno-cytotoxic and immuno-protective potential of catechin hydrate was also demonstrated by the non-significant expression of apoptosis-related genes after treatment with catechin hydrate. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparison of the physical and geotechnical properties of gas-hydrate-bearing sediments from offshore India and other gas-hydrate-reservoir systems

USGS Publications Warehouse

Winters, William J.; Wilcox-Cline, R.W.; Long, P.; Dewri, S.K.; Kumar, P.; Stern, Laura A.; Kerr, Laura A.

2014-01-01

The sediment characteristics of hydrate-bearing reservoirs profoundly affect the formation, distribution, and morphology of gas hydrate. The presence and type of gas, porewater chemistry, fluid migration, and subbottom temperature may govern the hydrate formation process, but it is the host sediment that commonly dictates final hydrate habit, and whether hydrate may be economically developed.In this paper, the physical properties of hydrate-bearing regions offshore eastern India (Krishna-Godavari and Mahanadi Basins) and the Andaman Islands, determined from Expedition NGHP-01 cores, are compared to each other, well logs, and published results of other hydrate reservoirs. Properties from the hydrate-free Kerala-Konkan basin off the west coast of India are also presented. Coarser-grained reservoirs (permafrost-related and marine) may contain high gas-hydrate-pore saturations, while finer-grained reservoirs may contain low-saturation disseminated or more complex gas-hydrates, including nodules, layers, and high-angle planar and rotational veins. However, even in these fine-grained sediments, gas hydrate preferentially forms in coarser sediment or fractures, when present. The presence of hydrate in conjunction with other geologic processes may be responsible for sediment porosity being nearly uniform for almost 500 m off the Andaman Islands.Properties of individual NGHP-01 wells and regional trends are discussed in detail. However, comparison of marine and permafrost-related Arctic reservoirs provides insight into the inter-relationships and common traits between physical properties and the morphology of gas-hydrate reservoirs regardless of location. Extrapolation of properties from one location to another also enhances our understanding of gas-hydrate reservoir systems. Grain size and porosity effects on permeability are critical, both locally to trap gas and regionally to provide fluid flow to hydrate reservoirs. Index properties corroborate more advanced consolidation and triaxial strength test results and can be used for predicting behavior in other NGHP-01 regions. Pseudo-overconsolidation is present near the seafloor and is underlain by underconsolidation at depth at some NGHP-01 locations.

Chemically Adjusting Plasma Temperature, Energy and Reactivity (CAPTEAR) Method Using NOx and Combustion for Selective Synthesis of Sc3N@C80 Metallic Nitride Fullerenes

PubMed Central

Stevenson, Steven; Thompson, M. Corey; Coumbe, H. Louie; Mackey, Mary A.; Coumbe, Curtis E.; Phillips, J. Paige

2008-01-01

Goals are (1) to selectively synthesize MNFs in lieu of empty-cage fullerenes (e.g., C60, C70) without compromising MNF yield and (2) to test our hypothesis that MNFs possess a different set of optimal formation parameters than empty-cage fullerenes. In this work, we introduce a novel approach for the selective synthesis of metallic nitride fullerenes (MNFs). This new method is “Chemically Adjusting Plasma Temperature, Energy and Reactivity” (CAPTEAR). The CAPTEAR approach with copper nitrate hydrate uses NOx vapor from NOx generating solid reagents, air and combustion to “tune” the temperature, energy and reactivity of the plasma environment. The extent of temperature, energy and reactive environment is stoichiometrically varied until optimal conditions for selective MNF synthesis are achieved. Analysis of soot extracts indicate that percentages of C60 and Sc3N@C80 are inversely related, whereas the percentages of C70 and higher empty-cage C2n fullerenes are largely unaffected. Hence, there may be a “competitive link” in the formation and mechanism of C60 and Sc3N@C80. Using this CAPTEAR method, purified MNFs (96% Sc3N@C80, 12 mg) have been obtained in soot extracts without a significant penalty in milligram yield when compared to control soot extracts (4% Sc3N@C80, 13 mg Sc3N@C80). The CAPTEAR process with Cu(NO3)2·2.5 H2O uses an exothermic nitrate moiety to suppress empty-cage fullerene formation, whereas Cu functions as a catalyst additive to offset the reactive plasma environment and boost the Sc3N@C80 MNF production. PMID:18052069

Fluoride-selective optical sensor based on aluminum(III)-octaethylporphyrin in thin polymeric film: further characterization and practical application.

PubMed

Badr, Ibrahim H A; Meyerhoff, Mark E

2005-10-15

More detailed analytical studies of a new fluoride-selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4',5'-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-visible spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band lambda(max) of the porphyrin and a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 microM-1.6 mM. Optical selectivity coefficients of <10(-6) for common anions (e.g., sulfate, chloride, nitrate, etc.) and <10(-4) for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3-based fluoride ion-selective electrode method.

Fluoride Selective Optical Sensor Based on Aluminum(III)-Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

PubMed Central

Badr, Ibrahim H. A.; Meyerhoff, Mark E.

2008-01-01

More detailed analytical studies of a new fluoride selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4′,5′-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-VIS spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band λmax of the porphyrin as well as a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 μM to 1.6 mM. Optical selectivity coefficients of < 10−6 for common anions (e.g., sulfate, chloride, nitrate etc.) and < 10−4 for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3 based fluoride ion-selective electrode method. PMID:16223262

Three-dimensional distribution of gas hydrate beneath southern Hydrate Ridge: Constraints from ODP Leg 204

USGS Publications Warehouse

Trehu, A.M.; Long, P.E.; Torres, M.E.; Bohrmann, G.; Rack, F.R.; Collett, T.S.; Goldberg, D.S.; Milkov, A.V.; Riedel, M.; Schultheiss, P.; Bangs, N.L.; Barr, S.R.; Borowski, W.S.; Claypool, G.E.; Delwiche, M.E.; Dickens, G.R.; Gracia, E.; Guerin, G.; Holland, M.; Johnson, J.E.; Lee, Y.-J.; Liu, C.-S.; Su, X.; Teichert, B.; Tomaru, H.; Vanneste, M.; Watanabe, M. E.; Weinberger, J.L.

2004-01-01

Large uncertainties about the energy resource potential and role in global climate change of gas hydrates result from uncertainty about how much hydrate is contained in marine sediments. During Leg 204 of the Ocean Drilling Program (ODP) to the accretionary complex of the Cascadia subduction zone, we sampled the gas hydrate stability zone (GHSZ) from the seafloor to its base in contrasting geological settings defined by a 3D seismic survey. By integrating results from different methods, including several new techniques developed for Leg 204, we overcome the problem of spatial under-sampling inherent in robust methods traditionally used for estimating the hydrate content of cores and obtain a high-resolution, quantitative estimate of the total amount and spatial variability of gas hydrate in this structural system. We conclude that high gas hydrate content (30-40% of pore space or 20-26% of total volume) is restricted to the upper tens of meters below the seafloor near the summit of the structure, where vigorous fluid venting occurs. Elsewhere, the average gas hydrate content of the sediments in the gas hydrate stability zone is generally <2% of the pore space, although this estimate may increase by a factor of 2 when patchy zones of locally higher gas hydrate content are included in the calculation. These patchy zones are structurally and stratigraphically controlled, contain up to 20% hydrate in the pore space when averaged over zones ???10 m thick, and may occur in up to ???20% of the region imaged by 3D seismic data. This heterogeneous gas hydrate distribution is an important constraint on models of gas hydrate formation in marine sediments and the response of the sediments to tectonic and environmental change. ?? 2004 Published by Elsevier B.V.

Volume change associated with formation and dissociation of hydrate in sediment

USGS Publications Warehouse

Ruppel, Carolyn D.; Lee, J.Y.; Santamarina, J. Carlos

2017-01-01

Gas hydrate formation and dissociation in sediments are accompanied by changes in the bulk volume of the sediment and can lead to changes in sediment properties, loss of integrity for boreholes, and possibly regional subsidence of the ground surface over areas where methane might be produced from gas hydrate in the future. Experiments on sand, silts, and clay subject to different effective stress and containing different saturations of hydrate formed from dissolved phase tetrahydrofuran are used to systematically investigate the impact of gas hydrate formation and dissociation on bulk sediment volume. Volume changes in low specific surface sediments (i.e., having a rigid sediment skeleton like sand) are much lower than those measured in high specific surface sediments (e.g., clay). Early hydrate formation is accompanied by contraction for all soils and most stress states in part because growing gas hydrate crystals buckle skeletal force chains. Dilation can occur at high hydrate saturations. Hydrate dissociation under drained, zero lateral strain conditions is always associated with some contraction, regardless of soil type, effective stress level, or hydrate saturation. Changes in void ratio during formation-dissociation decrease at high effective stress levels. The volumetric strain during dissociation under zero lateral strain scales with hydrate saturation and sediment compressibility. The volumetric strain during dissociation under high shear is a function of the initial volume average void ratio and the stress-dependent critical state void ratio of the sediment. Other contributions to volume reduction upon hydrate dissociation are related to segregated hydrate in lenses and nodules. For natural gas hydrates, some conditions (e.g., gas production driven by depressurization) might contribute to additional volume reduction by increasing the effective stress.

Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems: DIFFUSION-DRIVEN HYDRATE GROWTH IN SANDS

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

Nole, Michael; Daigle, Hugh; Cook, Ann E.

The goal of this study is to computationally determine the potential distribution patterns of diffusion-driven methane hydrate accumulations in coarse-grained marine sediments. Diffusion of dissolved methane in marine gas hydrate systems has been proposed as a potential transport mechanism through which large concentrations of hydrate can preferentially accumulate in coarse-grained sediments over geologic time. Using one-dimensional compositional reservoir simulations, we examine hydrate distribution patterns at the scale of individual sand layers (1 to 20 m thick) that are deposited between microbially active fine-grained material buried through the gas hydrate stability zone (GHSZ). We then extrapolate to two- dimensional and basin-scalemore » three-dimensional simulations, where we model dipping sands and multilayered systems. We find that properties of a sand layer including pore size distribution, layer thickness, dip, and proximity to other layers in multilayered systems all exert control on diffusive methane fluxes toward and within a sand, which in turn impact the distribution of hydrate throughout a sand unit. In all of these simulations, we incorporate data on physical properties and sand layer geometries from the Terrebonne Basin gas hydrate system in the Gulf of Mexico. We demonstrate that diffusion can generate high hydrate saturations (upward of 90%) at the edges of thin sands at shallow depths within the GHSZ, but that it is ineffective at producing high hydrate saturations throughout thick (greater than 10 m) sands buried deep within the GHSZ. As a result, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.« less

Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems: DIFFUSION-DRIVEN HYDRATE GROWTH IN SANDS

DOE PAGES

Nole, Michael; Daigle, Hugh; Cook, Ann E.; ...

2017-02-01

The goal of this study is to computationally determine the potential distribution patterns of diffusion-driven methane hydrate accumulations in coarse-grained marine sediments. Diffusion of dissolved methane in marine gas hydrate systems has been proposed as a potential transport mechanism through which large concentrations of hydrate can preferentially accumulate in coarse-grained sediments over geologic time. Using one-dimensional compositional reservoir simulations, we examine hydrate distribution patterns at the scale of individual sand layers (1 to 20 m thick) that are deposited between microbially active fine-grained material buried through the gas hydrate stability zone (GHSZ). We then extrapolate to two- dimensional and basin-scalemore » three-dimensional simulations, where we model dipping sands and multilayered systems. We find that properties of a sand layer including pore size distribution, layer thickness, dip, and proximity to other layers in multilayered systems all exert control on diffusive methane fluxes toward and within a sand, which in turn impact the distribution of hydrate throughout a sand unit. In all of these simulations, we incorporate data on physical properties and sand layer geometries from the Terrebonne Basin gas hydrate system in the Gulf of Mexico. We demonstrate that diffusion can generate high hydrate saturations (upward of 90%) at the edges of thin sands at shallow depths within the GHSZ, but that it is ineffective at producing high hydrate saturations throughout thick (greater than 10 m) sands buried deep within the GHSZ. As a result, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.« less

Adhesion force interactions between cyclopentane hydrate and physically and chemically modified surfaces.

PubMed

Aman, Zachary M; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2014-12-07

Interfacial interactions between liquid-solid and solid-solid phases/surfaces are of fundamental importance to the formation of hydrate deposits in oil and gas pipelines. This work establishes the effect of five categories of physical and chemical modification to steel on clathrate hydrate adhesive force: oleamide, graphite, citric acid ester, nonanedithiol, and Rain-X anti-wetting agent. Hydrate adhesive forces were measured using a micromechanical force apparatus, under both dry and water-wet surface conditions. The results show that the graphite coating reduced hydrate-steel adhesion force by 79%, due to an increase in the water wetting angle from 42 ± 8° to 154 ± 7°. Two chemical surface coatings (nonanedithiol and the citric acid ester) induced rapid hydrate growth in the hydrate particles; nonanedithiol increased hydrate adhesive force by 49% from the baseline, while the citric acid ester coating reduced hydrate adhesion force by 98%. This result suggests that crystal growth may enable a strong adhesive pathway between hydrate and other crystalline structures, however this effect may be negated in cases where water-hydrocarbon interfacial tension is minimised. When a liquid water droplet was placed on the modified steel surfaces, the graphite and citric acid ester became less effective at reducing adhesive force. In pipelines containing a free water phase wetting the steel surface, chemical or physical surface modifications alone may be insufficient to eliminate hydrate deposition risk. In further tests, the citric acid ester reduced hydrate cohesive forces by 50%, suggesting mild activity as a hybrid anti-agglomerant suppressing both hydrate deposition and particle agglomeration. These results demonstrate a new capability to develop polyfunctional surfactants, which simultaneously limit the capability for hydrate particles to aggregate and deposit on the pipeline wall.

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.

Level of hydration and renal function in healthy humans.

PubMed

Anastasio, P; Cirillo, M; Spitali, L; Frangiosa, A; Pollastro, R M; De Santo, N G

2001-08-01

High hydration is commonly used in renal studies to improve the completeness of urine collection. The renal effects of hydration are not well defined. Renal function was studied under fasting conditions (baseline) and after a meat meal (2 g of protein/kg body weight) in 12 healthy adults on a low and high hydration regimen of 0.5 and 4 mL of oral water per kg body weight/30 min, respectively. Urine flow, urinary and plasma Na, K, urea, and osmolality were stably different on low and high hydration regimens. At baseline, there were significant or borderline significant correlations of plasma and urine osmolality with glomerular filtration rate (GFR; inulin clearance) only in the low hydration regimen. GFR was higher in the low than the high hydration regimen at all time points. The difference was significant at baseline (19.2%) and at 90 to 180 minutes after the meal (14.4%). After the meal, GFR increased significantly over baseline values only in the high hydration regimen (30.0% at peak time). Urinary excretion of Na, urea, and osmoles was lower in the low than the high hydration regimen at all time points: The difference was significant for Na (at baseline) and osmoles (all time points). Urinary K excretion was not different in the two regimens. After the meal, there were significant increases in urinary excretion of Na (in the low hydration regimen) and urea (90 to 180 min after the meal). In fasting adults, high hydration lowered GFR and increased natriuresis. After a meat meal, GFR increased only in the high hydration regimen and natriuresis only in the low hydration regimen. Hydration affects GFR and natriuresis under fasting conditions and after a meat meal.

Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

NASA Astrophysics Data System (ADS)

Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

2007-12-01

A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

Indirect Determination of Pentaerythritol Tetranitrate (PETN) with a gold nanoparticles-based colorimetric sensor.

PubMed

Üzer, Ayşem; Yalçın, Uğur; Can, Ziya; Erçağ, Erol; Apak, Reşat

2017-12-01

Pentaerythritol tetranitrate (PETN) is the nitrate ester of pentaerythritol, used as an energetic and filling material for military and civilian purposes and rarely for terrorist actions. As there is no reliable nano-colorimetric method for PETN assay, we developed an indirect method based on the determination of nitrite, obtained by reduction of nitrate derived from the alkaline hydrolysis of PETN with H 2 O 2 . We colorimetrically determined the final product, nitrite, by both conventional Griess reaction and a recently developed gold nanoparticle-4-aminothiophenol-N-(1-naphthyl)-ethylenediamine (AuNP-4-ATP+NED) method. Nitramines (RDX and HMX), if present, could be degraded by alkaline hydrolysis, without affecting PETN. The analytical performance characteristics of the developed assays as molar absorptivity (ε), limits of detection (LOD) and quantification (LOQ) were: ɛ=1.06×10 5 L mol -1 cm -1 , LOD=0.03mgL -1 and LOQ=0.11mgL -1 for indirect Griess method; ɛ=1.9×10 4 Lmol -1 cm -1 ; LOD=0.12mgL -1 and LOQ=0.4mgL -1 for AuNP-4-ATP+NED method. Both methods were applied to a 1:1 (w/w) mixture of PETN and TNT (corresponding to the composition of military explosive 'Pentolite'). In order to eliminate the interference from TNT, the Meisenheimer anion of TNT formed in alkaline medium was retained on a strongly basic anion exchange resin column. As PETN had a very low solubility in water, common soil ions could be eliminated by prewashing the sample with water, or in acetone-water mixtures, Ca 2+ , K + , Cl - , SO 4 2- , and NO 3 - could be tolerated at equal (1:1) mass ratios. Soil nitrates and nitrites, at a mass ratio of 50:1, could be separated from PETN with the aid of their insolubilities in acetone and of their retention affinity toward a strongly basic anion-exchange resin. The developed method was statistically validated against a reference GC-MS method. Copyright © 2017 Elsevier B.V. All rights reserved.

Probing cation and vacancy ordering in the dry and hydrated yttrium-substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: implications for proton mobility.

PubMed

Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

2012-09-05

Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites.

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

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

Apparatus investigates geological aspects of gas hydrates

USGS Publications Warehouse

Booth, J.S.; Winters, W.J.; Dillon, William P.

1999-01-01

The US Geological Survey (USGS), in response to potential geohazards, energy resource potential, and climate issues associated with marine gas hydrates, has developed a laboratory research system that permits hydrate genesis and dissociation under deep-sea conditions, employing user-selected sediment types and pore fluids.The apparatus, GHASTI (gas hydrate and sediment test laboratory instrument), provides a means to link field studies and theory and serves as a tool to improve gas hydrate recognition and assessment, using remote sensing techniques.GHASTLI's use was proven in an exploration well project led by the Geological Survey of Canada and the Japanese National Oil Corp., collaborating with Japan Petroleum Exploration Co. and the USGS. The site was in the Mackenzie Delta region of the Northwest Territories (Mallik 2L-38 drillsite).From tests on natural methane hydrate-bearing sand recovered at about 1,000 m subsurface, the in situ quantity of hydrate was estimated from acoustic properties, and a substantial increase in shear strength due to the presence of the hydrate was measured.1 2GHASTI can mimic a wide range of geologic settings and processes. Initial goals involve improved recognition and mapping of gas hydrate-bearing sediments, understanding factors that control the occurrence and concentration of gas hydrates, knowledge of hydrate's significance to slope failure and foundation problems, and analysis of gas hydrate's potential use as an energy resource.

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

USGS Publications Warehouse

Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

2013-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under 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.

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.

Gas hydrate property measurements in porous sediments with resonant ultrasound spectroscopy

NASA Astrophysics Data System (ADS)

McGrail, B. P.; Ahmed, S.; Schaef, H. T.; Owen, A. T.; Martin, P. F.; Zhu, T.

2007-05-01

Resonant ultrasound spectroscopy was used to characterize a natural geological core sample obtained from the Mallik 5L-38 gas hydrate research well at high pressure and subambient temperatures. Using deuterated methane gas to form gas hydrate in the core sample, it was discovered that resonance amplitudes are correlated with the fraction of the pore space occupied by the gas hydrate crystals. A pore water freezing model was developed that utilizes the known pore size distribution and pore water chemistry to predict gas hydrate saturation as a function of pressure and temperature. The model showed good agreement with the experimental measurements and demonstrated that pore water chemistry is the most important factor controlling equilibrium gas hydrate saturations in these sediments when gas hydrates are formed artificially in laboratory pressure vessels. With further development, the resonant ultrasound technique can provide a rapid, nondestructive, field portable means of measuring the equilibrium P-T properties and dissociation kinetics of gas hydrates in porous media, determining gas hydrate saturations, and may provide new insights into the nature of gas hydrate formation mechanisms in geologic materials.

Seismic- and well-log-inferred gas hydrate accumulations on Richards Island

USGS Publications Warehouse

Collett, T.S.

1999-01-01

The gas hydrate stability zone is areally extensive beneath most of the Mackenzie Delta-Beaufort Sea region, with the base of the gas hydrate stability zone more than 1000 m deep on Richards Island. In this study, gas hydrate has been inferred to occur in nine Richards Island exploratory wells on the basis of well-log responses calibrated to the response of the logs within the cored gas-hydrate-bearing intervals of the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The integration of the available well-log data with more than 240 km of industry-acquired reflection seismic data have allowed us to map the occurrence of four significant gas hydrate and associated free-gas accumulations in the Ivik-Mallik-Taglu area on Richards Island. The occurrence of gas hydrate on Richards Island is mostly restricted to the crest of large anticlinal features that cut across the base of the gas hydrate stability zone. Combined seismic and well-log data analysis indicate that the known and inferred gas hydrate accumulations on Richards Island may contain as much as 187 178106 m3 of gas.

Amount of gas hydrate estimated from compressional- and shear-wave velocities at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

USGS Publications Warehouse

Lee, M.W.

1999-01-01

The amount of in situ gas hydrate concentrated in the sediment pore space at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well was estimated by using compressional-wave (P-wave) and shear-wave (S-wave) downhole log measurements. A weighted equation developed for relating the amount of gas hydrate concentrated in the pore space of unconsolidated sediments to the increase of seismic velocities was applied to the acoustic logs with porosities derived from the formation density log. A weight of 1.56 (W=1.56) and the exponent of 1 (n=1) provided consistent estimates of gas hydrate concentration from the S-wave and the P-wave logs. Gas hydrate concentration is as much as 80% in the pore spaces, and the average gas hydrate concentration within the gas-hydrate-bearing section from 897 m to 1110 m (excluding zones where there is no gas hydrate) was calculated at 39.0% when using P-wave data and 37.8% when using S-wave data.

Implication of seismic attenuation for gas hydrate resource characterization, Mallik, Mackenzie Delta, Canada

NASA Astrophysics Data System (ADS)

Bellefleur, G.; Riedel, M.; Brent, T.; Wright, F.; Dallimore, S. R.

2007-10-01

Wave attenuation is an important physical property of hydrate-bearing sediments that is rarely taken into account in site characterization with seismic data. We present a field example showing improved images of hydrate-bearing sediments on seismic data after compensation of attenuation effects. Compressional quality factors estimated from zero-offset Vertical Seismic Profiling data acquired at Mallik, Northwest Territories, Canada, demonstrate significant wave attenuation for hydrate-bearing sediments. These results are in agreement with previous attenuation estimates obtained from sonic logs and crosshole data at different frequency intervals. The application of an inverse Q-filter to compensate attenuation effects of permafrost and hydrate-bearing sediments improved the resolution of surface 3D seismic data and its correlation with log data, particularly for the shallowest gas hydrate interval. Compensation of the attenuation effects of the permafrost likely explains most of the improvements for the shallow gas hydrate zone. Our results show that characterization of the Mallik gas hydrates with seismic data not corrected for attenuation would tend to overestimate thicknesses and lateral extent of hydrate-bearing strata and hence, the volume of hydrates in place.

Acid/base equilibria in clusters and their role in proton exchange membranes: Computational insight

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

Glezakou, Vanda A; Dupuis, Michel; Mundy, Christopher J

2007-10-24

We describe molecular orbital theory and ab initio molecular dynamics studies of acid/base equilibria of clusters AH:(H 2O) n↔A -:H +(H 2O) n in low hydration regime (n = 1-4), where AH is a model of perfluorinated sulfonic acids, RSO 3H (R = CF 3CF 2), encountered in polymeric electrolyte membranes of fuel cells. Free energy calculations on the neutral and ion pair structures for n = 3 indicate that the two configurations are close in energy and are accessible in the fluctuation dynamics of proton transport. For n = 1,2 the only relevant configuration is the neutral form. Thismore » was verified through ab initio metadynamics simulations. These findings suggest that bases are directly involved in the proton transport at low hydration levels. In addition, the gas phase proton affinity of the model sulfonic acid RSO 3H was found to be comparable to the proton affinity of water. Thus, protonated acids can also play a role in proton transport under low hydration conditions and under high concentration of protons. This work was supported by the Division of Chemical Science, Office of Basic Energy Sciences, US Department of Energy (DOE under Contract DE-AC05-76RL)1830. Computations were performed on computers of the Molecular Interactions and Transformations (MI&T) group and MSCF facility of EMSL, sponsored by US DOE and OBER located at PNNL. This work was benefited from resource of the National Energy Research Scientific Computing Centre, supported by the Office of Science of the US DOE, under Contract No. DE-AC03-76SF00098.« less

Rapid gas hydrate formation processes: Will they work?

DOE PAGES

Brown, Thomas D.; Taylor, Charles E.; Bernardo, Mark P.

2010-06-07

Researchers at DOE’s National Energy Technology Laboratory (NETL) have been investigating the formation of synthetic gas hydrates, with an emphasis on rapid and continuous hydrate formation techniques. The investigations focused on unconventional methods to reduce dissolution, induction, nucleation and crystallization times associated with natural and synthetic hydrates studies conducted in the laboratory. Numerous experiments were conducted with various high-pressure cells equipped with instrumentation to study rapid and continuous hydrate formation. The cells ranged in size from 100 mL for screening studies to proof-of-concept studies with NETL’s 15-Liter Hydrate Cell. The results from this work demonstrate that the rapid and continuousmore » formation of methane hydrate is possible at predetermined temperatures and pressures within the stability zone of a Methane Hydrate Stability Curve.« less

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.

Effects of hydration in contrast-induced acute kidney injury after primary angioplasty: a randomized, controlled trial.

PubMed

Maioli, Mauro; Toso, Anna; Leoncini, Mario; Micheletti, Carlo; Bellandi, Francesco

2011-10-01

Intravascular volume expansion represents a beneficial measure against contrast-induced acute kidney injury (CI-AKI) in patients undergoing elective angiographic procedures. However, the efficacy of this preventive strategy has not yet been established for patients with ST-elevation-myocardial infarction (STEMI), who are at higher risk of this complication after primary percutaneous coronary intervention (PCI). In this randomized study we investigated the possible beneficial role of periprocedural intravenous volume expansion and we compared the efficacy of 2 different hydration strategies in patients with STEMI undergoing primary PCI. We randomly assigned 450 STEMI patients to receive (1) preprocedure and postprocedure hydration of sodium bicarbonate (early hydration group), (2) postprocedure hydration of isotonic saline (late hydration group), or (3) no hydration (control group). The primary end point was the development of CI-AKI, defined as an increase in serum creatinine of ≥25% or 0.5 mg/dL over the baseline value within 3 days after administration of the contrast medium. Moreover, we evaluated a possible relationship between the occurrence of CI-AKI and total hydration volume administered. There were no significant differences in baseline clinical, biochemical, and procedural characteristics in the 3 groups. Overall, CI-AKI occurred in 93 patients (20.6%): the incidence was significantly lower in the early hydration group (12%) with respect to both the late hydration group (22.7%) and the control group (27.3%) (P for trend=0.001). In hydrated patients (early and late hydration groups), lower infused volumes were associated with a significant increase in CI-AKI incidence, and the optimal cutoff point of hydration volume that best discriminates patients at higher risk was ≤960 mL. Adequate intravenous volume expansion may prevent CI-AKI in patients undergoing primary PCI. A regimen of preprocedure and postprocedure hydration therapy with sodium bicarbonate appears to be more efficacious than postprocedure hydration only with isotonic saline.

Stability of CO2 hydrate under very high pressure and low temperature

NASA Astrophysics Data System (ADS)

Hirai, H.; Honda, M.; Kawamura, T.; Yamamoto, Y.; Yagi, T.

2009-12-01

CO2 hydrate is a clathrate compound and the crystal structure type is sI at low pressure. CO2-reduction in the atmosphere is one of the most urgent subjects for mankind. Some technical developments to seclude CO2 as CO2 hydrate in ocean floor have been proceeded. Looking around the solar system, existence of CO2 hydrate in and beneath Martian permafrost has been predicted from spacecraft probes and theoretical studies. Thus, its stability and properties under high pressures and low temperatures are of great interest for fundamental understanding of clathrate hydrate, for the ocean sequestration technology, and for planetary science. CO2 hydrate exhibits characteristic properties different from those of other gas hydrate such as methane hydrate. For example, phase boundary between hydrate and gas + water for many gas hydrates shows positive slope in pressure versus temperature field, and the gas hydrates are kept at pressures up to several GPa at room temperature. On the other hand, for CO2 hydrate, the phase boundary turns to negative slope from positive one at a certain critical point [Nakano et al., 1998], and it can exist only at low temperature regions. And, a theoretical study predicted that CO2 hydrate decompose at low temperature region [Longhi, 2005]. In this study, high pressure and low temperature experiments were performed to examine stability and phase changes of CO2 hydrate using diamond anvil cell in a pressure range from 0.1 to 2.5 GPa and a the temperature range from 65 to 265 K. X-ray diffractometry and Raman spectroscopy revealed that the known phase boundary was extended into lower temperature region, and that CO2 hydrate was kept at low temperature regions at least 65 K despite the theoretical prediction of decomposition. References [1] S. Nakano, M. Moritoki, K. Ohgaki, J. Chem. Eng. Data, 43, 807 (1998). [2] J. Longhi, Geochim. Cosmochim. Acta, 69, 529 (2005)

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.

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.

Effects of Attenuation of Gas Hydrate-bearing Sediments on Seismic Data: Example from Mallik, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Bellefleur, G.; Riedel, M.; Brent, T.

2007-05-01

Wave attenuation is an important physical property of hydrate-bearing sediments that is rarely taken into account in site characterization with seismic data. We present a field example showing improved images of hydrate- bearing sediments on seismic data after compensation of attenuation effects. Compressional quality factors (Q) are estimated from zero-offset Vertical Seismic Profiling data acquired at Mallik, Northwest Territories, Canada. During the last 10 years, two internationally-partnered research drilling programs have intersected three major intervals of sub-permafrost gas hydrates at Mallik, and have successfully extracted core samples containing significant amount of gas hydrates. Individual gas hydrate intervals are up to 40m in thickness and are characterized by high in situ gas hydrate saturation, sometimes exceeding 80% of pore volume of unconsolidated clastic sediments having average porosities ranging from 25% to 40%. The Q-factors obtained from the VSP data demonstrate significant wave attenuation for permafrost and hydrate- bearing sediments. These results are in agreement with previous attenuation estimates from sonic logs and crosshole data at different frequency intervals. The Q-factors obtained from VSP data were used to compensate attenuation effects on surface 3D seismic data acquired over the Mallik gas hydrate research wells. Intervals of gas hydrate on surface seismic data are characterized by strong reflectivity and effects from attenuation are not perceptible from a simple visual inspection of the data. However, the application of an inverse Q-filter increases the resolution of the data and improves correlation with log data, particularly for the shallowest gas hydrate interval. Compensation of the attenuation effects of the permafrost likely explains most of the improvements for the shallow gas hydrate zone. Our results show that characterization of the Mallik gas hydrates with seismic data not corrected for attenuation would tend to overestimate thicknesses and lateral extent of hydrate-bearing strata and hence, the volume of hydrates in place.

Hydro-mechanical properties of pressure core sediments recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02

NASA Astrophysics Data System (ADS)

Yoneda, J.; Oshima, M.; Kida, M.; Kato, A.; Konno, Y.; Jin, Y.; Waite, W. F.; Jang, J.; Kumar, P.; Tenma, N.

2017-12-01

Pressure coring and analysis technology allows for gas hydrate to be recovered from the deep seabed, transferred to the laboratory and characterized while continuously maintaining gas hydrate stability. For this study, dozens of hydrate-bearing pressure core sediment subsections recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02 were tested with Pressure Core Non-destructive Analysis Tools (PNATs) through a collaboration between Japan and India. PNATs, originally developed by AIST as a part of the Japanese National hydrate research program (MH21, funded by METI) conducted permeability, compression and consolidation tests under various effective stress conditions, including the in situ stress state estimated from downhole bulk density measurements. At the in situ effective stress, gas hydrate-bearing sediments had an effective permeability range of 0.01-10mD even at pore-space hydrate saturations above 60%. Permeability increased by 10 to 100 times after hydrate dissociation at the same effective stress, but these post-dissociation gains were erased when effective stress was increased from in situ values ( 1 MPa) to 10MPa in a simulation of the depressurization method for methane extraction from hydrate. Vertical-to-horizontal permeability anisotropy was also investigated. First-ever multi-stage loading tests and strain-rate alternation compression tests were successfully conducted for evaluating sediment strengthening dependence on the rate and magnitude of effective confining stress changes. In addition, oedometer tests were performed up to 40MPa of consolidation stress to simulate the depressurization method in ultra-deep sea environments. Consolidation curves measured with and without gas hydrate were investigated over a wide range of effective confining stresses. Compression curves for gas hydrate-bearing sediments were convex downward due to high hydrate saturations. Consolidation tests show that, regardless of the consolidation history with hydrate in place, the consolidation behavior after dissociation will first return to, then follow, the original normal consolidation curve for the hydrate-free host sediment.

Estimation of potential distribution of gas hydrate in the northern South China Sea

NASA Astrophysics Data System (ADS)

Wang, Chunjuan; Du, Dewen; Zhu, Zhiwei; Liu, Yonggang; Yan, Shijuan; Yang, Gang

2010-05-01

Gas hydrate research has significant importance for securing world energy resources, and has the potential to produce considerable economic benefits. Previous studies have shown that the South China Sea is an area that harbors gas hydrates. However, there is a lack of systematic investigations and understanding on the distribution of gas hydrate throughout the region. In this paper, we applied mineral resource quantitative assessment techniques to forecast and estimate the potential distribution of gas hydrate resources in the northern South China Sea. However, current hydrate samples from the South China Sea are too few to produce models of occurrences. Thus, according to similarity and contrast principles of mineral outputs, we can use a similar hydrate-mining environment with sufficient gas hydrate data as a testing ground for modeling northern South China Sea gas hydrate conditions. We selected the Gulf of Mexico, which has extensively studied gas hydrates, to develop predictive models of gas hydrate distributions, and to test errors in the model. Then, we compared the existing northern South China Sea hydrate-mining data with the Gulf of Mexico characteristics, and collated the relevant data into the model. Subsequently, we applied the model to the northern South China Sea to obtain the potential gas hydrate distribution of the area, and to identify significant exploration targets. Finally, we evaluated the reliability of the predicted results. The south seabed area of Taiwan Bank is recommended as a priority exploration target. The Zhujiang Mouth, Southeast Hainan, and Southwest Taiwan Basins, including the South Bijia Basin, also are recommended as exploration target areas. In addition, the method in this paper can provide a useful predictive approach for gas hydrate resource assessment, which gives a scientific basis for construction and implementation of long-term planning for gas hydrate exploration and general exploitation of the seabed of China.

The influence of hydrogen bonding on partition coefficients

NASA Astrophysics Data System (ADS)

Borges, Nádia Melo; Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.; Ribeiro, Jean F. R.; Rocha, Josmar R.; Sartori, Geraldo Rodrigues

2017-02-01

This Perspective explores how consideration of hydrogen bonding can be used to both predict and better understand partition coefficients. It is shown how polarity of both compounds and substructures can be estimated from measured alkane/water partition coefficients. When polarity is defined in this manner, hydrogen bond donors are typically less polar than hydrogen bond acceptors. Analysis of alkane/water partition coefficients in conjunction with molecular electrostatic potential calculations suggests that aromatic chloro substituents may be less lipophilic than is generally believed and that some of the effect of chloro-substitution stems from making the aromatic π-cloud less available to hydrogen bond donors. Relationships between polarity and calculated hydrogen bond basicity are derived for aromatic nitrogen and carbonyl oxygen. Aligned hydrogen bond acceptors appear to present special challenges for prediction of alkane/water partition coefficients and this may reflect `frustration' of solvation resulting from overlapping hydration spheres. It is also shown how calculated hydrogen bond basicity can be used to model the effect of aromatic aza-substitution on octanol/water partition coefficients.

Global occurrences of gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Lorenson, T.D.

2001-01-01

Natural gas hydrate is found worldwide in sediments of outer continental margins of all oceans and in polar areas with continuous permafrost. There are currently 77 localities identified globally where geophysical, geochemical and/or geological evidence indicates the presence of gas hydrate. Details concerning individual gas-hydrate occurrences are compiled at a new world-wide-web (www) site (http://walrus.wr.usgs.gov/globalhydrate). This site has been created to facilitate global gas-hydrate research by providing information on each of the localities where there is evidence for gas hydrate. Also considered are the implications of gas hydrate as a potential (1) energy resource, (2) factor in global climate change, and (3) geohazard.

Kinetics of formation and dissociation of gas hydrates

NASA Astrophysics Data System (ADS)

Manakov, A. Yu; Penkov, N. V.; Rodionova, T. V.; Nesterov, A. N.; Fesenko, E. E., Jr.

2017-09-01

The review covers a wide range of issues related to the nucleation, growth and dissociation of gas hydrates. The attention is focused on publications of the last 10-15 years. Along with the mathematical models used to describe these processes, the results of relevant experimental studies are surveyed. Particular sections are devoted to the gas hydrate self-preservation effect, the water memory effect in the hydrate formation, development of catalysts for hydrate formation and the effect of substances dissolved in the aqueous phase on the formation of hydrates. The main experimental techniques used to study gas hydrates are briefly considered. The bibliography includes 230 references.

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.

Gas hydrate drilling transect across northern Cascadia margin - IODP Expedition 311

USGS Publications Warehouse

Riedel, M.; Collett, T.; Malone, M.J.; Collett, T.S.; Mitchell, M.; Guerin, G.; Akiba, F.; Blanc-Valleron, M.; Ellis, M.; Hashimoto, Y.; Heuer, V.; Higashi, Y.; Holland, M.; Jackson, P.D.; Kaneko, M.; Kastner, M.; Kim, J.-H.; Kitajima, H.; Long, P.E.; Malinverno, A.; Myers, Gwen E.; Palekar, L.D.; Pohlman, J.; Schultheiss, P.; Teichert, B.; Torres, M.E.; Trehu, A.M.; Wang, Jingyuan; Worthmann, U.G.; Yoshioka, H.

2009-01-01

A transect of four sites (U1325, U1326, U1327 and U1329) across the northern Cascadia margin was established during Integrated Ocean Drilling Program Expedition 311 to study the occurrence and formation of gas hydrate in accretionary complexes. In addition to the transect sites, a fifth site (U1328) was established at a cold vent with active fluid flow. The four transect sites represent different typical geological environments of gas hydrate occurrence across the northern Cascadia margin from the earliest occurrence on the westernmost first accreted ridge (Site U1326) to the eastward limit of the gas hydrate occurrence in shallower water (Site U1329). Expedition 311 complements previous gas hydrate studies along the Cascadia accretionary complex, especially ODP Leg 146 and Leg 204 by extending the aperture of the transect sampled and introducing new tools to systematically quantify the gas hydrate content of the sediments. Among the most significant findings of the expedition was the occurrence of up to 20 m thick sand-rich turbidite intervals with gas hydrate concentrations locally exceeding 50% of the pore space at Sites U1326 and U1327. Moreover, these anomalous gas hydrate intervals occur at unexpectedly shallow depths of 50-120 metres below seafloor, which is the opposite of what was expected from previous models of gas hydrate formation in accretionary complexes, where gas hydrate was predicted to be more concentrated near the base of the gas hydrate stability zone just above the bottom-simulating reflector. Gas hydrate appears to be mainly concentrated in turbidite sand layers. During Expedition 311, the visual correlation of gas hydrate with sand layers was clearly and repeatedly documented, strongly supporting the importance of grain size in controlling gas hydrate occurrence. The results from the transect sites provide evidence for a structurally complex, lithology-controlled gas hydrate environment on the northern Cascadia margin. Local shallow occurrences of high gas hydrate concentrations contradict the previous model of gas hydrate formation at an accretionary prism. However, long-lived fluid flow (part of the old model) is still required to explain the shallow high gas hydrate concentrations, although it is most likely not pervasive throughout the entire accretionary prism, but rather localized and focused by the tectonic processes. Differences in the fluid flow regime across all of the transect drill sites indicate site-specific and probably disconnected (compartmented) deeper fluid sources in the various parts of the accretionary prism. The data and future analyses will yield a better understanding of the geologic controls, evolution and ultimate fate of gas hydrate in an accretionary prism as an important contribution to the role of gas hydrate methane gas in slope stability and possibly in climate change. ?? The Geological Society of London 2009.

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.

Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane

NASA Astrophysics Data System (ADS)

Cai, W.; Lu, H.; Huang, X.

2016-12-01

In natural gas hydrates, some heavy hydrocarbons are always detected in addition to methane. However, it is still not well understood how the trace amount of heavy gas affect the hydrate properties. Intensive studies have been carried out to study the thermodynamic properties and structure types of mixed gases hydrates, but comparatively few investigations have been carried out on the cage occupancies of guest molecules in mixed gases hydrates. For understanding how trace amount of propane affects the formation of mixed methane-propane hydrates, X-ray diffraction, Raman spectroscopy, and gas chromatography were applied to the synthesized mixed methane-propane hydrate specimens, to get their structural characteristics (structure type, structural parameters, cage occupancy, etc.) and gas compositions. The mixed methane-propane hydrates were prepared by reacting fine ice powders with various gas mixtures of methane and propane. When the propane content was below 0.4%, the hydrates synthesized were found containing both sI methane hydrate and sII methane-propane hydrate; while the hydrates were found always sII when propane was over certain content. Detail studies about the cage occupancies of propane and methane in sII hydrate revealed that: 1) with the increase in propane content of methane-propane mixture, the occupancy of propane in large cage increased as accompanied with the decrease in methane occupancy in large cage, however the occupancy of methane in small cage didn't experience significant change; 2) temperature and pressure seemed no obvious influence on cage occupancy.

Natural gas hydrate occurrence and issues

USGS Publications Warehouse

Kvenvolden, K.A.

1994-01-01

Naturally occurring gas hydrate is found in sediment of two regions: (1) continental, including continental shelves, at high latitudes where surface temperatures are very cold, and (2) submarine outer continental margins where pressures are very high and bottom-water temperatures are near 0??C. Continental gas hydrate is found in association with onshore and offshore permafrost. Submarine gas hydrate is found in sediment of continental slopes and rises. The amount of methane present in gas hydrate is thought to be very large, but the estimates that have been made are more speculative than real. Nevertheless, at the present time there has been a convergence of ideas regarding the amount of methane in gas hydrate deposits worldwide at about 2 x 1016 m3 or 7 x 1017 ft3 = 7 x 105 Tcf [Tcf = trillion (1012) ft3]. The potentially large amount of methane in gas hydrate and the shallow depth of gas hydrate deposits are two of the principal factors driving research concerning this substance. Such a large amount of methane, if it could be commercially produced, provides a potential energy resource for the future. Because gas hydrate is metastable, changes of surface pressure and temperature affect its stability. Destabilized gas hydrate beneath the sea floor leads to geologic hazards such as submarine mass movements. Examples of submarine slope failures attributed to gas hydrate are found worldwide. The metastability of gas hydrate may also have an effect on climate. The release of methane, a 'greenhouse' gas, from destabilized gas hydrate may contribute to global warming and be a factor in global climate change.

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.

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.

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.

Hydrolysis studies on bismuth nitrate: synthesis and crystallization of four novel polynuclear basic bismuth nitrates.

PubMed

Miersch, L; Rüffer, T; Schlesinger, M; Lang, H; Mehring, M

2012-09-03

Hydrolysis of Bi(NO(3))(3) in aqueous solution gave crystals of the novel compounds [Bi(6)O(4)(OH)(4)(NO(3))(5)(H(2)O)](NO(3)) (1) and [Bi(6)O(4)(OH)(4)(NO(3))(6)(H(2)O)(2)]·H(2)O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(1)/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) Å, b = 13.4298(9) Å, c = 17.8471(14) Å, β = 94.531(6)°, V = 2210.5(3) Å(3); 2, a = 9.0149(3) Å, b = 16.9298(4) Å, c = 15.6864(4) Å, β = 90.129(3)°, V = 2394.06(12) Å(3). Variation of the conditions for partial hydrolysis of Bi(NO(3))(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·4DMSO] (3) and [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·0.5DMSO] (5), upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1 both with two crystallographically independent molecules in the asymmetric unit. The following lattice parameters are observed: 3, a = 20.3804(10) Å, b = 20.3871(9) Å, c = 34.9715(15) Å, α = 76.657(4)°, β = 73.479(4)°, γ = 60.228(5)°, V = 12021.7(9) Å(3); 5, a = 20.0329(4) Å, b = 20.0601(4) Å, c = 34.3532(6) Å, α = 90.196(1)°, β = 91.344(2)°, γ = 119.370(2)°, V = 12025.8(4) Å(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.

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.

The structural response of the cornea to changes in stromal hydration

PubMed Central

White, Tomas; Boote, Craig; Kamma-Lorger, Christina S.; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M.

2017-01-01

The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas (p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration (H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations (p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. PMID:28592658

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.

Towards understanding the role of amines in the SO2 hydration and the contribution of the hydrated product to new particle formation in the Earth's atmosphere.

PubMed

Lv, Guochun; Nadykto, Alexey B; Sun, Xiaomin; Zhang, Chenxi; Xu, Yisheng

2018-08-01

By theoretical calculations, the gas-phase SO 2 hydration reaction assisted by methylamine (MA) and dimethylamine (DMA) was investigated, and the potential contribution of the hydrated product to new particle formation (NPF) also was evaluated. The results show that the energy barrier for aliphatic amines (MA and DMA) assisted SO 2 hydration reaction is lower than the corresponding that of water and ammonia assisted SO 2 hydration. In these hydration reactions, nearly barrierless reaction (only a barrier of 0.1 kcal mol -1 ) can be found in the case of SO 2  + 2H 2 O + DMA. These lead us to conclude that the SO 2 hydration reaction assisted by MA and DMA is energetically facile. The temporal evolution for hydrated products (CH 3 NH 3 + -HSO 3 - -H 2 O or (CH 3 ) 2 NH 2 + -HSO 3 - -H 2 O) in molecular dynamics simulations indicates that these complexes can self-aggregate into bigger clusters and can absorb water and amine molecules, which means that these hydrated products formed by the hydration reaction may serve as a condensation nucleus to initiate the NPF. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiple stage multiple filter hydrate store

DOEpatents

Bjorkman, H.K. Jr.

1983-05-31

An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means for separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means. 7 figs.

Multiple stage multiple filter hydrate store

DOEpatents

Bjorkman, Jr., Harry K.

1983-05-31

An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means or separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means.

The inhibition of tetrahydrofuran clathrate-hydrate formation with antifreeze protein

NASA Astrophysics Data System (ADS)

Zeng, H.; Wilson, L. D.; Walker, V. K.; Ripmeester, J. A.

2003-01-01

The effect of Type I fish antifreeze protein (AFP) from the winter flounder, Pleuronectes americanus (Walbaum), (WfAFP) on the formation of tetrahydrofuran (THF) clathrate hydrate was studied by observing changes in THF crystal morphology and determining the induction time for nucleation. AFP retarded THF clathrate-hydrate growth at the tested temperatures and modified the THF clathrate-hydrate crystal morphology from octahedral to plate-like. AFP appears to be even more effective than the kinetic inhibitor, polyvinylpyrrolidone (PVP). Recombinant AFP from an insect, a spruce budworm, Choristoneura fumiferana (Clem.), moth, (Cf) was also tested for inhibition activity by observation of the THF-hydrate-crystal-growth habit. Like WfAFP, CfAFP appeared to show adsorption on multiple THF-hydrate-crystal faces. A protein with no antifreeze activity, cytochrome C, was used as a control and it neither changed the morphology of the THF clathrate-hydrate crystals, nor retarded the formation of the hydrate. Preliminary experiments on the inhibition activity of WfAFP on a natural gas hydrate assessed induction time and the amount of propane gas consumed. Similar to the observations for THF, the data indicated that WfAFP inhibited propane-hydrate growth. Taken together, these results support our hypothesis that AFPs can inhibit clathrate-hydrate growth and as well, offer promise for the understanding of the inhibition mechanism.

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.

The structural response of the cornea to changes in stromal hydration.

PubMed

Hayes, Sally; White, Tomas; Boote, Craig; Kamma-Lorger, Christina S; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M

2017-06-01

The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS 2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas ( p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration ( H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations ( p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. © 2017 The Authors.

An Analytical Solution and Numerical Modeling Study of Gas Hydrate Saturation Effects on Porosity and Permeability of Porous Media

NASA Astrophysics Data System (ADS)

Zerpa, L.; Gao, F.; Wang, S.

2017-12-01

There are two major types of natural gas hydrate distributions in porous media: pore filling and contact cementing. The difference between these two distribution types is related to hydrate nucleation and growth processes. In the pore filling distribution, hydrate nucleates from a gas-dissolved aqueous phase at the grain boundary and grows away from grain contacts and surfaces into the pore space. In the contact cementing distribution, hydrate nucleates and grows at the gas-water interface and at intergranular contacts. Previous attempts to correlate changes on porosity and permeability during hydrate formation/dissociation were based on the length difference between the pore body and pore throat, and only considered contact cementing hydrate distribution. This work consists of a study of mathematical models of permeability and porosity as a function of gas hydrate saturation during formation and dissociation of gas hydrates in porous media. In this work, first we derive the permeability equation for the pore filling hydrate deposition as a function of hydrate saturation. Then, a more comprehensive model considering both types of gas hydrate deposition is developed to represent changes in permeability and porosity during hydrate formation and dissociation. This resulted in a model that combines pore filling and contact cementing deposition types in the same reservoir. Finally, the TOUGH+Hydrate numerical reservoir simulator was modified to include these models to analyze the response of production and saturation during a depressurization process, considering different combinations of pore filling and contact cementing hydrate distributions. The empirical exponent used in the permeability adjustment factor model influences both production profile and saturation results. This empirical factor describes the permeability dependence to changes in porosity caused by solid phase formation in the porous medium. The use of the permeability exponent decreases the permeability of the system for a given hydrate saturation, which affects the hydraulic performance of the system. However, from published experimental work, there is only a rough estimation of this permeability exponent. This factor could be represented with an empirical equation if more laboratory and field data becomes available.

Investigating the Metastability of Clathrate Hydrates for Energy Storage

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

Koh, Carolyn Ann

2014-11-18

Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathratemore » hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate hydrate systems are pivotal in the fundamental understanding of crystalline clathrate hydrates and the discovery of new clathrate hydrate properties and novel materials for a broad spectrum of energy applications, including: energy storage (hydrogen, natural gas); carbon dioxide sequestration; controlling hydrate formation in oil/gas transportation in subsea pipelines. The Project has also enabled the training of undergraduate, graduate and postdoctoral students in computational methods, molecular spectroscopy and diffraction, and measurement methods at extreme conditions of high pressure and low temperature.« less

Simulation and Characterization of Methane Hydrate Formation

NASA Astrophysics Data System (ADS)

Dhakal, S.; Gupta, I.

2017-12-01

The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate saturation is followed by decrease in the porosity and permeability of the reservoir rock. Sensitivities on flow rates of gas and water are simulated, using different reservoir properties, fault angles and grid sizes to study the properties of hydrate formation and accumulation in the subsurface.

Gas Hydrate Petroleum System Analysis

NASA Astrophysics Data System (ADS)

Collett, T. S.

2012-12-01

In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is characterized by basal silt- to sand-rich clay dominated stratigraphic units. The upper most debris flow at Site UBGH2-5 extends into the overlying gas hydrate stability zone and IR core scans indicate that this section contains some amount of gas hydrate. The UBGH2 LWD and coring program also confirmed the occurrence of numerous volcaniclastic and siliciclastic sand reservoirs that were deposited as part of local to basin-wide turbidite events. Gas hydrate saturations within the turbidite sands ranged between 60-80 percent. In 2009, the Gulf of Mexico (GOM) Joint Industry Project (JIP) drilled seven wells at three sites, finding gas hydrate at high concentration in sands in four wells, with suspected gas hydrate at low to moderate saturations in two other wells. In the northern GOM, high sedimentation rates in conjunction with salt tectonism, has promoted the formation of complex seafloor topography. As a result, coarse-grained deposition can occur as gravity-driven sedimentation traversing the slope within intra-slope "ponded" accommodation spaces.

Free Radical Chemistry of Disinfection Byproducts. 3. Degradation Mechanisms of Chloronitromethane, Bromonitromethane and Dichloronitromethane

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

Bruce J. Mincher; Stephen P. Mezyk; William J. Cooper

2010-01-01

Halonitromethanes (HNMs) are byproducts formed through ozonation and chlorine/ chloramine disinfection processes in drinking waters that contain dissolved organic matter and bromide ions. These species occur at low concentration, but have been determined to have high cytotoxicity and mutagenicity and therefore may represent a human health hazard. In this study, we have investigated the chemistry involved in the mineralization of HNMs to non-hazardous inorganic products through the application of advanced oxidation and reduction processes. We have combined measured absolute reaction rate constants for the reactions of chloronitromethane, bromonitromethane and dichloronitromethane with the hydroxyl radical and the hydrated electron with amore » kinetic computer model in an attempt to elucidate the reaction pathways of these HNMs. The results are compared to measurements of stable products resulting from steady-state 60Co y-irradiations of the same compounds. The model predicted the decomposition of the parent compounds and ingrowth of chloride and bromide ions with excellent accuracy, but the prediction of the total nitrate ion concentration was slightly in error, reflecting the complexity of nitrogen oxide species reactions in irradiated solution.« less

Fish skin as a model membrane: structure and characteristics.

PubMed

Konrádsdóttir, Fífa; Loftsson, Thorsteinn; Sigfússon, Sigurdur Dadi

2009-01-01

Synthetic and cell-based membranes are frequently used during drug formulation development for the assessment of drug availability. However, most of the currently used membranes do not mimic mucosal membranes well, especially the aqueous mucous layer of the membranes. In this study we evaluated catfish (Anarichas lupus L) skin as a model membrane. Permeation of hydrocortisone, lidocaine hydrochloride, benzocaine, diethylstilbestrol, naproxen, picric acid and sodium nitrate through skin from a freshly caught catfish was determined in Franz diffusion cells. Both lipophilic and hydrophilic molecules permeate through catfish skin via hydrated channels or aqueous pores. No correlation was observed between the octanol/water partition coefficient of the permeating molecules and their permeability coefficient through the skin. Permeation through catfish skin was found to be diffusion controlled. The results suggest that permeation through the fish skin proceeds via a diffusion-controlled process, a process that is similar to drug permeation through the aqueous mucous layer of a mucosal membrane. In addition, the fish skin, with its collagen matrix structure, appears to possess similar properties to the eye sclera.

New insights into hydrothermal vent processes in the unique shallow-submarine arc-volcano, Kolumbo (Santorini), Greece

PubMed Central

Kilias, Stephanos P.; Nomikou, Paraskevi; Papanikolaou, Dimitrios; Polymenakou, Paraskevi N.; Godelitsas, Athanasios; Argyraki, Ariadne; Carey, Steven; Gamaletsos, Platon; Mertzimekis, Theo J.; Stathopoulou, Eleni; Goettlicher, Joerg; Steininger, Ralph; Betzelou, Konstantina; Livanos, Isidoros; Christakis, Christos; Bell, Katherine Croff; Scoullos, Michael

2013-01-01

We report on integrated geomorphological, mineralogical, geochemical and biological investigations of the hydrothermal vent field located on the floor of the density-stratified acidic (pH ~ 5) crater of the Kolumbo shallow-submarine arc-volcano, near Santorini. Kolumbo features rare geodynamic setting at convergent boundaries, where arc-volcanism and seafloor hydrothermal activity are occurring in thinned continental crust. Special focus is given to unique enrichments of polymetallic spires in Sb and Tl (±Hg, As, Au, Ag, Zn) indicating a new hybrid seafloor analogue of epithermal-to-volcanic-hosted-massive-sulphide deposits. Iron microbial-mat analyses reveal dominating ferrihydrite-type phases, and high-proportion of microbial sequences akin to "Nitrosopumilus maritimus", a mesophilic Thaumarchaeota strain capable of chemoautotrophic growth on hydrothermal ammonia and CO2. Our findings highlight that acidic shallow-submarine hydrothermal vents nourish marine ecosystems in which nitrifying Archaea are important and suggest ferrihydrite-type Fe3+-(hydrated)-oxyhydroxides in associated low-temperature iron mats are formed by anaerobic Fe2+-oxidation, dependent on microbially produced nitrate. PMID:23939372

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.

Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

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

Collett, Tim; Bahk, Jang-Jun; Frye, Matt

2013-12-31

This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, butmore » these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.« less

Oil & Natural Gas Technology A new approach to understanding the occurrence and volume of natural gas hydrate in the northern Gulf of Mexico using petroleum industry well logs

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

Cook, Ann; Majumdar, Urmi

The northern Gulf of Mexico has been the target for the petroleum industry for exploration of conventional energy resource for decades. We have used the rich existing petroleum industry well logs to find the occurrences of natural gas hydrate in the northern Gulf of Mexico. We have identified 798 wells with well log data within the gas hydrate stability zone. Out of those 798 wells, we have found evidence of gas hydrate in well logs in 124 wells (15% of wells). We have built a dataset of gas hydrate providing information such as location, interval of hydrate occurrence (if any)more » and the overall quality of probable gas hydrate. Our dataset provides a wide, new perspective on the overall distribution of gas hydrate in the northern Gulf of Mexico and will be the key to future gas hydrate research and prospecting in the area.« less

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.

Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

NASA Astrophysics Data System (ADS)

Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

2017-12-01

Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

Preliminary Experimental Examination Of Controls On Methane Expulsion During Melting Of Natural Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Flemings, P. B.; Bryant, S. L.; You, K.; Polito, P. J.

2013-12-01

Global climate change will cause warming of the oceans and land. This will affect the occurrence, behavior, and location of subseafloor and subterranean methane hydrate deposits. We suggest that in many natural systems local salinity, elevated by hydrate formation or freshened by hydrate dissociation, may control gas transport through the hydrate stability zone. We are performing experiments and modeling the experiments to explore this behavior for different warming scenarios. Initially, we are exploring hydrate association/dissociation in saline systems with constant water mass. We compare experiments run with saline (3.5 wt. %) water vs. distilled water in a sand mixture at an initial water saturation of ~0.5. We increase the pore fluid (methane) pressure to 1050 psig. We then stepwise cool the sample into the hydrate stability field (~3 degrees C), allowing methane gas to enter as hydrate forms. We measure resistivity and the mass of methane consumed. We are currently running these experiments and we predict our results from equilibrium thermodynamics. In the fresh water case, the modeled final hydrate saturation is 63% and all water is consumed. In the saline case, the modeled final hydrate saturation is 47%, the salinity is 12.4 wt. %, and final water saturation is 13%. The fresh water system is water-limited: all the water is converted to hydrate. In the saline system, pore water salinity is elevated and salt is excluded from the hydrate structure during hydrate formation until the salinity drives the system to three phase equilibrium (liquid, gas, hydrate) and no further hydrate forms. In our laboratory we can impose temperature gradients within the column, and we will use this to investigate equilibrium conditions in large samples subjected to temperature gradients and changing temperature. In these tests, we will quantify the hydrate saturation and salinity over our meter-long sample using spatially distributed temperature sensors, spatially distributed resistivity probes, compressional wave velocities, and X-ray computed tomography scanning. Modeling of hydrate formation and dissociation for these conditions indicates that the transport of bulk fluid phases (gas and water) plays a crucial role in the overall behavior, and we will explore open-system boundary conditions in the experiments to test this prediction.

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.

In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

NASA Astrophysics Data System (ADS)

Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

2004-12-01

During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in concentrations too low to be detected by the current DORISS instrument. In situ analyses of the hydrates show them to be structure I hydrates with methane as the primary guest molecule; the data compare well to laboratory data.

Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

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

Myers, Greg

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Projectmore » Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.« less

Gas hydrate and humans

USGS Publications Warehouse

Kvenvolden, K.A.

2000-01-01

The potential effects of naturally occurring gas hydrate on humans are not understood with certainty, but enough information has been acquired over the past 30 years to make preliminary assessments possible. Three major issues are gas hydrate as (1) a potential energy resource, (2) a factor in global climate change, and (3) a submarine geohazard. The methane content is estimated to be between 1015 to 1017 m3 at STP and the worldwide distribution in outer continental margins of oceans and in polar regions are significant features of gas hydrate. However, its immediate development as an energy resource is not likely because there are various geological constraints and difficult technological problems that must be solved before economic recovery of methane from hydrate can be achieved. The role of gas hydrate in global climate change is uncertain. For hydrate methane to be an effective greenhouse gas, it must reach the atmosphere. Yet there are many obstacles to the transfer of methane from hydrate to the atmosphere. Rates of gas hydrate dissociation and the integrated rates of release and destruction of the methane in the geo/hydro/atmosphere are not adequately understood. Gas hydrate as a submarine geohazard, however, is of immediate and increasing importance to humans as our industrial society moves to exploit seabed resources at ever-greater depths in the waters of our coastal oceans. Human activities and installations in regions of gas-hydrate occurrence must take into account the presence of gas hydrate and deal with the consequences of its presence.

In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

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

2011-01-01

In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

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.

Natural Gas Hydrates Estimation Using Seismic Inversion and Rock Physics

NASA Astrophysics Data System (ADS)

Dutta, N.; Dai, J.; Kleinberg, R.; Xu, H.

2005-05-01

Gas hydrate drilling worldwide indicates that the formation of gas hydrates in shallow sediments tends to increase P- and S-wave velocities of the hosting rocks. Rock physics models of gas hydrates provide the links between velocity anomalies and gas hydrate concentration. In this abstract, we evaluate the numerical predictions of some of the major rock physics models of gas hydrates and validate those with well log data from the Mallik and Blake Ridge wells. We find that a model in which the gas hydrate is a part of the rock framework produces results that are consistent with well log data. To enhance the accuracy of seismic estimation, we adopt a five-step, integrated workflow that enables us to identify and quantify gas hydrates in the deepwater Gulf of Mexico (GOM). It includes: 1) Reprocessing conventional 3D seismic data at high resolution using an amplitude-preserving flow with prestack time migration, 2) A detailed stratigraphic evaluation to identify potential hydrate zones, 3) Seismic attribute analysis to further delineate anomalous zones, 4) Full waveform prestack inversion to characterize acoustic properties of gas hydrates in 1D (Mallick, 1995; Mallick, 1999) and map in 3D using hybrid inversion techniques (Dutta, 2002; Mallick and Dutta, 2002), and 5) Quantitative estimation of gas hydrate saturation using rock property models. We illustrate the procedure using 3D seismic data, and estimate gas hydrate saturation in the study area in the GOM.

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.

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.

Assessing the feasibility of hydrate deposition on pipeline walls--adhesion force measurements of clathrate hydrate particles on carbon steel.

PubMed

Nicholas, Joseph W; Dieker, Laura E; Sloan, E Dendy; Koh, Carolyn A

2009-03-15

Adhesive forces between cyclopentane (CyC5) hydrates and carbon steel (CS) were measured. These forces were found to be substantially lower than CyC5 hydrate-CyC5 hydrate particle measurements and were also lower than ice-CS measurements. The measured adhesive forces were used in a force balance to predict particle removal from the pipeline wall, assuming no free water was present. The force balance predicted entrained hydrate particles of 3 microns and larger diameter would be removed at typical operating flow rates in offshore oil and gas pipelines. These predictions also suggest that hydrate deposition will not occur in stabilized (cold) flow practices.

Gas hydrate in nature

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

Laboratory formation of non-cementing, methane hydrate-bearing sands

USGS Publications Warehouse

Waite, William F.; Bratton, Peter M.; Mason, David H.

2011-01-01

Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

ERIC Educational Resources Information Center

Barlag, Rebecca; Nyasulu, Frazier

2011-01-01

The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

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.

A method to predict equilibrium conditions of gas hydrate formation in porous media

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

Clarke, M.A.; Pooladi-Darvish, M.; Bishnoi, P.R.

1999-06-01

In the petroleum industry, it is desirable to avoid the formation of gas hydrates. When gas hydrates form, they tend to agglomerate and block pipelines and process equipment. However, naturally occurring gas hydrates that form in the permafrost region or in deep oceans represent a vast untouched natural gas reserve. Although the exact amount of gas in the hydrate form is not known, it is believed to be comparable to the known amount of gas in the free state. Numerous methods for the recovery of natural gas from hydrate fields have been proposed. These techniques include thermal decomposition, depressurization, andmore » chemical injection. To fully exploit hydrate reserves, it will be necessary to know the decomposition/formation conditions of the gas hydrate in porous media. A predictive model has been developed to determine the incipient hydrate formation conditions in porous media. The only additional information that is needed to determine the incipient hydrate formation conditions is the pore radius, surface energy per unit area, and wetting angle. It was found that the model performed well in predicting the experimental data of Handa and Stupin.« less

Methane hydrate formation in turbidite sediments of northern Cascadia, IODP Expedition 311

USGS Publications Warehouse

Torres, M.E.; Trehu, A.M.; Cespedes, N.; Kastner, M.; Wortmann, U.G.; Kim, J.-H.; Long, P.; Malinverno, A.; Pohlman, J.W.; Riedel, M.; Collett, T.

2008-01-01

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8??km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49??mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23??cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63????m) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245??mbsf. ?? 2008 Elsevier B.V.

Gas hydrates of outer continental margins

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

Kvenvolden, K.A.

1990-05-01

Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf ofmore » Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.« less

Quality Improvement Initiative to Increase the Use of Nasogastric Hydration in Infants With Bronchiolitis.

PubMed

Srinivasan, Mythili; Pruitt, Cassandra; Casey, Erin; Dhaliwal, Keerat; DeSanto, Cori; Markus, Richard; Rosen, Ayelet

2017-08-01

Intravenous (IV) hydration is used primarily in children with bronchiolitis at our institution. Because nasogastric (NG) hydration can provide better nutrition, the goal of our quality improvement (QI) initiative was to increase the rate of NG hydration in eligible children 1 to 23 months old with bronchiolitis by 20% over 6 months. We used Plan-Do-Study-Act cycles to increase the use of NG hydration in eligible children. Interventions included educational and system-based changes and sharing parental feedback with providers. Chart reviews were performed to identify the rates of NG hydration, which were plotted over time in a statistical process control p chart. The balancing measure was the rate of complications in children with NG versus IV hydration. Two hundred and ninety-three children who were hospitalized with bronchiolitis needed supplemental hydration during the QI initiative (January 2016-April 2016). Ninety-one children were candidates for NG hydration, and 53 (58%) received NG hydration. The rates of NG hydration increased from a baseline of 0% pre-QI bronchiolitis season (January 2015-April 2015) to 58% during the initiative. There was no aspiration and no accidental placement of the NG tube into a child's airway. Nine patients (17%) in the NG group had a progression of disease requiring nil per os status, and 6 of these were transferred to the PICU whereas none of those in the IV group were transferred to the PICU. Post-QI initiative, the majority of nurses (63%) and physicians (95%) stated that they are more likely to consider NG hydration in children with bronchiolitis. We successfully increased the rates of NG hydration in eligible children with bronchiolitis by using educational and system-based interventions. Copyright © 2017 by the American Academy of Pediatrics.

Natural-gas hydrates: Resource of the twenty-first century?

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Although considerable uncertainty and disagreement prevail concerning the world's gas-hydrate resources, the estimated amount of gas in those gas-hydrate accumulations greatly exceeds the volume of known conventional gas reserves. However, the role that gas hydrates will play in contributing to the world's energy requirements will ultimately depend less on the volume of gas-hydrate resources than on the cost to extract them. Gas hydrates occur in sedimentary deposits under conditions of pressure and temperature present in permafrost regions and beneath the sea in outer continental margins. The combined information from arctic gas-hydrate studies shows that in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 m to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors (known as bottom-simulating reflectors) that have been mapped at depths below the seafloor ranging from approximately 100 m to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas-hydrate accumulations are in rough accord at about 20,000 trillion m3. Gas hydrate as an energy commodity is often grouped with other unconventional hydrocarbon resources. In most cases, the evolution of a nonproducible unconventional resource to a producible energy resource has relied on significant capital investment and technology development. To evaluate the energy-resource potential of gas hydrates will also require the support of sustained research and development programs. Despite the fact that relatively little is known about the ultimate resource potential of gas hydrates, it is certain that they are a vast storehouse of natural gas, and significant technical challenges will need to be met before this enormous resource can be considered an economically producible reserve.

Methane gas hydrate effect on sediment acoustic and strength properties

USGS Publications Warehouse

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

2007-01-01

To improve our understanding of the interaction of methane gas hydrate with host sediment, we studied: (1) the effects of gas hydrate and ice on acoustic velocity in different sediment types, (2) effect of different hydrate formation mechanisms on measured acoustic properties (3) dependence of shear strength on pore space contents, and (4) pore pressure effects during undrained shear.A wide range in acoustic p-wave velocities (Vp) were measured in coarse-grained sediment for different pore space occupants. Vp ranged from less than 1 km/s for gas-charged sediment to 1.77–1.94 km/s for water-saturated sediment, 2.91–4.00 km/s for sediment with varying degrees of hydrate saturation, and 3.88–4.33 km/s for frozen sediment. Vp measured in fine-grained sediment containing gas hydrate was substantially lower (1.97 km/s). Acoustic models based on measured Vp indicate that hydrate which formed in high gas flux environments can cement coarse-grained sediment, whereas hydrate formed from methane dissolved in the pore fluid may not.The presence of gas hydrate and other solid pore-filling material, such as ice, increased the sediment shear strength. The magnitude of that increase is related to the amount of hydrate in the pore space and cementation characteristics between the hydrate and sediment grains. We have found, that for consolidation stresses associated with the upper several hundred meters of sub-bottom depth, pore pressures decreased during shear in coarse-grained sediment containing gas hydrate, whereas pore pressure in fine-grained sediment typically increased during shear. The presence of free gas in pore spaces damped pore pressure response during shear and reduced the strengthening effect of gas hydrate in sands.

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.

Effect of pH and temperature on the stability of UV-induced repairable pyrimidine hydrates in DNA.

PubMed

O'Donnell, R E; Boorstein, R J; Cunningham, R P; Teebor, G W

1994-08-23

UV irradiation of cytosine yields 6-hydroxy-5,6-dihydrocytosine (cytosine hydrate) whether the cytosine is in solution as base, nucleoside, or nucleotide or on the DNA backbone. Cytosine hydrate decomposes by elimination of water, yielding cytosine, or by irreversible deamination, yielding uracil hydrate, which, in turn, decomposes by dehydration yielding uracil. To determine how pH and temperature affect these decomposition reactions, alternating poly(dG-[3H]dC) copolymer was irradiated at 254 nm and incubated under different conditions of pH and temperature. The cytosine hydrate and uracil hydrate content of the DNA was determined by the use of Escherichia coli endonuclease III, which releases pyrimidine hydrates from DNA by virtue of its DNA glycosylase activity. Uracil content was determined by using uracil-DNA glycosylase. The rate of decomposition of cytosine hydrate to cytosine was determined at 4 temperatures at pH 3.1, 5.4, and 7.4. The Ea was determined from the rates by using the Arrhenius equation and proved to be the same at pH 5.4 and 7.4, although the decomposition rate at pH 5.4 was faster at all temperatures. At pH 3.1, the Ea was reduced. These results suggest that the dehydration reaction is affected by two discrete protonations, most probably of the N-3 and the OH group of C-6 of cytosine hydrate. The deamination of cytosine hydrate to uracil hydrate was maximal at pH 3.1 at all temperatures. The doubly protonated cytosine hydrate probably is the common intermediate for both competing decomposition reactions, explaining why cytosine hydrate is prone to deamination at acid pH.(ABSTRACT TRUNCATED AT 250 WORDS)

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

Reservoir controls on the occurrence and production of gas hydrates in nature

USGS Publications Warehouse

Collett, Timothy Scott

2014-01-01

modeling has shown that concentrated gas hydrate occurrences in sand reservoirs are conducive to existing well-based production technologies. The resource potential of gas hydrate accumulations in sand-dominated reservoirs have been assessed for several polar terrestrial basins. In 1995, the U.S. Geological Survey (USGS) assigned an in-place resource of 16.7 trillion cubic meters of gas for hydrates in sand-dominated reservoirs on the Alaska North Slope. In a more recent assessment, the USGS indicated that there are about 2.42 trillion cubic meters of technically recoverable gas resources within concentrated, sand-dominated, gas hydrate accumulations in northern Alaska. Estimates of the amount of in-place gas in the sand dominated gas hydrate accumulations of the Mackenzie Delta Beaufort Sea region of the Canadian arctic range from 1.0 to 10 trillion cubic meters of gas. Another prospective gas hydrate resources are those of moderate-to-high concentrations within sandstone reservoirs in marine environments. In 2008, the Bureau of Ocean Energy Management estimated that the Gulf of Mexico contains about 190 trillion cubic meters of gas in highly concentrated hydrate accumulations within sand reservoirs. In 2008, the Japan Oil, Gas and Metals National Corporation reported on a resource assessment of gas hydrates in which they estimated that the volume of gas within the hydrates of the eastern Nankai Trough at about 1.1 trillion cubic meters, with about half concentrated in sand reservoirs. Because conventional production technologies favor sand-dominated gas hydrate reservoirs, sand reservoirs are considered to be the most viable economic target for gas hydrate production and will be the prime focus of most future gas hydrate exploration and development projects.

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.

The characteristics of gas hydrates occurring in natural environment

NASA Astrophysics Data System (ADS)

Lu, H.; Moudrakovski, I.; Udachin, K.; Enright, G.; Ratcliffe, C.; Ripmeester, J.

2009-12-01

In the past few years, extensive analyses have been carried out for characterizing the natural gas hydrate samples from Cascadia, offshore Vancouver Island; Mallik, Mackenzie Delta; Mount Elbert, Alaska North Slope; Nankai Trough, offshore Japan; Japan Sea and offshore India. With the results obtained, it is possible to give a general picture of the characteristics of gas hydrates occurring in natural environment. Gas hydrate can occur in sediments of various types, from sands to clay, although it is preferentially enriched in sediments of certain types, for example coarse sands and fine volcanic ash. Most of the gas hydrates in sediments are invisible, occurring in the pores of the sediments, while some hydrates are visible, appearing as massive, nodular, planar, vein-like forms and occurring around the seafloor, in the fractures related to fault systems, or any other large spaces available in sediments. Although methane is the main component of most of the natural gas hydrates, C2 to C7 hydrocarbons have been recognized in hydrates, sometimes even in significant amounts. Shallow marine gas hydrates have been found generally to contain minor amounts of hydrogen sulfide. Gas hydrate samples with complex gas compositions have been found to have heterogeneous distributions in composition, which might reflect changes in the composition of the available gas in the surrounding environment. Depending on the gas compositions, the structure type of a natural gas hydrate can be structure I, II or H. For structure I methane hydrate, the large cages are almost fully occupied by methane molecules, while the small cages are only partly occupied. Methane hydrates occurring in different environments have been identified with almost the same crystallographic parameters.

Permafrost-associated natural gas hydrate occurrences on the Alaska North Slope

USGS Publications Warehouse

Collett, T.S.; Lee, M.W.; Agena, W.F.; Miller, J.J.; Lewis, K.A.; Zyrianova, M.V.; Boswell, R.; Inks, T.L.

2011-01-01

In the 1960s Russian scientists made what was then a bold assertion that gas hydrates should occur in abundance in nature. Since this early start, the scientific foundation has been built for the realization that gas hydrates are a global phenomenon, occurring in permafrost regions of the arctic and in deep water portions of most continental margins worldwide. In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually become a producible energy resource, yet technical and economic hurdles have historically made gas hydrate development a distant goal. This view began to change in recent years with the realization that this unconventional resource could be developed with existing conventional oil and gas production technology. One of the most significant developments was the completion of the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope, which along with the Mallik project in Canada, have for the first time allowed the rational assessment of gas hydrate production technology and concepts. Almost 40 years of gas hydrate research in northern Alaska has confirmed the occurrence of at least two large gas hydrate accumulations on the North Slope. We have also seen in Alaska the first ever assessment of how much gas could be technically recovered from gas hydrates. However, significant technical concerns need to be further resolved in order to assess the ultimate impact of gas hydrate energy resource development in northern Alaska. ?? 2009 Elsevier Ltd.

Pre- and post-drill comparison of the Mount Elbert gas hydrate prospect, Alaska North Slope

USGS Publications Warehouse

Lee, M.W.; Agena, W.F.; Collett, T.S.; Inks, T.L.

2011-01-01

In 2006, the United States Geological Survey (USGS) completed a detailed analysis and interpretation of available 2-D and 3-D seismic data, along with seismic modeling and correlation with specially processed downhole well log data for identifying potential gas hydrate accumulations on the North Slope of Alaska. A methodology was developed for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area. The study revealed a total of 14 gas hydrate prospects in this area.In order to validate the gas hydrate prospecting protocol of the USGS and to acquire critical reservoir data needed to develop a longer-term production testing program, a stratigraphic test well was drilled at the Mount Elbert prospect in the Milne Point area in early 2007. The drilling confirmed the presence of two prominent gas-hydrate-bearing units in the Mount Elbert prospect, and high quality well logs and core data were acquired. The post-drill results indicate pre-drill predictions of the reservoir thickness and the gas-hydrate saturations based on seismic and existing well data were 90% accurate for the upper unit (hydrate unit D) and 70% accurate for the lower unit (hydrate unit C), confirming the validity of the USGS approach to gas hydrate prospecting. The Mount Elbert prospect is the first gas hydrate accumulation on the North Slope of Alaska identified primarily on the basis of seismic attribute analysis and specially processed downhole log data. Post-drill well log data enabled a better constraint of the elastic model and the development of an improved approach to the gas hydrate prospecting using seismic attributes. ?? 2009.

Strategies to overcome pH-dependent solubility of weakly basic drugs by using different types of alginates.

PubMed

Gutsche, S; Krause, M; Kranz, H

2008-12-01

Weakly basic drugs demonstrate higher solubility at lower pH, thus often leading to faster drug release at lower pH. The objective of this study was to achieve pH-independent release of weakly basic drugs from extended release formulations based on the naturally occurring polymer sodium alginate. Three approaches to overcome the pH-dependent solubility of the weakly basic model drug verapamil hydrochloride were investigated. First, matrix tablets were prepared by direct compression of drug substance with different types of sodium alginate only. Second, pH-modifiers were added to the drug/alginate matrix systems. Third, press-coated tablets consisting of an inner pH-modifier tablet core and an outer drug/sodium alginate coat were prepared. pH-Independent drug release was achieved from matrix tablets consisting of selected alginates and drug substance only. Alginates are better soluble at higher pH. Therefore, they are able to compensate the poor solubility of weakly basic drugs at higher pH as the matrix of the tablets dissolves faster. This approach was successful when using alginates that demonstrated fast hydration and erosion at higher pH. The approach failed for alginates with less-pronounced erosion at higher pH. The addition of fumaric acid to drug/alginate-based matrix systems decreased the microenvironmental pH within the tablets thus increasing the solubility of the weakly basic drug at higher pH. Therefore, pH-independent drug release was achieved irrespective of the type of alginate used. Drug release from press-coated tablets did not provide any further advantages as compound release remained pH-dependent.

Gulf of Mexico Gas Hydrate Joint Industry Project Leg II logging-while-drilling data acquisition and analysis

USGS Publications Warehouse

Collett, Timothy S.; Lee, Wyung W.; Zyrianova, Margarita V.; Mrozewski, Stefan A.; Guerin, Gilles; Cook, Ann E.; Goldberg, Dave S.

2012-01-01

One of the objectives of the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II (GOM JIP Leg II) was the collection of a comprehensive suite of logging-while-drilling (LWD) data within gas-hydrate-bearing sand reservoirs in order to make accurate estimates of the concentration of gas hydrates under various geologic conditions and to understand the geologic controls on the occurrence of gas hydrate at each of the sites drilled during this expedition. The LWD sensors just above the drill bit provided important information on the nature of the sediments and the occurrence of gas hydrate. There has been significant advancements in the use of downhole well-logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From using electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells to where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Recent integrated sediment coring and well-log studies have confirmed that electrical resistivity and acoustic velocity data can yield accurate gas hydrate saturations in sediment grain supported (isotropic) systems such as sand reservoirs, but more advanced log analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. In support of the GOM JIP Leg II effort, well-log data montages have been compiled and presented in this report which includes downhole logs obtained from all seven wells drilled during this expedition with a focus on identifying and characterizing the potential gas-hydrate-bearing sedimentary section in each of the wells. Also presented and reviewed in this report are the gas-hydrate saturation and sediment porosity logs for each of the wells as calculated from available downhole well logs.

Shifting Focus: From Hydration for Performance to Hydration for Health.

PubMed

Perrier, Erica T

2017-01-01

Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the relationships between water intake, hydration, vasopressin, and health outcomes. Thus, this emerging field represents an excellent opportunity, particularly for young researchers, to develop relevant and novel lines of research. © 2017 The Author(s) Published by S. Karger AG, Basel.

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.

Basin-Wide Temperature Constraints On Gas Hydrate Stability In The Gulf Of Mexico

NASA Astrophysics Data System (ADS)

MacDonald, I. R.; Reagan, M. T.; Guinasso, N. L.; Garcia-Pineda, O. G.

2012-12-01

Gas hydrate deposits commonly occur at the seafloor-water interface on marine margins. They are especially prevalent in the Gulf of Mexico where they are associated with natural oil seeps. The stability of these deposits is potentially challenged by fluctuations in bottom water temperature, on an annual time-scale, and under the long-term influence of climate change. We mapped the locations of natural oil seeps where shallow gas hydrate deposits are known to occur across the entire Gulf of Mexico basin based on a comprehensive review of synthetic aperture radar (SAR) data (~200 images). We prepared a bottom water temperature map based on the archive of CTD casts from the Gulf (~6000 records). Comparing the distribution of gas hydrate deposits with predicted bottom water temperature, we find that a broad area of the upper slope lies above the theoretical stability horizon for structure 1 gas hydrate, while all sites where gas hydrate deposits occur are within the stability horizon for structure 2 gas hydrate. This is consistent with analytical results that structure 2 gas hydrates predominate on the upper slope (Klapp et al., 2010), where bottom water temperatures fluctuate over a 7 to 10 C range (approx. 600 m depth), while pure structure 1 hydrates are found at greater depths (approx. 3000 m). Where higher hydrocarbon gases are available, formation of structure 2 gas hydrate should significantly increase the resistance of shallow gas hydrate deposits to destabilizing effects variable or increasing bottom water temperature. Klapp, S.A., Bohrmann, G., Kuhs, W.F., Murshed, M.M., Pape, T., Klein, H., Techmer, K.S., Heeschen, K.U., and Abegg, F., 2010, Microstructures of structure I and II gas hydrates from the Gulf of Mexico: Marine and Petroleum Geology, v. 27, p. 116-125.Bottom temperature and pressure for Gulf of Mexico gas hydrate outcrops and stability horizons for sI and sII hydrate.

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.

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

Structural study of the Fox-1 RRM protein hydration reveals a role for key water molecules in RRM-RNA recognition

PubMed Central

Blatter, Markus; Cléry, Antoine; Damberger, Fred F.

2017-01-01

Abstract The Fox-1 RNA recognition motif (RRM) domain is an important member of the RRM protein family. We report a 1.8 Å X-ray structure of the free Fox-1 containing six distinct monomers. We use this and the nuclear magnetic resonance (NMR) structure of the Fox-1 protein/RNA complex for molecular dynamics (MD) analyses of the structured hydration. The individual monomers of the X-ray structure show diverse hydration patterns, however, MD excellently reproduces the most occupied hydration sites. Simulations of the protein/RNA complex show hydration consistent with the isolated protein complemented by hydration sites specific to the protein/RNA interface. MD predicts intricate hydration sites with water-binding times extending up to hundreds of nanoseconds. We characterize two of them using NMR spectroscopy, RNA binding with switchSENSE and free-energy calculations of mutant proteins. Both hydration sites are experimentally confirmed and their abolishment reduces the binding free-energy. A quantitative agreement between theory and experiment is achieved for the S155A substitution but not for the S122A mutant. The S155 hydration site is evolutionarily conserved within the RRM domains. In conclusion, MD is an effective tool for predicting and interpreting the hydration patterns of protein/RNA complexes. Hydration is not easily detectable in NMR experiments but can affect stability of protein/RNA complexes. PMID:28505313

An experimental challenge: Unraveling the dependencies of ultrasonic and electrical properties of sandy sediments with pore-filling gas hydrates

NASA Astrophysics Data System (ADS)

Heeschen, Katja; Spangenberg, Erik; Seyberth, Karl; Priegnitz, Mike; Schicks, Judith M.

2016-04-01

The accuracy of gas hydrate quantification using seismic or electric measurements fundamentally depends on the knowledge of any factor describing the dependencies of physical properties on gas hydrate saturation. Commonly, these correlations are the result of laboratory measurements on artificially produced gas hydrates of exact saturation. Thus, the production of gas hydrates and accurate determination of gas hydrate concentrations or those of a substitute are a major concern. Here we present data of both, seismic and electric measurements on accurately quantified pore-filling ice as a substitute for natural gas hydrates. The method was validated using selected gas hydrate saturations in the same experimental set-up as well as literature data from glass bead samples [Spangenberg and Kulenkampff, 2006]. The environmental parameters were chosen to fit those of a possible gas hydrate reservoir in the Danube Delta, which is in the focus of models for joint inversions of seismic and electromagnetic data in the SUGAR III project. The small effective pressures present at this site proved to be yet another challenge for the experiments. Using a more powerful pulse generator and a 4 electrode electric measurement, respectively, models for a wide range of gas hydrate saturations between 20 - 90 % vol. could be established. Spangenberg, E. and Kulenkampff, J., Influence of methane hydrate content on electrical sediment properties. Geophysical Research Letters 2006, 33, (24).

Gas hydrate in seafloor sediments: Impact on future resources and drilling safety

USGS Publications Warehouse

Dillon, William P.; Max, Michael D.

2001-01-01

Gas hydrate concentrates methane and sometimes other gases in its crystal lattice and this gas can be released intentionally creating a resource or escape accidentally forming a hazard. The densest accumulations of gas hydrate tend to occur at sites where the base of the gas hydrate stability zone (commonly the upper several hundred m of the sedimentary section) is configured to trap gas, often as a broad arch. The gas may rise from below or form by bacterial activity at shallow depth, but gas commonly is concentrated near the base of the gas hydrate stability zone by recycling. This gas accumulates in presumably leaky traps, then enriches the hydrate above as it migrates upward by diffusion, fluid movement through sedimentary pores, or flow along fracture channelways. Analysis of seismic reflection profiles is beginning to identify such concentrations and the circumstances that create them. The first attempt to explore for gas hydrate off Japan by the Japanese National Oil Corporation produced quite favorable results, showing high gas hydrate contents in permeable sediments. Gas hydrate dissociation can be a safety concern in drilling and production. The volume of water and gas released in dissociation is often greater than the volume of the hydrate, so overpressures can be created. Furthermore, the gas hydrate can provide shallow seals, so the possibility of high-pressure flows or generation of slides is apparent. 

Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

NASA Astrophysics Data System (ADS)

Avdellidou, C.; Delbo', M.; Fienga, A.

2018-04-01

Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

Glacial Cycles Influence Marine Methane Hydrate Formation

NASA Astrophysics Data System (ADS)

Malinverno, A.; Cook, A. E.; Daigle, H.; Oryan, B.

2018-01-01

Methane hydrates in fine-grained continental slope sediments often occupy isolated depth intervals surrounded by hydrate-free sediments. As they are not connected to deep gas sources, these hydrate deposits have been interpreted as sourced by in situ microbial methane. We investigate here the hypothesis that these isolated hydrate accumulations form preferentially in sediments deposited during Pleistocene glacial lowstands that contain relatively large amounts of labile particulate organic carbon, leading to enhanced microbial methanogenesis. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent organic carbon deposition controlled by glacioeustatic sea level variations. In the model, hydrate forms in sediments with greater organic carbon content deposited during the penultimate glacial cycle ( 120-240 ka). The model predictions match hydrate-bearing intervals detected in three sites drilled on the northern Gulf of Mexico continental slope, supporting the hypothesis of hydrate formation driven by enhanced organic carbon burial during glacial lowstands.

Water retention curve for hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Dai, Sheng; Santamarina, J. Carlos

2013-11-01

water retention curve plays a central role in numerical algorithms that model hydrate dissociation in sediments. The determination of the water retention curve for hydrate-bearing sediments faces experimental difficulties, and most studies assume constant water retention curves regardless of hydrate saturation. This study employs network model simulation to investigate the water retention curve for hydrate-bearing sediments. Results show that (1) hydrate in pores shifts the curve to higher capillary pressures and the air entry pressure increases as a power function of hydrate saturation; (2) the air entry pressure is lower in sediments with patchy rather than distributed hydrate, with higher pore size variation and pore connectivity or with lower specimen slenderness along the flow direction; and (3) smaller specimens render higher variance in computed water retention curves, especially at high water saturation Sw > 0.7. Results are relevant to other sediment pore processes such as bioclogging and mineral precipitation.

Roles of Sodium Dodecyl Sulfate on Tetrahydrofuran-Assisted Methane Hydrate Formation.

PubMed

Siangsai, Atsadawuth; Inkong, Katipot; Kulprathipanja, Santi; Kitiyanan, Boonyarach; Rangsunvigit, Pramoch

2018-06-01

Sodium dodecyl sulfate (SDS) markedly improved tetrahydrofuran (THF) - assisted methane hydrate formation. Firstly, methane hydrate formation with different THF amount, 1, 3, and 5.56 mol%, was studied. SDS with 1, 4, and 8 mM was then investigated for its roles on the methane hydrate formation with and without THF. The experiments were conducted in a quiescent condition in a fixed volume crystallizer at 8 MPa and 4°C. The results showed that almost all studied THF and SDS concentrations enhanced the methane hydrate formation kinetics and methane consumption compared to that without the promoters, except 1 mol% THF. Although, with 1 mol% THF, there were no hydrates formed for 48 hours, the addition of just 1 mM SDS surprisingly promoted the hydrate formation with a significant increased in the kinetics. This prompts the use of methane hydrate technology for natural gas storage application with minimal promoters.

Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation

PubMed Central

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Park, Da-Hye; Han, Kunwoo; Lee, Kun-Hong

2013-01-01

As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media. PMID:23938301

Formation and decomposition of ethane, propane, and carbon dioxide hydrates in silica gel mesopores under high pressure.

PubMed

Aladko, E Ya; Dyadin, Yu A; Fenelonov, V B; Larionov, E G; Manakov, A Yu; Mel'gunov, M S; Zhurko, F V

2006-10-05

The experimental data on decomposition temperatures for the gas hydrates of ethane, propane, and carbon dioxide dispersed in silica gel mesopores are reported. The studies were performed at pressures up to 1 GPa. It is shown that the experimental dependence of hydrate decomposition temperature on the size of pores that limit the size of hydrate particles can be described on the basis of the Gibbs-Thomson equation only if one takes into account changes in the shape coefficient that is present in the equation; in turn, the value of this coefficient depends on a method of mesopore size determination. A mechanism of hydrate formation in mesoporous medium is proposed. Experimental data providing evidence of the possibility of the formation of hydrate compounds in hydrophobic matrixes under high pressure are reported. Decomposition temperature of those hydrate compounds is higher than that for the bulk hydrates of the corresponding gases.

Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

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

McConnell, Dan

Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydratesmore » and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.« less

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.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

β-Subunits of the SnRK1 Complexes Share a Common Ancestral Function Together with Expression and Function Specificities; Physical Interaction with Nitrate Reductase Specifically Occurs via AKINβ1-Subunit1[C][OA

PubMed Central

Polge, Cécile; Jossier, Mathieu; Crozet, Pierre; Gissot, Lionel; Thomas, Martine

2008-01-01

The SNF1/AMPK/SnRK1 kinases are evolutionary conserved kinases involved in yeast, mammals, and plants in the control of energy balance. These heterotrimeric enzymes are composed of one α-type catalytic subunit and two γ- and β-type regulatory subunits. In yeast it has been proposed that the β-type subunits regulate both the localization of the kinase complexes within the cell and the interaction of the kinases with their targets. In this work, we demonstrate that the three β-type subunits of Arabidopsis (Arabidopsis thaliana; AKINβ1, AKINβ2, and AKINβ3) restore the growth phenotype of the yeast sip1Δsip2Δgal83Δ triple mutant, thus suggesting the conservation of an ancestral function. Expression analyses, using AKINβ promoter∷β-glucuronidase transgenic lines, reveal different and specific patterns of expression for each subunit according to organs, developmental stages, and environmental conditions. Finally, our results show that the β-type subunits are involved in the specificity of interaction of the kinase with the cytosolic nitrate reductase. Together with previous cell-free phosphorylation data, they strongly support the proposal that nitrate reductase is a real target of SnRK1 in the physiological context. Altogether our data suggest the conservation of ancestral basic function(s) together with specialized functions for each β-type subunit in plants. PMID:18768910

Trimethyl chitosan-capped silver nanoparticles with positive surface charge: Their catalytic activity and antibacterial spectrum including multidrug-resistant strains of Acinetobacter baumannii.

PubMed

Chang, T Y; Chen, C C; Cheng, K M; Chin, C Y; Chen, Y H; Chen, X A; Sun, J R; Young, J J; Chiueh, T S

2017-07-01

We report a facile route for the green synthesis of trimethyl chitosan nitrate-capped silver nanoparticles (TMCN-AgNPs) with positive surface charge. In this synthesis, silver nitrate, glucose, and trimethyl chitosan nitrate (TMCN) were used as silver precursor, reducing agent, and stabilizer, respectively. The reaction was carried out in a stirred basic aqueous medium at room temperature without the use of energy-consuming or expensive equipment. We investigated the effects of the concentrations of NaOH, glucose, and TMCN on the particle size, zeta potential, and formation yield. The AgNPs were characterized by UV-vis spectroscopy, photon correlation spectroscopy, laser Doppler anemometry, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalytic activity of the TMCN-AgNPs was studied by the reduction of 4-nitrophenol using NaBH 4 as a reducing agent. We evaluated the antibacterial effects of the TMCN-AgNPs on Acinetobacter baumannii, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus using the broth microdilution method. The results showed that both gram-positive and gram-negative bacteria were killed by the TMCN-AgNPs at very low concentration (<6.13μg/mL). Moreover, the TMCN-AgNPs also showed high antibacterial activity against clinically isolated multidrug-resistant A. baumannii strains, and the minimum inhibitory concentration (MIC) was ≤12.25μg/mL. Copyright © 2017 Elsevier B.V. All rights reserved.

Gas hydrate saturation from acoustic impedance and resistivity logs in the shenhu area, south china sea

USGS Publications Warehouse

Wang, X.; Wu, S.; Lee, M.; Guo, Y.; Yang, S.; Liang, J.

2011-01-01

During the China's first gas hydrate drilling expedition -1 (GMGS-1), gas hydrate was discovered in layers ranging from 10 to 25 m above the base of gas hydrate stability zone in the Shenhu area, South China Sea. Water chemistry, electrical resistivity logs, and acoustic impedance were used to estimate gas hydrate saturations. Gas hydrate saturations estimated from the chloride concentrations range from 0 to 43% of the pore space. The higher gas hydrate saturations were present in the depth from 152 to 177 m at site SH7 and from 190 to 225 m at site SH2, respectively. Gas hydrate saturations estimated from the resistivity using Archie equation have similar trends to those from chloride concentrations. To examine the variability of gas hydrate saturations away from the wells, acoustic impedances calculated from the 3 D seismic data using constrained sparse inversion method were used. Well logs acquired at site SH7 were incorporated into the inversion by establishing a relation between the water-filled porosity, calculated using gas hydrate saturations estimated from the resistivity logs, and the acoustic impedance, calculated from density and velocity logs. Gas hydrate saturations estimated from acoustic impedance of seismic data are ???10-23% of the pore space and are comparable to those estimated from the well logs. The uncertainties in estimated gas hydrate saturations from seismic acoustic impedances were mainly from uncertainties associated with inverted acoustic impedance, the empirical relation between the water-filled porosities and acoustic impedances, and assumed background resistivity. ?? 2011 Elsevier Ltd.

Theoretical modeling insights into elastic wave attenuation mechanisms in marine sediments with pore-filling methane hydrate

NASA Astrophysics Data System (ADS)

Marín-Moreno, H.; Sahoo, S. K.; Best, A. I.

2017-03-01

The majority of presently exploitable marine methane hydrate reservoirs are likely to host hydrate in disseminated form in coarse grain sediments. For hydrate concentrations below 25-40%, disseminated or pore-filling hydrate does not increase elastic frame moduli, thus making impotent traditional seismic velocity-based methods. Here, we present a theoretical model to calculate frequency-dependent P and S wave velocity and attenuation of an effective porous medium composed of solid mineral grains, methane hydrate, methane gas, and water. The model considers elastic wave energy losses caused by local viscous flow both (i) between fluid inclusions in hydrate and pores and (ii) between different aspect ratio pores (created when hydrate grows); the inertial motion of the frame with respect to the pore fluid (Biot's type fluid flow); and gas bubble damping. The sole presence of pore-filling hydrate in the sediment reduces the available porosity and intrinsic permeability of the sediment affecting Biot's type attenuation at high frequencies. Our model shows that attenuation maxima due to fluid inclusions in hydrate are possible over the entire frequency range of interest to exploration seismology (1-106 Hz), depending on the aspect ratio of the inclusions, whereas maxima due to different aspect ratio pores occur only at sonic to ultrasound frequencies (104-106 Hz). This frequency response imposes further constraints on possible hydrate saturations able to reproduce broadband elastic measurements of velocity and attenuation. Our results provide a physical basis for detecting the presence and amount of pore-filling hydrate in seafloor sediments using conventional seismic surveys.

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.

Brookian sequence well log correlation sections and occurrence of gas hydrates, north-central North Slope, Alaska

USGS Publications Warehouse

Lewis, Kristen A.; Collett, Timothy S.

2013-01-01

Gas hydrates are naturally occurring crystalline, ice-like substances that consist of natural gas molecules trapped in a solid-water lattice. Because of the compact nature of their structure, hydrates can effectively store large volumes of gas and, consequently, have been identified as a potential unconventional energy source. First recognized to exist geologically in the 1960s, significant accumulations of gas hydrate have been found throughout the world. Gas hydrate occurrence is limited to environments such as permafrost regions and subsea sediments because of the pressure and temperature conditions required for their formation and stability. Permafrost-associated gas hydrate accumulations have been discovered in many regions of the Arctic, including Russia, Canada, and the North Slope of Alaska. Gas hydrate research has a long history in northern Alaska. This research includes the drilling, coring, and well log evaluation of two gas hydrate stratigraphic test wells and two resource assessments of gas hydrates on the Alaska North Slope. Building upon these previous investigations, this report provides a summary of the pertinent well log, gas hydrate, and stratigraphic data for key wells related to gas hydrate occurrence in the north-central North Slope. The data are presented in nine well log correlation sections with 122 selected wells to provide a regional context for gas hydrate accumulations and the relation of the accumulations to key stratigraphic horizons and to the base of the ice-bearing permafrost. Also included is a well log database that lists the location, available well logs, depths, and other pertinent information for each of the wells on the correlation section.

Consequences of CO2 solubility for hydrate formation from carbon dioxide containing water and other impurities.

PubMed

Kvamme, Bjørn; Kuznetsova, Tatiana; Jensen, Bjørnar; Stensholt, Sigvat; Bauman, Jordan; Sjøblom, Sara; Nes Lervik, Kim

2014-05-14

Deciding on the upper bound of water content permissible in a stream of dense carbon dioxide under pipeline transport conditions without facing the risks of hydrate formation is a complex issue. In this work, we outline and analyze ten primary routes of hydrate formation inside a rusty pipeline, with hydrogen sulfide, methane, argon, and nitrogen as additional impurities. A comprehensive treatment of equilibrium absolute thermodynamics as applied to multiple hydrate phase transitions is provided. We also discuss in detail the implications of the Gibbs phase rule that make it necessary to consider non-equilibrium thermodynamics. The analysis of hydrate formation risk has been revised for the dominant routes, including the one traditionally considered in industrial practice and hydrate calculators. The application of absolute thermodynamics with parameters derived from atomistic simulations leads to several important conclusions regarding the impact of hydrogen sulfide. When present at studied concentrations below 5 mol%, the presence of hydrogen sulfide will only support the carbon-dioxide-dominated hydrate formation on the phase interface between liquid water and hydrate formers entering from the carbon dioxide phase. This is in contrast to a homogeneous hydrate nucleation and growth inside the aqueous solution bulk. Our case studies indicate that hydrogen sulfide at higher than 0.1 mol% concentration in carbon dioxide can lead to growth of multiple hydrate phases immediately adjacent to the adsorbed water layers. We conclude that hydrate formation via water adsorption on rusty pipeline walls will be the dominant contributor to the hydrate formation risk, with initial concentration of hydrogen sulfide being the critical factor.

Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

DOE PAGES

Calero, Carles; Stanley, H.; Franzese, Giancarlo

2016-04-27

Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs). We calculate the rotational and translational slowdown of the dynamics of water confinedmore » in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i) to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii) to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii) to the higher probability of water–lipid HBs as the hydration decreases. Lastly, our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.« less

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.

Fracturing Behavior of Methane-Hydrate-Bearing Sediment

NASA Astrophysics Data System (ADS)

Konno, Y.; Jin, Y.; Yoneda, J.; Uchiumi, T.; Shinjou, K.; Nagao, J.

2016-12-01

As a part of a Japanese national hydrate research program (MH21, funded by the Ministry of Economy, Trade, and Industry), we performed laboratory experiments of hydraulic fracturing in methane-hydrate-bearing sediment. Distilled water was injected into methane-hydrate-bearing sand which was artificially made in a tri-axial pressure cell. X-ray computed tomography revealed that tensile failure was occurred after a rapid drop in the injection pressure. It was found that generated fractures cause a significant increase in the effective water permeability of hydrate-bearing sand. The result contributes fundamental understanding of the accumulation mechanism of gas hydrates in sediments and shows that hydraulic fracturing is one of promising enhanced recovery methods for low-permeable gas hydrate reservoirs.

Electronic structure and magnetic properties of the strong-rung spin-1 ladder compound Rb3Ni2(NO3)7

NASA Astrophysics Data System (ADS)

Pchelkina, Z. V.; Mazurenko, V. V.; Volkova, O. S.; Deeva, E. B.; Morozov, I. V.; Shutov, V. V.; Troyanov, S. I.; Werner, J.; Koo, C.; Klingeler, R.; Vasiliev, A. N.

2018-04-01

Rb3Ni2(NO3)7 was obtained by crystallization from anhydrous nitric acid solution of rubidium nitrate and nickel nitrate hexahydrate. The crystal structure determined on single crystals implies isolated spin-1 two-leg ladders of Ni2 + ions connected by (NO3)- groups as basic elements. Magnetic susceptibility, specific heat in magnetic fields up to 9 T, magnetization, and high-frequency electron spin resonance studies performed on powder samples show the absence of long-range magnetic order at T ≥2 K. Electronic structure calculations and the detailed analysis of the experimental data enable quantitative estimates of the relevant parameters of the S =1 ladders in Rb3Ni2(NO3)7 . The rung coupling J1=10.16 K, the leg coupling J2=1.5 K, and the Ising-type anisotropy |A |=8.6 K are obtained. The scenario of a valence-bond solidlike quantum ground state realized in the two-leg Ni2 + ladders is further corroborated by model simulations of the magnetic susceptibility.

Bio-reduction of free and laden perchlorate by the pure and mixed perchlorate reducing bacteria: Considering the pH and coexisting nitrate.

PubMed

Shang, Yanan; Wang, Ziyang; Xu, Xing; Gao, Baoyu; Ren, Zhongfei

2018-08-01

Pure bacteria cell (Azospira sp. KJ) and mixed perchlorate reducing bacteria (MPRB) were employed for decomposing the free perchlorate in water as well as the laden perchlorate on surface of quaternary ammonium wheat residuals (QAWR). Results indicated that perchlorate was decomposed by the Azospira sp. KJ prior to nitrate while MPRB was just the reverse. Bio-reduction of laden perchlorate by Azospira sp. KJ was optimal at pH 8.0. In contrast, bio-reduction of laden perchlorate by MPRB was optimal at pH 7.0. Generally, the rate of perchlorate reduction was controlled by the enzyme activity of PRB. In addition, perchlorate recovery (26.0 mg/g) onto bio-regenerated QAWR by MPRB was observed with a small decrease as compared with that (31.1 mg/g) by Azospira sp. KJ at first 48 h. Basically, this study is expected to offer some different ideas on bio-regeneration of perchlorate-saturated adsorbents using biological process, which may provide the economically alternative to conventional methods. Copyright © 2018 Elsevier Ltd. All rights reserved.

A novel method to delaminate nitrate-intercalated MgAl layered double hydroxides in water and application in heavy metals removal from waste water.

PubMed

Rahman, Mir Tamzid; Kameda, Tomohito; Kumagai, Shogo; Yoshioka, Toshiaki

2018-07-01

Nitrate-intercalated MgAl layered double hydroxide (LDH) was successfully delaminated in water by a facile and effective method upon reflux at 120 °C for 24 h followed by sonication at 40 °C for 5 h. This process is environmentally friendly since water is the only solvent used. The delaminated nanosheets were characterized by microscopic, spectroscopic, and particle size analyses. The delamination process successfully produced octahedron-shaped single-layer nanosheets 50-150 nm in size. X-ray photoelectron spectroscopy (XPS) data confirmed that the surface elements and their chemical status are consistent with the basic layer of MgAl LDH. The delaminated nanosheets displayed higher adsorption capacity for removing heavy metals from waste water than the original powdered LDH. After treating the waste water, a sharp and intense peak in the X-ray powder diffraction (XRD) pattern of the precipitate confirms the restacking of the LDH nanosheets. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

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

Mamontov, Eugene

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

A primer on the geological occurrence of gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.

1998-01-01

This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert).Natural gas hydrates occur world-wide in polar regions, usually associated with onshore and offshore permafrost, and in sediment of outer continental and insular margins. The total amount of methane in gas hydrates probably exceeds 1019 g of methane carbon. Three aspects of gas hydrates are important: their fossil fuel resource potential; their role as a submarine geohazard; and their effects on global climate change. Because gas hydrates represent a large amount of methane within 2000 m of the Earth's surface, they are considered to be an unconventional, unproven source of fossil fuel. Because gas hydrates are metastable, changes of pressure and temperature affect their stability. Destabilized gas hydrates beneath the sea floor lead to geological hazards such as submarine slumps and slides, examples of which are found world-wide. Destabilized gas hydrates may also affect climate through the release of methane, a 'greenhouse' gas, which may enhance global warming and be a factor in global climate change.

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.

Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311: indications for heterogeneous compositions in hydrate crystals.

PubMed

Schicks, J M; Ziemann, M A; Lu, H; Ripmeester, J A

2010-12-01

Natural gas hydrates usually are found in the form of structure I, encasing predominantly methane in the hydrate lattices as guest molecules, sometimes also minor amount of higher hydrocarbons, CO2 or H2S. Raman spectroscopy is an approved tool to determine the composition of the hydrate phase. Thus, in this study Raman spectroscopic analyses have been applied to hydrate samples obtained from Integrated Ocean Drilling Program (IODP) Expedition 311 in two different approaches: studying the samples randomly taken from the hydrate core, and--as a new application--mapping small areas on the surface of clear hydrate crystals. The results obtained imply that the gas composition of hydrate, in terms of relative concentrations of CH4 and H2S, is not homogeneous over a core or even within a crystal. The mapping method yielded results with very high lateral resolution, indicating the coexistence of different phases with the same structure but different compositions within a hydrate crystal. Copyright © 2010 Elsevier B.V. All rights reserved.

New hydrate formation methods in a liquid-gas medium

NASA Astrophysics Data System (ADS)

Chernov, A. A.; Pil'Nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

New hydrate formation methods in a liquid-gas medium.

PubMed

Chernov, A A; Pil'nik, A A; Elistratov, D S; Mezentsev, I V; Meleshkin, A V; Bartashevich, M V; Vlasenko, M G

2017-01-18

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

DOE PAGES

Mamontov, Eugene

2017-05-24

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

Gas Hydrate Estimation Using Rock Physics Modeling and Seismic Inversion

NASA Astrophysics Data System (ADS)

Dai, J.; Dutta, N.; Xu, H.

2006-05-01

ABSTRACT We conducted a theoretical study of the effects of gas hydrate saturation on the acoustic properties (P- and S- wave velocities, and bulk density) of host rocks, using wireline log data from the Mallik wells in the Mackenzie Delta in Northern Canada. We evaluated a number of gas hydrate rock physics models that correspond to different rock textures. Our study shows that, among the existing rock physics models, the one that treats gas hydrate as part of the solid matrix best fits the measured data. This model was also tested on gas hydrate hole 995B of ODP leg 164 drilling at Blake Ridge, which shows adequate match. Based on the understanding of rock models of gas hydrates and properties of shallow sediments, we define a procedure that quantifies gas hydrate using rock physics modeling and seismic inversion. The method allows us to estimate gas hydrate directly from seismic information only. This paper will show examples of gas hydrates quantification from both 1D profile and 3D volume in the deepwater of Gulf of Mexico.

Models for Gas Hydrate-Bearing Sediments Inferred from Hydraulic Permeability and Elastic Velocities

USGS Publications Warehouse

Lee, Myung W.

2008-01-01

Elastic velocities and hydraulic permeability of gas hydrate-bearing sediments strongly depend on how gas hydrate accumulates in pore spaces and various gas hydrate accumulation models are proposed to predict physical property changes due to gas hydrate concentrations. Elastic velocities and permeability predicted from a cementation model differ noticeably from those from a pore-filling model. A nuclear magnetic resonance (NMR) log provides in-situ water-filled porosity and hydraulic permeability of gas hydrate-bearing sediments. To test the two competing models, the NMR log along with conventional logs such as velocity and resistivity logs acquired at the Mallik 5L-38 well, Mackenzie Delta, Canada, were analyzed. When the clay content is less than about 12 percent, the NMR porosity is 'accurate' and the gas hydrate concentrations from the NMR log are comparable to those estimated from an electrical resistivity log. The variation of elastic velocities and relative permeability with respect to the gas hydrate concentration indicates that the dominant effect of gas hydrate in the pore space is the pore-filling characteristic.

New hydrate formation methods in a liquid-gas medium

PubMed Central

Chernov, A. A.; Pil’nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated. PMID:28098194

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.

2016-04-01

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

Exploring the synthesis and characterization of nanoenergetic materials from sol-gel chemistry

NASA Astrophysics Data System (ADS)

Walker, Jeremy D.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed 'proton scavenging' mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. Gelation mechanisms for the formation of FeIIIxOyHz from THF and pyridine have been presented and confirmed through pH, XPS, and IR studies. THF follows a similar mechanism as PO, where the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide, which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Energetic properties for the Fe2O3/Al and RuO 2/Al sol-gel synthesized systems are also presented. Sol-gel chemistry synthesizes x-ray amorphous oxide matrices which contain substantial quantities of residual water and organic species. The iron (III) matrix, formed from the addition of a weak base epoxide molecule to a hydrated iron (III) nitrate solution, consists of stoichiometric Fe2O3, FeO(OH), and Fe(OH)3 and can only definitely be described as of Fe IIIxOyHz. XPS characterization of the metal oxide matrix synthesized from the addition of the weak base propylene oxide to a hydrated ruthenium (III) chloride solution corresponds to that of hydrous ruthenium (IV) oxide. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Energetic systems formed from each epoxide were each synthesized with different components, including: varying concentrations of nano-scale Al, micron Al, and carbon nanotubes. Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide surface area available for contact with the aluminum particles. Also, within systems, 1:1 Fe:nano Al samples possess the highest heat of reaction. Samples with nano-scale Al particles start reaction at 430°C, before the melting point of Al, whereas samples containing micron-Al do not react until ˜800°C, after the melting point of Al. The RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles. This results in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al. Post-reaction analysis of these samples reveals the sole existence of ruthenium (IV) oxide as the exothermic reaction vaporizes the aluminum particles.

Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRH-Theory): three-dimensional PC validation

NASA Astrophysics Data System (ADS)

Kadyshevich, E. A.; Dzyabchenko, A. V.; Ostrovskii, V. E.

2014-04-01

Size compatibility of the CH4-hydrate structure II and multi-component DNA fragments is confirmed by three-dimensional simulation; it is validation of the Life Origination Hydrate Theory (LOH-Theory).

Natural gas hydrates; vast resource, uncertain future

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Gas hydrates are naturally occurring icelike solids in which water molecules trap gas molecules in a cagelike structure known as a clathrate. Although many gases form hydrates in nature, methane hydrate is by far the most common; methane is the most abundant natural gas. The volume of carbon contained in methane hydrates worldwide is estimated to be twice the amount contained in all fossil fuels on Earth, including coal.

Hydration reactivity of crystalline and vitrified diopside under hydrothermal conditions

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

Grzeszczyk, S.; Szuba, J.

1990-07-01

Hydration reactivity of diopside in both the crystalline and amorphous (glassy) phase was studied under hydrothermal conditions. Samples were treated in an autoclave at 200{degrees}C in saturated vapor for 24 and 72 h. The progress of hydration was determined by X-ray powder diffractometry and IR spectroscopy. Results indicate that crystalline diopside possessed poor hydraulic activity. However, once vitrified it proved to be much more reactive. The principal hydration products found for the glassy diopside after 24 and 72 h of treatment were calcium silicate hydrate (xonotlite) and magnesium silicate hydrates (chrysotile and tremolite).

Gas hydrates from the continental slope, offshore Sakhalin Island, Okhotsk Sea

USGS Publications Warehouse

Ginsburg, G.D.; Soloviev, V.A.; Cranston, R.E.; Lorenson, T.D.; Kvenvolden, K.A.

1993-01-01

Ten gas-vent fields were discovered in the Okhotsk Sea on the northeast continental slope offshore from Sakhalin Island in water depths of 620-1040 m. At one vent field, estimated to be more than 250 m across, gas hydrates, containing mainly microbial methane (??13C = -64.3???), were recovered from subbottom depths of 0.3-1.2 m. The sediment, having lenses and bedded layers of gas hydrate, contained 30-40% hydrate per volume of wet sediment. Although gas hydrates were not recovered at other fields, geochemical and thermal measurements suggest that gas hydrates are present. ?? 1993 Springer-Verlag.

Results at Mallik highlight progress in gas hydrate energy resource research and development

USGS Publications Warehouse

Collett, T.S.

2005-01-01

The recent studies that project the role of gas hydrates in the future energy resource management are reviewed. Researchers have long speculated that gas hydrates could eventually be a commercial resource for the future. A Joint Industry Project led by ChevronTexaco and the US Department of Energy is designed to characterize gas hydrates in the Gulf of Mexico. Countries including Japan, canada, and India have established large gas hydrate research and development projects, while China, Korea and Mexico are investigating the viability of forming government-sponsored gas hydrate research projects.

The analysis of magnesium oxide hydration in three-phase reaction system

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

Tang, Xiaojia; Guo, Lin; Chen, Chen

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phasemore » system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.« less

Quantitative assessment of combination bathing and moisturizing regimens on skin hydration in atopic dermatitis.

PubMed

Chiang, Charles; Eichenfield, Lawrence F

2009-01-01

Standard recommendations for skin care for patients with atopic dermatitis stress the importance of skin hydration and the application of moisturizers. However, objective data to guide recommendations regarding the optimal practice methods of bathing and emollient application are scarce. This study quantified cutaneous hydration status after various combination bathing and moisturizing regimens. Four bathing/moisturizer regimens were evaluated in 10 subjects, five pediatric subjects with atopic dermatitis and five subjects with healthy skin. The regimens consisted of bathing alone without emollient application, bathing and immediate emollient application, bathing and delayed application, and emollient application alone. Each regimen was evaluated in all subjects, utilizing a crossover design. Skin hydration was assessed with standard capacitance measurements. In atopic dermatitis subjects, emollient alone yielded a significantly (p < 0.05) greater mean hydration over 90 minutes (206.2% baseline hydration) than bathing with immediate emollient (141.6%), bathing and delayed emollient (141%), and bathing alone (91.4%). The combination bathing and emollient application regimens demonstrated hydration values at 90 minutes not significantly greater than baseline. Atopic dermatitis subjects had a decreased mean hydration benefit compared with normal skin subjects. Bathing without moisturizer may compromise skin hydration. Bathing followed by moisturizer application provides modest hydration benefits, though less than that of simply applying moisturizer alone.

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

PubMed

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Modeling of acoustic wave dissipation in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Guerin, Gilles; Goldberg, David

2005-07-01

Recent sonic and seismic data in gas hydrate-bearing sediments have indicated strong waveform attenuation associated with a velocity increase, in apparent contradiction with conventional wave propagation theory. Understanding the reasons for such energy dissipation could help constrain the distribution and the amounts of gas hydrate worldwide from the identification of low amplitudes in seismic surveys. A review of existing models for wave propagation in frozen porous media, all based on Biot's theory, shows that previous formulations fail to predict any significant attenuation with increasing hydrate content. By adding physically based components to these models, such as cementation by elastic shear coupling, friction between the solid phases, and squirt flow, we are able to predict an attenuation increase associated with gas hydrate formation. The results of the model agree well with the sonic logging data recorded in the Mallik 5L-38 Gas Hydrate Research Well. Cementation between gas hydrate and the sediment grains is responsible for the increase in shear velocity. The primary mode of energy dissipation is found to be friction between gas hydrate and the sediment matrix, combined with an absence of inertial coupling between gas hydrate and the pore fluid. These results predict similar attenuation increase in hydrate-bearing formations over most of the sonic and seismic frequency range.

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.

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.

A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

PubMed Central

Jo, Byung-Wan; Chakraborty, Sumit

2015-01-01

To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

Experimental investigation of gas hydrate formation, plugging and transportability in partially dispersed and water continuous systems

NASA Astrophysics Data System (ADS)

Vijayamohan, Prithvi

As oil/gas subsea fields mature, the amount of water produced increases significantly due to the production methods employed to enhance the recovery of oil. This is true especially in the case of oil reservoirs. This increase in the water hold up increases the risk of hydrate plug formation in the pipelines, thereby resulting in higher inhibition cost strategies. A major industry concern is to reduce the severe safety risks associated with hydrate plug formation, and significantly extending subsea tieback distances by providing a cost effective flow assurance management/safety tool for mature fields. Developing fundamental understanding of the key mechanistic steps towards hydrate plug formation for different multiphase flow conditions is a key challenge to the flow assurance community. Such understanding can ultimately provide new insight and hydrate management guidelines to diminish the safety risks due to hydrate formation and accumulation in deepwater flowlines and facilities. The transportability of hydrates in pipelines is a function of the operating parameters, such as temperature, pressure, fluid mixture velocity, liquid loading, and fluid system characteristics. Specifically, the hydrate formation rate and plugging onset characteristics can be significantly different for water continuous, oil continuous, and partially dispersed systems. The latter is defined as a system containing oil/gas/water, where the water is present both as a free phase and partially dispersed in the oil phase (i.e., entrained water in the oil). Since hydrate formation from oil dispersed in water systems and partially dispersed water systems is an area which is poorly understood, this thesis aims to address some key questions in these systems. Selected experiments have been performed at the University of Tulsa flowloop to study the hydrate formation and plugging characteristics for the partially dispersed water/oil/gas systems as well as systems where the oil is completely dispersed in water. These experiments indicate that the partially dispersed systems tend to be problematic and are more severe cases with respect to flow assurance when compared to systems where the water is completely dispersed in oil. We have found that the partially dispersed systems are distinct, and are not an intermediate case between water dominated, and water-in-oil emulsified systems. Instead the experiments indicate that the hydrate formation and plugging mechanism for these systems are very complex. Hydrate growth is very rapid for such systems when compared to 100% water cut systems. The plugging mechanism for these systems is a combination of various phenomena (wall growth, agglomeration, bedding/settling, etc). Three different oils with different viscosities have been used to investigate the transportability of hydrates with respect to oil properties. The experiments indicate that the transportability of hydrates increases with increase in oil viscosity. The data from the tests performed provide the basis for a mechanistic model for hydrate formation and plugging in partially dispersed systems. It is found that in systems that were in stratified flow regime before hydrate onset, the hydrates eventually settled on the pipe walls thereby decreasing the flow area for the flow of fluids. In systems that were in the slug flow regime before hydrate formation, moving beds of hydrates were the main cause for plugging. In both the flow regimes, the systems studied entered a plugging regime beyond a certain hydrate concentration. This is termed as φplugging onset and can be used as an indicator to calculate the amount of hydrates that can be transported safely without requiring any additional treatment for a given set of flow characteristics. A correlation to calculate this hydrate concentration based on easily accessible parameters is developed in terms of flow characteristics and oil properties. The work performed in this thesis has enhanced the understanding of the hydrate plug mechanism in pipelines having high amounts of water. This work has also shown the effect of hydrate formation in different flow regimes thereby shedding light on the effects of hydrates on multiphase flow and vice versa. Lessons resulting from this work could be incorporated into flow assurance models, as well as operating company production strategies to reduce or mitigate hydrate plugging risks in complex multiphase systems.

Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2011-12-01

Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. 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. 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. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it 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, liquid CO2, 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 simulation of 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. This paper describes and demonstrates a numerical solution scheme for ternary hydrate systems that seeks a balance between accuracy and computational efficiency. This scheme uses a generalize cubic equation of state, functional forms for the hydrate equilibria and cage occupancies, variable switching scheme for phase transitions, and kinetic exchange of hydrate formers (i.e., CH4, CO2, and N2) between the mobile phases (i.e., aqueous, liquid CO2, and gas) and hydrate phase. Accuracy of the scheme will be evaluated by comparing property values and phase equilibria against experimental data. Computational efficiency of the scheme will be evaluated by comparing the base scheme against variants. The application of interest will 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.

Detection and Production of Methane Hydrate

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

George Hirasaki; Walter Chapman; Gerald Dickens

This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remotemore » quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand processes that control production potential of hydrates in marine settings, Mallik was included because of the extensive data collected in a producible hydrate accumulation. To date, such a location had not been studied in the oceanic environment. The project worked closely with ongoing projects (e.g. GOM JIP and offshore India) that are actively investigating potentially economic hydrate accumulations in marine settings. The overall approach was fivefold: (1) collect key data concerning hydrocarbon fluxes which is currently missing at all locations to be included in the study, (2) use this and existing data to build numerical models that can explain gas hydrate variance at all four locations, (3) simulate how natural gas could be produced from each location with different production strategies, (4) collect new sediment property data at these locations that are required for constraining fluxes, production simulations and assessing sediment stability, and (5) develop a method for remotely quantifying heterogeneities in gas hydrate and free gas distributions. While we generally restricted our efforts to the locations where key parameters can be measured or constrained, our ultimate aim was to make our efforts universally applicable to any hydrate accumulation.« less

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.

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.

Efficacy of oral hydration in the prevention of contrast-induced acute kidney injury in patients undergoing coronary angiography or intervention.

PubMed

Akyuz, Sukru; Karaca, Mehmet; Kemaloglu Oz, Tugba; Altay, Servet; Gungor, Baris; Yaylak, Baris; Yazici, Selcuk; Ozden, Kivilcim; Karakus, Gultekin; Cam, Nese

2014-01-01

Efficacy of intravenous (IV) volume expansion in preventing contrast-induced acute kidney injury (CI-AKI) is well known. However, the role of oral hydration has not been well established. The aim of this work was to evaluate the efficacy of oral hydration in preventing CI-AKI. We prospectively randomized 225 patients undergoing coronary angiography and/or percutaneous coronary intervention in either oral hydration or IV hydration groups. Patients who have at least one of the high-risk factors for developing CI-AKI (advanced age, type 2 diabetes mellitus, anemia, hyperuricemia, a history of cardiac failure or systolic dysfunction) were included in the study. All patients had normal renal function or stage 1-2 chronic kidney disease. Patients in the oral hydration group were encouraged to drink unrestricted amounts of fluids freely whereas isotonic saline infusion was performed by the standard protocol in the IV hydration group. CI-AKI occurred in 8/116 patients (6.9%) in the oral hydration group and 8/109 patients (7.3%) in the IV hydration group (p = 0.89). There was also no statistically significant difference between the two groups when different CI-AKI definitions were taken into account. Oral hydration is as effective as IV hydration in preventing CI-AKI in patients with normal kidney function or stage 1-2 chronic kidney disease, and who also have at least one of the other high-risk factors for developing CI-AKI. © 2014 S. Karger AG, Basel.

Stress and Dilatancy Relation of Methane Hydrate Bearing Sand with Various Fines Content

NASA Astrophysics Data System (ADS)

Hyodo, M.

2016-12-01

This study presents an experimental and numerical study on the shear behaviour of methane hydrate bearing sand with variable confining pressures and methane hydrate saturations. A representative grading curve of Nankai Trough is selected as the grain size distribution of host sand to artificially produce the methane hydrate bearing sand. A shear strength estimation equation for methane hydrate bearing sand from test results is established. A simple constitutive model has been proposed to predict the stress-strain response of methane hydrate bearing sand based on a few well-known relationships. Experimental results indicate that the inclination of stress-dilatancy curve becomes steeper with a rise in methane hydrate saturation. A revised stress-dilatancy equation has been integrated with this simple model to consider the variance in the inclination of stress-dilatancy curve. The mean stress Pcr at critical state when the peak stress ratio reduces to the residual stress ratio increases with the level of methane hydrate saturation. The dilatancy parameter a tends to increase with the methane hydrate saturation. The shear deformability parameter A exhibits a decreasing tendency with the rise in methane hydrate saturation at each confining pressure. This model is capable of reasonably predicting the strength and stiffness enhancement and the dilation behaviour as methane hydrate saturation increases. The volumetric variation from contraction to expansion of MH bearing sand at a lower confining pressure and only pure volumetric contraction a higher confining pressure can be represented by this simple model.

Water-wetting surfaces as hydrate promoters during transport of carbon dioxide with impurities.

PubMed

Kuznetsova, Tatiana; Jensen, Bjørnar; Kvamme, Bjørn; Sjøblom, Sara

2015-05-21

Water condensing as liquid drops within the fluid bulk has traditionally been the only scenario accepted in the industrial analysis of hydrate risks. We have applied a combination of absolute thermodynamics and molecular dynamics modeling to analyze the five primary routes of hydrate formation in a rusty pipeline carrying dense carbon dioxide with methane, hydrogen sulfide, argon, and nitrogen as additional impurities. We have revised the risk analysis of all possible routes in accordance with the combination of the first and the second laws of thermodynamics to determine the highest permissible content of water. It was found that at concentrations lower than five percent, hydrogen sulfide will only support the formation of carbon dioxide-dominated hydrate from adsorbed water and hydrate formers from carbon dioxide phase rather than formation in the aqueous phase. Our results indicate that hydrogen sulfide leaving carbon dioxide for the aqueous phase will be able to create an additional hydrate phase in the aqueous region adjacent to the first adsorbed water layer. The growth of hydrate from different phases will decrease the induction time by substantially reducing the kinetically limiting mass transport across the hydrate films. Hydrate formation via adsorption of water on rusty walls will play the decisive role in hydrate formation risk, with the initial concentration of hydrogen sulfide being the critical factor. We concluded that the safest way to eliminate hydrate risks is to ensure that the water content of carbon dioxide is low enough to prevent water dropout via the adsorption mechanism.