Science.gov

Sample records for acid hydrate abundance

  1. Correlation of Sulfuric Acid Hydrate Abundance with Charged Particle Flux at the Surface of Europa

    NASA Astrophysics Data System (ADS)

    Dalton, James B.; Paranicas, C. P.; Cassidy, T. A.; Shirley, J. H.

    2010-10-01

    The trailing hemisphere of Jupiter's moon Europa is bombarded by charged particles trapped within Jupiter's magnetosphere. Sulfur ion implantation and impacting energetic electrons strongly affect the surface chemistry of Europa. Understanding these processes is important for disentangling the extrinsic and intrinsic components of Europa's surface chemistry. In the sulfur cycle model of Carlson et al. (Science 286, 97, 1999), hydrated sulfuric acid represents the dominant reaction product of radiolytic surface modification processes on Europa. In recent compositional investigations employing linear mixture modeling, Dalton et al. (LPSC XV, #2511, 2009) and Shirley et al. (Icarus, in press, 2010) document a well-defined gradient of hydrated sulfuric acid abundance for a study area spanning the leading side - trailing side boundary in Argadnel Regio. Sulfuric acid hydrate abundance in this region increases toward the trailing side apex. Here we compare the derived sulfuric acid hydrate abundances at 41 locations on Europa's surface with independent model results describing 1) the sulfur ion flux (Hendrix et al., 2010, in preparation), and 2) the energetic electron flux, at the same locations. We improve upon the prior calculation of electron energy into the surface of Paranicas et al. (2009, in Europa, U. Arizona, p529; Pappalardo, McKinnon, & Khurana eds.) by incorporating a realistic pitch angle dependence of the distribution. While the sulfur ion implantation and electron energy deposition model distributions differ in important details, both show trailing side gradients similar to that found for the sulfuric acid hydrate. Correlation coefficients exceed 0.9 in comparisons of each of these models with the sulfuric acid hydrate distribution. Our results support models in which the electron energy flux drives reactions that utilize implanted sulfur to produce sulfuric acid hydrate. This work was performed at the California Institute of Technology-Jet Propulsion

  2. Inelastic Neutron Scattering of Nitric Acid Hydrates

    NASA Astrophysics Data System (ADS)

    Baloh, P.; Grothe, H.; Martín-Llorente, B.; Parker, S.

    2009-04-01

    The IPCC report 2007 underlines the particular importance of aerosol particles for the water cycle and the radiation balance, and thus for the global climate.[1] The contribution of aerosols and clouds to radiative forcing might be comparable to the most important greenhouse gases like CO2 but is comparatively less understood. Nitric acid hydrates are important constituents of solid cloud particles in the lower polar Stratosphere (Polar Stratospheric Clouds) and the upper Troposphere (Cirrus clouds). The exact phase composition of these particles is still a matter of controversial discussion.[2] Especially, metastable modifications have, as recent measurements show, a particular relevance for the atmosphere, which has been ignored up to now.[3] Spectroscopic data for their detection are urgently needed and can be gathered with laboratory models. Only recently we have recorded the FTIR and Raman spectra of all nitric acid hydrates, stable and metastable.[4,5] These data have been corroborated by X-ray diffraction measurements.[6] However, when interpreting the spectroscopic data it became evident that not all bands could be explained reasonably. Here, DFT calculations were extremely helpful,[7] but still the translational and librational bands were not fully understood. Hence, inelastic neutron scattering was employed in order to investigate this region. The INS measurements were carried out with the instrument TOSCA at the ISIS of the Rutherford Appleton Laboratory, UK. The samples were prepared ex-situ in an amorphous state and were transferred into a helium-bath-cryostat, where the sample has been annealed between 20 K and 220 K. Characteristic changes of translational and librational modes have been observed and have been correlated with phase transitions. [1] Intergovernmental Panel on Climate Change, 4th Assessment Report "Climate Change 2007: The Physical Science Basis, Summary for Policymakers", Geneva, 2007; www.ipcc.ch [2] H. Grothe, H. Tizek and I. K

  3. Carbon abundances, major element chemistry, and mineralogy of hydrated interplanetary dust particles

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Thomas, K. L.; Mckay, D. S.

    1993-01-01

    Hydrated interplanetary dust particles (IDP's) comprise a major fraction of the interplanetary dust particles collected in the stratosphere. While much is known about the mineralogy and chemistry of hydrated IDP's, little is known about the C abundance in this class of IDP's, the nature of the C-bearing phases, and how the C abundance is related to other physical properties of hydrated IDP's. Bulk compositional data (including C and O) for 11 hydrated IDP's that were subsequently examined by the transition electron microscopy (TEM) to determine their mineralogy and mineral chemistry are reported. Our analysis indicates that these hydrated IDP's are strongly enriched in C relative to the most C-rich meteorites. The average abundance of C in these hydrated IDP's is 4X CI chondrite values. The bulk compositions (including C and O) of 11 hydrated IDP's were determined by thin-window, energy-dispersive x ray (EDX) spectroscopy of the uncoated IDP's on Be substrates in the scanning electron microscopy (SEM). As a check on our C measurements, one of the IDP's (L2006H5) was embedded in glassy S, and microtome thin sections were prepared and placed onto Be substrates. Thin-film EDX analyses of multiple thin sections of L2006H5 show good agreement with the bulk value determined in the SEM. Following EDX analysis, the mineralogy and mineral chemistry of each IDP was determined by analyzing ultramicrotome thin sections in a TEM equipped with an EDX spectrometer.

  4. Hydrate sulfuric acid after sulfur implantation in water ice

    NASA Astrophysics Data System (ADS)

    Strazzulla, G.; Baratta, G. A.; Leto, G.; Gomis, O.

    2007-12-01

    For many years an ongoing research program performed at our laboratory has had the aim to investigate the implantation of reactive ions in ices relevant to planetology by using IR spectroscopy. We present new results obtained by implanting 200 keV sulfur ions into water ice at 80 K. We have looked at the formation of sulfur-bearing molecules such as sulfuric acid, sulfur dioxide and hydrogen sulfide. We find that hydrated sulfuric acid is formed with high yield ( 0.65±0.1 molecules/ion). An upper limit to the production yield of SO 2 ( Y⩽0.025 molecules/ion) has been estimated; no hydrogen sulfide has been detected. The formation of hydrogen peroxide is confirmed. Ozone is not detected. The results are discussed relevant to the inquiry on the radiolytic sulfur cycle considered responsible for the formation of sulfur-bearing molecules on the surfaces of the Galilean satellites. We demonstrate that sulfur implantation efficiently forms hydrated sulfuric acid whose observed abundance is explained as caused by an exogenic process. It is more difficult to say if the observed sulfur dioxide is quantitatively supported by only sulfur implantation; additional experimental studies are necessary along with direct observations, especially at UV wavelengths such as those that could be performed by instruments on board Hubble Space Telescope or by the forthcoming World Space Observatory (WSO/UV).

  5. Formation of nitric acid hydrates - A chemical equilibrium approach

    NASA Technical Reports Server (NTRS)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

  6. Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

    NASA Technical Reports Server (NTRS)

    Loeffler, Mark J.; Hudson, Reggie L.

    2012-01-01

    In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

  7. Solid-state forms of zoledronic acid: polymorphism in hydrates.

    PubMed

    Ruscica, Romina; Bianchi, Micaela; Quintero, Mariano; Martinez, Andrea; Vega, Daniel R

    2010-12-01

    Solid-state forms of zoledronic acid, a nitrogen-containing bisphosphonate used for treatment of bone diseases are studied using different experimental techniques (DSC, TG, and XRD). Two degrees of hydration have been obtained, containing one and three water molecules per zoledronic acid molecule. The crystal structure of the trihydrated form is reported. Two different anhydrated forms have been obtained when the hydrated ones were heated. Besides, during the dehydration process, an amount of metastable amorphous phase appears, as a function of the dehydration rate. The stability of the obtained crystalline forms is examined under high humidity and a different trihydrated form was obtained, setting clear that the same degree of hydration (trihydrated) can be obtained in two different crystalline forms, and then very different thermal behaviors have been observed.

  8. FLASH: FLITECAM Limits on the Abundance of Silicate Hydrates in the ISM

    NASA Astrophysics Data System (ADS)

    Chiar, Jean

    2014-10-01

    The Science Vision for SOFIA identifies the Interstellar Medium (ISM) as a key area where SOFIA is well poised to make substantial contributions. As the SOFIA Vision points out, dust undergoes constant recycling in the ISM, from its creation in stellar outflows to its incorporation into protoplanetary disks. The observations we propose here will enable us to better understand the evolution of the silicate dust component, specifically the processing it undergoes in the ISM. The structure of the silicate, i.e., whether it is crystalline or amorphous, is a clue to its past evolution. In order to explain the extremely low abundance of crystalline silicates in the diffuse ISM, the process that amorphizes the stardust silicates must be efficient. Experiments show that one of the most efficient processes likely to occur in the diffuse ISM is irradiation by low-energy ions. This process will not only amorphize the grains, but also lead to formation of OH bonds within the grains. Just how much the grains are hydrated can be carefully measured by the SOFIA FLITECAM observations we propose here. To this end, we propose to use FLITECAM Grisms A and C to observe the OH stretching mode in hydrated silicates in the 2.216 to 3.467 micron region. Our targets are three bright highly reddened field stars that probe diffuse ISM dust. These observations are impossible from ground-based facilities due to telluric CO2 absorption, and existing spectra are only moderately reddened and/or of poor quality. The high S/N FLITECAM spectra will enable us to make a careful measurement of the actual hydration level of silicates, thus leading to a better understanding of the processes that affect silicates in the ISM.

  9. FLASH: FLITECAM Limits on the Abundance of Silicate Hydrates in the ISM

    NASA Astrophysics Data System (ADS)

    Chiar, Jean

    2012-10-01

    The Science Vision for SOFIA identifies the Interstellar Medium (ISM) as a key area where SOFIA is well poised to make substantial contributions. As the SOFIA Vision points out, dust undergoes constant recycling in the ISM, from its creation in stellar outflows to its incorporation into protoplanetary disks. The observations we propose here will enable us to better understand the evolution of the silicate dust component, specifically the processing it undergoes in the ISM. The structure of the silicate, i.e., whether it is crystalline or amorphous, is a clue to its past evolution. In order to explain the extremely low abundance of crystalline silicates in the diffuse ISM, the process that amorphizes the stardust silicates must be efficient. Experiments show that one of the most efficient processes likely to occur in the diffuse ISM is irradiation by low-energy ions. This process will not only amorphize the grains, but also lead to formation of OH bonds within the grains. Just how much the grains are hydrated can be carefully measured by the SOFIA FLITECAM observations we propose here. To this end, we propose to use FLITECAM Grisms A and C to observe the OH stretching mode in hydrated silicates in the 2.216 to 3.467 micron region. Our targets are three bright highly reddened field stars that probe diffuse ISM dust. These observations are impossible from ground-based facilities due to telluric CO2 absorption, and existing spectra are only moderately reddened and/or of poor quality. The high S/N FLITECAM spectra will enable us to make a careful measurement of the actual hydration level of silicates, thus leading to a better understanding of the processes that affect silicates in the ISM.

  10. Hydration of amino acids: FTIR spectra and molecular dynamics studies.

    PubMed

    Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

    2015-11-01

    The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

  11. Rejuvenating Hydrator: Restoring Epidermal Hyaluronic Acid Homeostasis With Instant Benefits.

    PubMed

    Narurkar, Vic A; Fabi, Sabrina G; Bucay, Vivian W; Tedaldi, Ruth; Downie, Jeanine B; Zeichner, Joshua A; Butterwick, Kimberly; Taub, Amy; Kadoya, Kuniko; Makino, Elizabeth T; Mehta, Rahul C; Vega, Virginia L

    2016-01-01

    Skin aging is a combination of multifactorial mechanisms that are not fully understood. Intrinsic and extrinsic factors modulate skin aging, activating distinctive processes that share similar molecular pathways. One of the main characteristics of youthful skin is its large capacity to retain water, and this decreases significantly as we age. A key molecule involved in maintaining skin hydration is hyaluronic acid (HA). Concentration of HA in the skin is determined by the complex balance between its synthesis, deposition, association with cellular structures, and degradation. HA bio-equivalency and bio-compatibility have been fundamental in keeping this macromolecule as the favorite of the skincare industry for decades. Scientific evidence now shows that topically applied HA is unable to penetrate the skin and is rapidly degraded on the skin surface. SkinMedica's HA5 Rejuvenating Hydrator (SkinMedica Inc., an Allergan company, Irvine, CA) promotes restoration of endogenous epidermal HA homeostasis and provides instant smoothing and hydration of the skin. These dual benefits are accomplished through the combination of 2 breakthrough technologies: 1) a unique blend of actives powered by SkinMedica proprietary flower-derived stem cell extract that restores the endogenous production of HA; and 2) a proprietary mix of 5 HA forms that plump the skin, decreasing the appearance of fine lines/wrinkles. Pre-clinical studies demonstrated that HA5 induces expression of key epidermal differentiation and barrier markers as well as epidermal HA synthases. A decrease expression of hyaluronidases was also observed upon HA5 application. Initial clinical studies showed that within 15 minutes of application, HA5 instantly improves the appearance of fine lines/wrinkles and skin hydration. Subjects that continue using HA5 (for 8 weeks) demonstrated significant improvements in fine lines/wrinkles, tactile roughness, and skin hydration. In summary, the blend of these 2 key technologies

  12. Periodic quantum chemical studies on anhydrous and hydrated acid clinoptilolite.

    PubMed

    Valdiviés Cruz, Karell; Lam, Anabel; Zicovich-Wilson, Claudio M

    2014-08-07

    Periodic quantum chemistry methods as implemented in the crystal09 code were considered to study acid clinoptilolite (HEU framework type), both anhydrous and hydrated. The most probable location of acid sites and water molecules together with other structural details has been the object of particular attention. Calculations were performed at hybrid and pristine DFT levels of theory with a VDZP quality basis set in order to compare performances. It arises that PBE0 provides the best agreement with experimental data as concerns structural features and the most stable Al distribution in the framework. The role of the water molecule distribution in the stability of the systems, the most probable structure that they induce in the material, and their eventual influence on further chemical modification processes, such as dealumination, are discussed in detail. Results show that, apart from the usually considered interactions of water molecules with the zeolite framework, that is, a H-bond with Brönsted acid sites and coordination with framework Al as Lewis ones, it is necessary to consider cooperation of other weaker effects so as to fully understand the hydration effect in this kind of materials.

  13. 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

  14. Growth of nitric acid hydrates on thin sulfuric acid films

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Middlebrook, Ann M.; Wilson, Margaret A.; Tolbert, Margaret A.

    1994-01-01

    Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

  15. 49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Chloric acid solution or chlorine dioxide hydrate, frozen. 173.229 Section 173.229 Transportation Other Regulations Relating to Transportation PIPELINE AND... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When...

  16. 49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Chloric acid solution or chlorine dioxide hydrate, frozen. 173.229 Section 173.229 Transportation Other Regulations Relating to Transportation PIPELINE AND... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When...

  17. 49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Chloric acid solution or chlorine dioxide hydrate, frozen. 173.229 Section 173.229 Transportation Other Regulations Relating to Transportation PIPELINE AND... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When...

  18. 49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Chloric acid solution or chlorine dioxide hydrate, frozen. 173.229 Section 173.229 Transportation Other Regulations Relating to Transportation PIPELINE AND... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When...

  19. 49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Chloric acid solution or chlorine dioxide hydrate, frozen. 173.229 Section 173.229 Transportation Other Regulations Relating to Transportation PIPELINE AND... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When...

  20. Rates and mechanisms of conversion of ice nanocrystals to hydrates of HCl and HBr: acid diffusion in the ionic hydrates.

    PubMed

    Devlin, J Paul; Gulluru, Dheeraj B; Buch, Victoria

    2005-03-03

    This FTIR study focuses on solid-state chemistry associated with formation and interconversion of the ionic HX (X = Cl, Br) hydrates. Kinetic data are reported for conversions of ice nanocrystal arrays exposed to the saturation pressure of the acids in the 110 approximately 125 K range. The product is amorphous acid dihydrate in the case of HBr, and amorphous monohydrate for HCl. The rate-determining step is identified as HX diffusion through the hydrate product crust toward the interfacial reaction zone, rather than diffusion through ice, as commonly believed. Slowing of the conversion process is thus observed with increasing thickness of the crust. The diffusion coefficient (D(e)) and activation energy values for HX diffusion through the hydrates were evaluated with the help of the shrinking-core model. Hydrate crystallization occurs as a separate step, upon heating above 130 K. Subsequently, rates of reversible transitions between crystal di- and monohydrates were observed upon exposure to acid vapor and acid evacuation. In conversion from di- to monohydrate, the rate slows after fast formation of several layers; subsequently, diffusion through the product crust appears to be the rate-controlling step. The activation energy for HBr diffusion through crystal dihydrate is found to be significantly higher than that for the amorphous analogue. Conjecture is offered for a molecular mechanism of HX transport through the crystal hydrate, based on (i) spectroscopic/computational evidence for the presence of molecular HX bonded to X(-) in each of the ionic hydrate phases and (ii) the relative E(a) values found for HBr and HCl diffusion. Monte Carlo modeling suggests acid transport to the reaction zone along boundaries between "nanocrystallites" generated by multiple hydrate nucleation events at the particle surfaces. The reverse conversion, of crystalline monohydrate particles to the dihydrate phase, as well as dihydrate to trihydrate, displays nearly constant rate

  1. Hydration structures of lactic acid: characterization of the ionic clathrate hydrate formed with a biological organic acid anion.

    PubMed

    Muromachi, Sanehiro; Abe, Toru; Yamamoto, Yoshitaka; Takeya, Satoshi

    2014-10-21

    Ionic clathrate hydrates are water-based materials that have unique properties, such as a wide range of melting temperatures and high gas capacities. In their structure, water molecules coordinate around ionic substances, which is regarded as the actual hydration structure and also linking of the hydrate clusters, giving insight into the dynamics of the water molecules and ions. This paper reports the synthesis and characterization of the ionic clathrate hydrate of tetra-n-butylammonium lactate (TBAL), the anion of which is a biological organic material. Phase equilibrium measurements and optical observations of the crystal morphology and crystal structure analysis were performed. The TBAL hydrate has a melting temperature of 284.8 K suitable for cool energy storage applications. The actual hydration patterns around a lactate anion are shown in the form of ionic clathrate hydrate structure.

  2. Structure of the ordered hydration of amino acids in proteins: analysis of crystal structures

    SciTech Connect

    Biedermannová, Lada Schneider, Bohdan

    2015-10-27

    The hydration of protein crystal structures was studied at the level of individual amino acids. The dependence of the number of water molecules and their preferred spatial localization on various parameters, such as solvent accessibility, secondary structure and side-chain conformation, was determined. Crystallography provides unique information about the arrangement of water molecules near protein surfaces. Using a nonredundant set of 2818 protein crystal structures with a resolution of better than 1.8 Å, the extent and structure of the hydration shell of all 20 standard amino-acid residues were analyzed as function of the residue conformation, secondary structure and solvent accessibility. The results show how hydration depends on the amino-acid conformation and the environment in which it occurs. After conformational clustering of individual residues, the density distribution of water molecules was compiled and the preferred hydration sites were determined as maxima in the pseudo-electron-density representation of water distributions. Many hydration sites interact with both main-chain and side-chain amino-acid atoms, and several occurrences of hydration sites with less canonical contacts, such as carbon–donor hydrogen bonds, OH–π interactions and off-plane interactions with aromatic heteroatoms, are also reported. Information about the location and relative importance of the empirically determined preferred hydration sites in proteins has applications in improving the current methods of hydration-site prediction in molecular replacement, ab initio protein structure prediction and the set-up of molecular-dynamics simulations.

  3. Hydration of nucleic acid bases: a Car-Parrinello molecular dynamics approach.

    PubMed

    Furmanchuk, Al'ona; Isayev, Olexandr; Shishkin, Oleg V; Gorb, Leonid; Leszczynski, Jerzy

    2010-04-14

    Comprehensive study on interactions between nucleic acid bases (NABs) and bulk water environment has been performed with use of Car-Parrinello molecular dynamics. Detailed analysis of average number, lifetimes and mobility of water molecules, orientation and 3D organization of hydrogen bond network in the first hydration shell of adenine, guanine, cytosine and thymine has been carried out. Effect of hydration by bulk water environment has been compared with the data from polyhydrated complexes of NABs. During bulk water hydration the presence of mixed Hw...N/Hw...pi type of bonding is detected for imino nitrogen atoms. The formation of three hydrogen bonds to carbonyl groups reflects the significance of polarizing effects of aqueous environments. Hydration of hydrophobic sites revealed the presence of extremely weak bonding. Hydration of C6-H6 site of thymine is standing significantly apart from the hydration of other hydrophobic sites. An average coordination numbers of adenine, guanine, cytosine and thymine in bulk water environment are 6.87, 8.52, 6.12 and 6.42 water molecules, correspondingly. The lifetime of water molecules in the first hydration shell varies from 1 to 3 ps. Some differences in hydration studied by CPMD (bulk water) and quantum chemical (less than 20 water molecules) methods indicate a significant effect of the second hydration shell on structure and properties of the first hydration shell for the considered compounds.

  4. Phase behavior and bilayer properties of fatty acids: hydrated 1:1 acid-soaps.

    PubMed

    Cistola, D P; Atkinson, D; Hamilton, J A; Small, D M

    1986-05-20

    The physical properties in water of a series of 1:1 acid-soap compounds formed from fatty acids and potassium soaps with saturated (10-18 carbons) and omega-9 monounsaturated (18 carbons) hydrocarbon chains have been studied by using differential scanning calorimetry (DSC), X-ray diffraction, and direct and polarized light microscopy. DSC showed three phase transitions corresponding to the melting of crystalline water, the melting of crystalline lipid hydrocarbon chains, and the decomposition of the 1:1 acid-soap compound into its parent fatty acid and soap. Low- and wide-angle X-ray diffraction patterns revealed spacings that corresponded (with increasing hydration) to acid-soap crystals, hexagonal type II liquid crystals, and lamellar liquid crystals. The lamellar phase swelled from bilayer repeat distances of 68 (at 45% H2O) to 303 A (at 90% H2O). Direct and polarized light micrographs demonstrated the formation of myelin figures as well as birefringent optical textures corresponding to hexagonal and lamellar mesophases. Assuming that 1:1 potassium hydrogen dioleate and water were two components, we constructed a temperature-composition phase diagram. Interpretation of the data using the Gibbs phase rule showed that, at greater than 30% water, hydrocarbon chain melting was accompanied by decomposition of the 1:1 acid-soap compound and the system changed from a two-component to a three-component system. Comparison of hydrated 1:1 fatty acid/soap systems with hydrated soap systems suggests that the reduced degree of charge repulsion between polar groups causes half-ionized fatty acids in excess water to form bilayers rather than micelles.(ABSTRACT TRUNCATED AT 250 WORDS)

  5. Computational study of the hydration of sulfuric acid dimers: implications for acid dissociation and aerosol formation.

    PubMed

    Temelso, Berhane; Phan, Thuong Ngoc; Shields, George C

    2012-10-04

    We have investigated the thermodynamics of sulfuric acid dimer hydration using ab initio quantum mechanical methods. For (H(2)SO(4))(2)(H(2)O)(n) where n = 0-6, we employed high-level ab initio calculations to locate the most stable minima for each cluster size. The results presented herein yield a detailed understanding of the first deprotonation of sulfuric acid as a function of temperature for a system consisting of two sulfuric acid molecules and up to six waters. At 0 K, a cluster of two sulfuric acid molecules and one water remains undissociated. Addition of a second water begins the deprotonation of the first sulfuric acid leading to the di-ionic species (the bisulfate anion HSO(4)(-), the hydronium cation H(3)O(+), an undissociated sulfuric acid molecule, and a water). Upon the addition of a third water molecule, the second sulfuric acid molecule begins to dissociate. For the (H(2)SO(4))(2)(H(2)O)(3) cluster, the di-ionic cluster is a few kcal mol(-1) more stable than the neutral cluster, which is just slightly more stable than the tetra-ionic cluster (two bisulfate anions, two hydronium cations, and one water). With four water molecules, the tetra-ionic cluster, (HSO(4)(-))(2)(H(3)O(+))(2)(H(2)O)(2), becomes as favorable as the di-ionic cluster H(2)SO(4)(HSO(4)(-))(H(3)O(+))(H(2)O)(3) at 0 K. Increasing the temperature favors the undissociated clusters, and at room temperature we predict that the di-ionic species is slightly more favorable than the neutral cluster once three waters have been added to the cluster. The tetra-ionic species competes with the di-ionic species once five waters have been added to the cluster. The thermodynamics of stepwise hydration of sulfuric acid dimer is similar to that of the monomer; it is favorable up to n = 4-5 at 298 K. A much more thermodynamically favorable pathway forming sulfuric acid dimer hydrates is through the combination of sulfuric acid monomer hydrates, but the low concentration of sulfuric acid relative to

  6. Perfluorobutane sulfonic acid hydration and interactions with O2 adsorbed on Pt3.

    PubMed

    Yan, Liuming; Balbuena, Perla B; Seminario, Jorge M

    2006-04-06

    The side chain of NAFION, a proton conductive membrane used as electrolyte in low-temperature fuel cells, is modeled with perfluorobutane sulfonic acid. Density functional theory is used to characterize structures and energetics of hydration of the model system interacting with a proton solvated with up to 24 water molecules and analyze interactions of some of these hydrated complexes with O(2) adsorbed on Pt(3). It is found that at least three water molecules are needed to ionize the sulfonic acid, and higher degrees of hydration induce the formation of cages where the water molecules are held together via complex hydrogen-bond networks. The interaction between the complex formed by the ionized acid and the hydrated proton, in contact with a bridge-adsorbed O(2)-Pt(3), promotes the protonation of the adsorbed O(2). Upon protonation, the O(2)-Pt(3) system evolves from hydrophobic to hydrophilic behavior, which may facilitate further interfacial contact.

  7. Structure of the ordered hydration of amino acids in proteins: analysis of crystal structures.

    PubMed

    Biedermannová, Lada; Schneider, Bohdan

    2015-11-01

    Crystallography provides unique information about the arrangement of water molecules near protein surfaces. Using a nonredundant set of 2818 protein crystal structures with a resolution of better than 1.8 Å, the extent and structure of the hydration shell of all 20 standard amino-acid residues were analyzed as function of the residue conformation, secondary structure and solvent accessibility. The results show how hydration depends on the amino-acid conformation and the environment in which it occurs. After conformational clustering of individual residues, the density distribution of water molecules was compiled and the preferred hydration sites were determined as maxima in the pseudo-electron-density representation of water distributions. Many hydration sites interact with both main-chain and side-chain amino-acid atoms, and several occurrences of hydration sites with less canonical contacts, such as carbon-donor hydrogen bonds, OH-π interactions and off-plane interactions with aromatic heteroatoms, are also reported. Information about the location and relative importance of the empirically determined preferred hydration sites in proteins has applications in improving the current methods of hydration-site prediction in molecular replacement, ab initio protein structure prediction and the set-up of molecular-dynamics simulations.

  8. Structure of the ordered hydration of amino acids in proteins: analysis of crystal structures

    PubMed Central

    Biedermannová, Lada; Schneider, Bohdan

    2015-01-01

    Crystallography provides unique information about the arrangement of water molecules near protein surfaces. Using a nonredundant set of 2818 protein crystal structures with a resolution of better than 1.8 Å, the extent and structure of the hydration shell of all 20 standard amino-acid residues were analyzed as function of the residue conformation, secondary structure and solvent accessibility. The results show how hydration depends on the amino-acid conformation and the environment in which it occurs. After conformational clustering of individual residues, the density distribution of water molecules was compiled and the preferred hydration sites were determined as maxima in the pseudo-electron-density representation of water distributions. Many hydration sites interact with both main-chain and side-chain amino-acid atoms, and several occurrences of hydration sites with less canonical contacts, such as carbon–donor hydrogen bonds, OH–π interactions and off-plane interactions with aromatic heteroatoms, are also reported. Information about the location and relative importance of the empirically determined preferred hydration sites in proteins has applications in improving the current methods of hydration-site prediction in molecular replacement, ab initio protein structure prediction and the set-up of molecular-dynamics simulations. PMID:26527137

  9. Gas-Phase Hydration Thermochemistry of Sodiated and Potassiated Nucleic Acid Bases

    NASA Astrophysics Data System (ADS)

    Wincel, Henryk

    2012-09-01

    Hydration reactions of sodiated and potassiated nucleic acid bases (uracil, thymine, cytosine, and adenine) produced by electrospray have been studied in a gas phase using the pulsed ion-beam high-pressure mass spectrometer. The thermochemical properties, ΔH o n , ΔS o n , and ΔG o n , for the hydrated systems were obtained from hydration equilibrium measurement. The structural aspects of the hydrated complexes are discussed in conjunction with available literature data. The correlation between water binding energies in the hydrated complexes and the corresponding metal ion affinities of nucleobases suggests that a significant (if not dominant) amount of the canonical structure of cytosine undergoes tautomerization during electrospray ionization, and the thermochemical values for cationized cytosine probably correspond to a mixture of tautomeric complexes.

  10. Gas-phase hydration thermochemistry of sodiated and potassiated nucleic acid bases.

    PubMed

    Wincel, Henryk

    2012-09-01

    Hydration reactions of sodiated and potassiated nucleic acid bases (uracil, thymine, cytosine, and adenine) produced by electrospray have been studied in a gas phase using the pulsed ion-beam high-pressure mass spectrometer. The thermochemical properties, ΔH(o)(n), ΔS(o)(n), and ΔG(o)(n), for the hydrated systems were obtained from hydration equilibrium measurement. The structural aspects of the hydrated complexes are discussed in conjunction with available literature data. The correlation between water binding energies in the hydrated complexes and the corresponding metal ion affinities of nucleobases suggests that a significant (if not dominant) amount of the canonical structure of cytosine undergoes tautomerization during electrospray ionization, and the thermochemical values for cationized cytosine probably correspond to a mixture of tautomeric complexes.

  11. Infrared optical constants of H2O ice, amorphous nitric acid solutions, and nitric acid hydrates

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Koehler, Birgit G.; Middlebrook, Ann M.; Tolbert, Margaret A.; Jordon, Joseph

    1994-01-01

    We determined the infrared optical constants of nitric acid trihydrate, nitric acid dihydrate, nitric acid monohydrate, and solid amorphous nitric acid solutions which crystallize to form these hydrates. We have also found the infrared optical constants of H2O ice. We measured the transmission of infrared light throught thin films of varying thickness over the frequency range from about 7000 to 500/cm at temperatures below 200 K. We developed a theory for the transmission of light through a substrate that has thin films on both sides. We used an iterative Kramers-Kronig technique to determine the optical constants which gave the best match between measured transmission spectra and those calculated for a variety of films of different thickness. These optical constants should be useful for calculations of the infrared spectrum of polar stratospheric clouds.

  12. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  13. Abnormal incorporation of amino acids into the gas hydrate crystal lattice.

    PubMed

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Ahn, Docheon; Lee, Kun-Hong

    2014-12-28

    Gas hydrates are crystalline ice-like solid materials enclosing gas molecules inside. The possibility of the presence of gas hydrates with amino acids in the universe is of interest when revealing the potential existence of life as they are evidence of a source of water and organic precursors, respectively. However, little is known about how they can naturally coexist, and their crystallization behavior would become far more complex as both crystallize with formation of hydrogen bonds. Here, we report abnormal incorporation of amino acids into the gas hydrate crystal lattice that is contrary to the generally accepted crystallization mode, and this resulted in lattice distortion and expansion. The present findings imply the potential for their natural coexistence by sharing the crystal lattice, and will be helpful for understanding the role of additives in the gas hydrate crystallization.

  14. Origins of hydration differences in homochiral and racemic crystals of aspartic acid.

    PubMed

    Juliano, Thomas R; Korter, Timothy M

    2015-02-26

    The propensity for crystalline hydrates of organic molecules to form is related to the strength of the interactions between molecules, including the chiral composition of the molecular solids. Specifically, homochiral versus racemic crystalline samples can exhibit distinct differences in their ability to form energetically stable hydrates. The focus of the current study is a comparison of the crystal structures and intermolecular forces found in solid-state L-aspartic acid, DL-aspartic acid, and L-aspartic acid monohydrate. The absence of experimental evidence for the DL-aspartic acid monohydrate is considered here in terms of the enhanced thermodynamic stability of the DL-aspartic acid anhydrate crystal as compared to the L-aspartic acid anhydrate as revealed through solid-state density functional theory calculations and terahertz spectroscopic measurements. The results indicate that anhydrous DL-aspartic acid is the more stable solid, not due to intermolecular forces alone but also due to the improved conformations of the molecules within the racemic solid. Hemihydrated and monohydrated forms of DL-aspartic acid have been computationally evaluated, and in each case, the hydrates produce destabilized aspartic acid conformations that prevent DL-aspartic acid hydrate formation from occurring.

  15. Exploring Jupiter's icy moons with old techniques and big facilities - new insights on sulfuric acid hydrates

    NASA Astrophysics Data System (ADS)

    Maynard-Casely, H. E.; Avdeev, M.; Brand, H.; Wallwork, K.

    2013-12-01

    Sulfuric acid hydrates have been proposed to be abundant on the surface of Europa [1], and hence would be important planetary forming materials for this moon and its companions Ganymede and Callisto. Understanding of the surface features and subsurface of these moons could be advanced by firmer knowledge of the icy materials that comprise them [2], insight into which can be drawn from firmer knowledge of physical properties and phase behaviour of the candidate materials. We wish to present results from a study that started with the question ';What form of sulfuric acid hydrate would form on the surface of Europa'. The intrinsic hydrogen-domination of planetary ices, makes studying these materials with laboratory powder diffraction very challenging. Insights into their crystalline phase behavior and the extraction of a number of thermal and mechanical properties is often only accessible with high-flux synchrotron x-ray diffraction and utilization of the large scattering cross section with neutron diffraction. We have used the Powder Diffraction beamline at Australian synchrotron [4] and the Echidna (High-resolution neutron powder diffraction) instrument of the Australian Nuclear Science and Technology Organization, [5] to obtain an number of new insights into the crystalline phases formed from sulfruic acid and water mixtures. These instruments have enabled the discovery a new water-rich sulfuric acid hydrate form [6], improved structural characterisation of existing forms [7] and a charting the phase diagram of this fundamental binary system [8]. This has revealed exciting potential for understanding more about the surface of Europa from space, perhaps even providing a window into its past. [1] Carlson, R.W., R.E. Johnson, and M.S. Anderson, Science, 1999. 286(5437): p. 97-99. [2] Fortes, A.D. and M. Choukroun. Space Sci Rev, 2010. 153(1-4): p. 185-218. [3] Blake, D., et al., Space Sci Rev,, 2012. 170(1-4): p. 341-399. [4] Wallwork, K.S., Kennedy B. J. and Wang, D

  16. The mechanism of the dehydration of alcohols and the hydration of alkenes in acid solution

    NASA Astrophysics Data System (ADS)

    Vinnik, M. I.; Obraztsov, P. A.

    1990-01-01

    Kinetic data for the hydration of unsaturated compounds, the dehydration of alcohols, and the isotope exchange of the oxygen atom in alcohols and aqueous solutions of strong acids are analysed to establish the detailed mechanisms of these reactions. The catalytic action of the acid is caused not only by its ability to protonate the reactant but also by the possibility of the formation of reactive complexes of the reactant with the acid hydrates or the molecules of the undissociated acids. Equations are presented whereby the influence of the ionising capacity of the medium on the effective rate constants for the reactions indicated can be taken into account quantitatively. The question of the involvement of carbonium ions as reactive intermediates in reactions involving the dehydration of alcohols, the hydration of unsaturated compounds, and the isotope exchange of the oxygen atom in alcohols is examined. Complexes of the reactant with a solvated proton, the acid molecules, and the acid hydrates are the intermediates in these reactions. The relative contributions of the complexes to the effective rate constant depend on the acid concentration in the aqueous solution. The bibliography includes 65 references

  17. Sialic acid-to-urea ratio as a measure of airway surface hydration.

    PubMed

    Esther, Charles R; Hill, David B; Button, Brian; Shi, Shuai; Jania, Corey; Duncan, Elizabeth A; Doerschuk, Claire M; Chen, Gang; Ranganathan, Sarath; Stick, Stephen M; Boucher, Richard C

    2017-03-01

    Although airway mucus dehydration is key to pathophysiology of cystic fibrosis (CF) and other airways diseases, measuring mucus hydration is challenging. We explored a robust method to estimate mucus hydration using sialic acid as a marker for mucin content. Terminal sialic acid residues from mucins were cleaved by acid hydrolysis from airway samples, and concentrations of sialic acid, urea, and other biomarkers were analyzed by mass spectrometry. In mucins purified from human airway epithelial (HAE), sialic acid concentrations after acid hydrolysis correlated with mucin concentrations (r(2) = 0.92). Sialic acid-to-urea ratios measured from filters applied to the apical surface of cultured HAE correlated to percent solids and were elevated in samples from CF HAEs relative to controls (2.2 ± 1.1 vs. 0.93 ± 1.8, P < 0.01). Sialic acid-to-urea ratios were elevated in bronchoalveolar lavage fluid (BALF) from β-epithelial sodium channel (ENaC) transgenic mice, known to have reduced mucus hydration, and mice sensitized to house dust mite allergen. In a translational application, elevated sialic acid-to-urea ratios were measured in BALF from young children with CF who had airway infection relative to those who did not (5.5 ± 3.7 vs. 1.9 ± 1.4, P < 0.02) and could be assessed simultaneously with established biomarkers of inflammation. The sialic acid-to-urea ratio performed similarly to percent solids, the gold standard measure of mucus hydration. The method proved robust and has potential to serve as flexible techniques to assess mucin hydration, particularly in samples like BALF in which established methods such as percent solids cannot be utilized.

  18. Stability of prostacyclin analogues: an unusual lack of reactivity in acid-catalyzed alkene hydration.

    PubMed

    Magill, A; O'Yang, C; Powell, M F

    1988-04-01

    Prostacyclin analogue 5 undergoes specific acid-catalyzed hydration (kH+ = 1.9 x 10(-7)M-1 sec-1 at 25 degrees C) and a pH-independent oxidation reaction (k0 = 1.2 x 10(-10) sec-1 at 25 degrees C) above pH approximately 5. The hydration reaction for 5 is much slower than for other structurally similar exocyclic alkenes, even though the rate-determining step is proton transfer. This slowness of reaction and an analysis of the pH-rate profile show that 5 does not exhibit significant intramolecular general acid catalysis, as does prostacyclin.

  19. Microwave Spectra of Fluorinated Propionic Acids and Their Hydrates

    NASA Astrophysics Data System (ADS)

    Obenchain, Daniel A.; Grubbs, G. S. Grubbs, Ii; Novick, Stewart E.; Cooke, Stephen A.; Serrato, Agapito Serrato, Iii; Lin, Wei

    2013-06-01

    The microwave spectra of three fluorinated propionic acids, namely pentafluoropropionic acid, 2,2,3,3-tetrafluoropropionic acid, and 2,3,3,3-tetrafluoropropionic acid have been observed and assigned. The spectra of pentafluoropropionic acid and its monohydrate were reported in this meeting last year. The conformational analysis of 2,2,3,3-tetrafluoropropionic acid and 2,3,3,3-tetrafluoropropionic acid will be compared to that of pentafluoropropionic acid. The structures of the three monohydrates will be discussed in terms of hydrogen bonding.

  20. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    PubMed

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  1. Prediction of phase equilibrium and hydration free energy of carboxylic acids by Monte Carlo simulations.

    PubMed

    Ferrando, Nicolas; Gedik, Ibrahim; Lachet, Véronique; Pigeon, Laurent; Lugo, Rafael

    2013-06-13

    In this work, a new transferable united-atom force field has been developed to predict phase equilibrium and hydration free energy of carboxylic acids. To take advantage of the transferability of the AUA4 force field, all Lennard-Jones parameters of groups involved in the carboxylic acid chemical function are reused from previous parametrizations of this force field. Only a unique set of partial electrostatic charges is proposed to reproduce the experimental gas phase dipole moment, saturated liquid densities and vapor pressures. Phase equilibrium properties of various pure carboxylic acids (acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid) and one diacid (1,5-pentanedioic) are studied through Monte Carlo simulations in the Gibbs ensemble. A good accuracy is obtained for pure compound saturated liquid densities and vapor pressures (average deviation of 2% and 6%, respectively), as well as for critical points. The vaporization enthalpy is, however, poorly predicted for short acids, probably due to a limitation of the force field to correctly describe the significant dimerization in the vapor phase. Pressure-composition diagrams for two binary mixtures (acetic acid + n-butane and propanoic acid + pentanoic acid) are also computed with a good accuracy, showing the transferability of the proposed force field to mixtures. Hydration free energies are calculated for three carboxylic acids using thermodynamic integration. A systematic overestimation of around 10 kJ/mol is observed compared to experimental data. This new force field parametrized only on saturated equilibrium properties appears insufficient to reach an acceptable precision for this property, and only relative hydration free energies between two carboxylic acids can be correctly predicted. This highlights the limitation of the transferability feature of force fields to properties not included in the parametrization database.

  2. Theoretical study of the hydration of atmospheric nucleation precursors with acetic acid.

    PubMed

    Zhu, Yu-Peng; Liu, Yi-Rong; Huang, Teng; Jiang, Shuai; Xu, Kang-Ming; Wen, Hui; Zhang, Wei-Jun; Huang, Wei

    2014-09-11

    While atmosphere is known to contain a significant fraction of organic substance and the effect of acetic acid to stabilize hydrated sulfuric acids is found to be close that of ammonia, the details about the hydration of (CH3COOH)(H2SO4)2 are poorly understood, especially for the larger clusters with more water molecules. We have investigated structural characteristics and thermodynamics of the hydrates using density functional theory (DFT) at PW91PW91/6-311++G(3df,3pd) level. The phenomena of the structural evolution may exist during the early stage of the clusters formation, and we tentatively proposed a calculation path for the Gibbs free energies of the clusters formation via the structural evolution. The results in this study supply a picture of the first deprotonation of sulfuric acids for a system consisting of two sulfuric acid molecules, an acetic acid molecule, and up to three waters at 0 and 298.15 K, respectively. We also replace one of the sulfuric acids with a bisulfate anion in (CH3COOH)(H2SO4)2 to explore the difference of acid dissociation between two series of clusters and interaction of performance in clusters growth between ion-mediated nucleation and organics-enhanced nucleation.

  3. Hydrated arrays of acidic surface groups as model systems for interfacial structure and mechanisms in PEMs.

    PubMed

    Roudgar, A; Narasimachary, S P; Eikerling, M

    2006-10-19

    We utilize ab initio quantum mechanical calculations in order to explore structural conformations and cooperative mechanisms at a minimally hydrated 2D array of flexible acidic surface groups. This system serves as a model for rationalizing interactions and correlations of protons and water with ionized side chains that are affixed to hydrophobic polymer aggregates in polymer electrolyte membranes (PEMs). The model exhibits two basic minimum energy configurations upon varying the separation of surface groups from 5 to 12 A. In the "upright" structure at small separation, surface groups are fully dissociated and oriented perpendicular to the basal plane. Together with hydronium ions (H3O+) they form a highly ordered network with long-range correlations. At larger separations we found the transition to a "tilted" structure with cluster-like conformation of surface groups. This structure retains only short-range correlations. Moreover, we investigated the strength of water binding to the minimally hydrated structures. At small separations between surface groups, an additional water molecule interacts only weakly with the minimally hydrated array (binding energy < 0.1 eV) while the energy needed to remove one water molecule exceeds 1 eV. This shows that the minimally hydrated systems are very stable. Ideally, these studies would expedite the design of cheap, highly performing PEMs for fuel cells, with a major focus on membranes that could operate stably at minimal hydration and elevated temperatures (>120 degrees C).

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-08-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  7. Salt hydrates for in situ water activity control have acid-base effects on enzymes in nonaqueous media.

    PubMed

    Fontes, Nuno; Harper, Neil; Halling, Peter J; Barreiros, Susana

    2003-06-30

    Salt hydrates very frequently are utilized as in situ water activity buffers in reaction mixtures of enzymes in nonaqueous media. In addition to buffering water activity, there is evidence that salt hydrates also often affect initial rates in other ways. This has been generally overlooked or thought to be related to water transfer effects. Here we show that salt hydrates can have important acid-base effects on enzymes in nonaqueous media. We performed transesterification reactions in n-hexane and in supercritical ethane catalyzed by cross-linked crystals of subtilisin, differing in the method used to set a(W), and confirmed that the presence of salt hydrate pairs significantly affected the catalytic performance of the enzyme. However, in the presence of a solid-state acid-base buffer, salt hydrates had no effect on enzymatic activity. Direct evidence for the acid-base effects of salt hydrates was obtained by testing their effect on the protonation state of an organo-soluble H(+)/Na(+) indicator. The four salt hydrate pairs tested affected the indicator to very different extents. By promoting the exchange of H(+) for Na(+), salt hydrates will tend to affect the ionization state of acidic residues in the protein and, hence, enzymatic activity. In fact, salt hydrates were able to affect the pH memory of subtilisin lyophilized from different aqueous pHs, bringing about up to 20-fold enhancements and up to 5-fold decreases in catalytic activity. The possibility of such acid-base effects need to be considered in all experiments using salt hydrates to control water activity.

  8. Effect of minodronic acid hydrate on hip geometry in Japanese women with postmenopausal osteoporosis.

    PubMed

    Ito, Masako; Sone, Teruki; Fukunaga, Masao

    2010-05-01

    Dual-energy X-ray absorptiometry-based hip structural analysis was performed to evaluate the effect of a bisphosphonate, minodronic acid hydrate, on the geometry of the proximal femur in Japanese patients with osteoporosis. The subjects were 103 postmenopausal patients (average age 63.9 +/- 6.4 years) with primary osteoporosis. Minodronic acid hydrate was administered orally at a dose of 1 mg/day for 12 months. Significant early responses at 3-6 months after the start of administration were observed in all three regions of the proximal femur (narrow neck, intertrochanter, and shaft) in terms of bone density, geometry, and bone strength indices. The outcomes of therapy included a reduction of the internal diameter of the cortical bone (-0.1, -0.6, and -0.2% in the neck, intertrochanter, and shaft, respectively, at 12 months; not significant) and a significant increase in cortical thickness (3.1, 3.7, and 2.0% in the respective regions at 12 months). Furthermore, minodronic acid hydrate induced a significant enlargement of the cross-sectional bone area, which is related to compressive strength; a significant increase in cross-sectional moment of inertia and section modulus (SM 4.9, 5.8, and 2.9% in the neck, intertrochanter, and shaft, respectively, at 12 months; P < 0.001), which are related to the bending strength; and a significant reduction in buckling ratio (BR -3.0% (P < 0.001), -4.2% (P < 0.001), and -1.4% (P < 0.05) in the respective regions at 12 months), which reflects improved cortical stability. These findings show that minodronic acid hydrate reduces age-related endocortical bone resorption, leading to increased cortical thickness and sustained or enhanced bone strength.

  9. Interactions between hydrated cement paste and organic acids: Thermodynamic data and speciation modeling

    SciTech Connect

    De Windt, Laurent; Bertron, Alexandra; Larreur-Cayol, Steeves; Escadeillas, Gilles

    2015-03-15

    Interactions of short-chain organic acids with hydrated cement phases affect structure durability in the agro-food and nuclear waste industries but can also be used to modify cement properties. Most previous studies have been experimental, performed at fixed concentrations and pH, without quantitatively discriminating among polyacidity effects, or complexation and salt precipitation processes. This paper addresses such issues by thermodynamic equilibrium calculations for acetic, citric, oxalic, succinic acids and a simplified hydrated CEM-I. The thermodynamic constants collected from the literature allow the speciation to be modeled over a wide range of pH and concentrations. Citric and oxalic had a stronger chelating effect than acetic acid, while succinic acid was intermediate. Similarly, Ca-citrate and Ca-oxalate salts were more insoluble than Ca-acetate and Ca-succinate salts. Regarding aluminium complexation, hydroxyls, sulfates, and acid competition was highlighted. The exploration of acid mixtures showed the preponderant effect of oxalate and citrate over acetate and succinate.

  10. Negative ion photoelectron spectroscopy of the copper-aspartic acid anion and its hydrated complexes

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.; Martínez, Ana; Salpin, Jean-Yves; Schermann, Jean-Pierre

    2010-08-01

    Negative ions of copper-aspartic acid Cu(Asp)- and its hydrated complexes have been produced in the gas phase and studied by anion photoelectron spectroscopy. The vertical detachment energies (VDE) of Cu(Asp)- and Cu(Asp)-(H2O)1,2 were determined to be 1.6, 1.95, and 2.20 eV, respectively. The spectral profiles of Cu(Asp)-(H2O)1 and Cu(Asp)-(H2O)2 closely resembled that of Cu(Asp)-, indicating that hydration had not changed the structure of Cu(Asp)- significantly. The successive shifts to higher electron binding energies by the spectra of the hydrated species provided measures of their stepwise solvation energies. Density functional calculations were performed on anionic Cu(Asp)- and on its corresponding neutral. The agreement between the calculated and measured VDE values implied that the structure of the Cu(Asp)- complex originated with a zwitterionic form of aspartic acid in which a copper atom had inserted into the N-H bond.

  11. An NMR study of structure and dynamics of hydrated poly (aspartic acid) sodium salt

    NASA Astrophysics Data System (ADS)

    Wang, Pixin; Ando, Isao

    1998-06-01

    High-resolution 13C CP/MAS NMR and pulse 1H NMR experiments were carried out for hydrated poly(aspartic acid) sodium salt, in order to investigate the conformation and molecular motion of the polymer. From these experimental results, it is found that the main-chain conformation of poly(aspartic acid) sodium salt which takes an α-helix form in the dry state is not drastically affected by an addition of water. In the 13C CP/MAS NMR spectrum, a new peak at ca. 184 ppm appears, which comes from the formation of hydrogen bond between the carbonyl carbon of the side chains and water, and the intensity of the peak is associated with the water content. The 13C spin-lattice relaxation time ( T1) experiments show that the T1 values for the individual carbons of the polymer are decreased with an increase in the water content. This shows that the mobility of the polymer is increased with an increase in the water content. Further, the 1H spin-spin relaxation time ( T2) experiments show that the polymer has the two or three components with different molecular motion. With an increase in the water content or temperature, the T2 values of hydrated PAANa are increased. This shows that the molecular motion is increased. In the high water content, the polymer has a signal component in the molecular motion. This shows that the polymer is uniformly hydrated.

  12. Examination of Portland cement paste hydrated in the presence of malic acid

    SciTech Connect

    Rai, Sarita; Chaturvedi, Shivani; Singh, N.B

    2004-03-01

    When malic acid (MA) solutions are added to ordinary Portland cement (OPC), rapid heat evolution takes place, but the hydration is retarded considerably at all the MA concentrations. To understand the mechanism of retardation, UV-visible and IR spectral studies were made and the results have revealed that some interaction occurs between MA and certain constituents of OPC. X-ray diffraction (XRD) and thermogravimetric (TG)/differential thermal analysis (DTA) studies have proved the formation of a new reaction product due to interaction between MA and some of the mineral phases of Portland cement. The retardation of the hydration of Portland cement may be attributed to the formation of this new compound.

  13. Vapor pressures of solid hydrates of nitric acid - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas R.; Fox, Lewis E.; Zahniser, Mark S.; Wofsy, Steven C.

    1993-01-01

    Thermodynamic data are presented for hydrates of nitric acid: HNO3.H2O, HNO3.2H2O, HNO3.3H2O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO3.2H2O may be favored in polar stratospheric clouds over the slightly more stable HNO3.3H2O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO3.2H2O and HNO3.3H2O. Vapor transfer from HNO3.2H2O to HNO3.3H2O could be a key step in the sedimentation of HNO3, which plays an important role in the depletion of polar ozone.

  14. High abundance of Crenarchaeota in a temperate acidic forest soil.

    PubMed

    Kemnitz, Dana; Kolb, Steffen; Conrad, Ralf

    2007-06-01

    The objective of the study was to elucidate the depth distribution and community composition of Archaea in a temperate acidic forest soil. Numbers of Archaea and Bacteria were measured in the upper 18 cm of the soil, and soil cores were sampled on two separate occasions using quantitative PCR targeting 16S rRNA genes. Maximum numbers of Archaea were 0.6-3.8 x 10(8) 16S rRNA genes per gram of dry soil. Numbers of Bacteria were generally higher, but Archaea always accounted for a high percentage of the total gene numbers (12-38%). The archaeal community structure was analysed by the construction of clone libraries and by terminal restriction length polymorphism (T-RFLP) using the same Archaea-specific primers. With the reverse primer labelled, T-RFLP analysis led to the detection of four T-RFs. Three had lengths of 83, 185 and 218 bp and corresponded to uncultured Crenarchaeota. One (447 bp) was assigned to Thermoplasmales. Labelling of the forward primer allowed further separation of the T-RF into Crenarchaeota Group I.1c and Group I.1b, and indicated that Crenarchaeota of the Group I.1c were the predominant 16S rRNA genotype (abundance of Archaea and concentration of ammonia and nitrate decreased with soil depth. Hence it is unclear if the detected Crenarchaeota Group I.1c participated in ammonia oxidation or had another phenotype.

  15. Determination of pKa and Hydration Constants for a Series of α-Keto-Carboxylic Acids Using Nuclear Magnetic Resonance Spectrometry

    PubMed Central

    Lopalco, Antonio; Douglas, Justin; Denora, Nunzio; Stella, Valentino J.

    2015-01-01

    The determination of the acid-base dissociation constants, and thus the pKa values, of α-keto acids such as pyruvic acid is complex due to the existence of these acids in their hydrated and non-hydrated or oxo-state. Equilibria involved in the hydration and dehydration of the α-keto group of pyruvic acid and three other α-keto acids, 3-methyl-2-oxobutanoic acid, 4-methyl-2-oxopentanoic acid, and 2-oxo-2-phenylacetic acid, were investigated by proton and carbon nuclear magnetic resonance spectrometry, NMR, at constant ionic strength, 0.15, and 25°C. Dissociation constants for the oxo (pKaoxo) and hydrated (pKahyd) acids of each compound were estimated from the change in the degree of hydration with changes in pH and directly from the changes in chemical shifts of various hydrogen and carbons nuclei with pH. α-Keto acids showed greater hydration in their acidic forms than their carboxylate forms. The degree of hydration was sensitive to steric and electronic/resonance factors. As expected, the oxo forms of the acids were stronger acids compared with their hydrated analogs, and their dissociation constants were also sensitive to steric and electronic factors. PMID:26149194

  16. Hydration studies of electrospray ions from amino acids and small peptides

    NASA Astrophysics Data System (ADS)

    Nguyen, Chuong (Steve)

    This project was undertaken to gain a better understanding of the hydration behaviors of gas phase ions from solutions containing amino acids and peptides. In order to characterize their hydration behavior, the molecules of interest in solutions were first converted into gas phase ions by electrospray ionization (ESI). The completely desolvated ions were then deliberately dispersed into an inert bath gas, usually nitrogen, containing accurately known concentrations of solvent vapor. The resulting mixtures of ions and bath gas were subsequently passed into a vacuum chamber by way of an adiabatic supersonic free jet expansion. The cooling during that expansion caused solvation of the ions, the extent of which was determined by a quadrupole mass analyzer. Mass analysis of the solute ions in the absence of vapor showed peaks with the mass to charge ratios corresponding to the desolvated ions. On the other hand, mass spectrometric analyses of ions in the presence of solvent vapor showed sequences of peaks corresponding to the solvated ions with varying numbers of water molecules. The extent of the ion solvation was controlled by varying the concentration of solvent vapor in the bath gas. Two different scales were proposed for the evaluation of the relative affinities of amino acids for water molecules. One was based primarily on the assumption that the affinities of amino acids for water molecules are directly proportional to their gas phase solvation rate constants ( k). An alternative approach produced an affinity scale based on the extent of ion hydration occurred during the free jet expansion. It was found that the addition of a polar solvent vapor to the bath gas at low concentrations substantially enhanced the production of the bare solute ions from the evaporating charged droplets. This remarkable result not only provided a means to increase the ion production and thus detection sensitivity of mass spectrometric analyses, but also yielded important information

  17. A laboratory study of the nucleation kinetics of nitric acid hydrates under stratospheric conditions

    NASA Astrophysics Data System (ADS)

    James, Alexander D.; Murray, Benjamin J.; Plane, John M. C.

    2016-04-01

    Measurements of the kinetics of crystallisation of ternary H2O-H2SO4-HNO3 mixtures to produce nitric acid hydrate phases, as occurs in the lower stratosphere, have been a long-standing challenge for investigators in the laboratory. Understanding polar stratospheric chlorine chemistry and thereby ozone depletion is increasingly limited by descriptions of nucleation processes. Meteoric smoke particles have been considered in the past as heterogeneous nuclei, however recent studies suggest that these particles will largely dissolve, leaving mainly silica and alumina as solid inclusions. In this study the nucleation kinetics of nitric acid hydrate phases have been measured in microliter droplets at polar stratospheric cloud (PSC) temperatures, using a droplet freezing assay. A clear heterogeneous effect was observed when silica particles were added. A parameterisation based on the number of droplets activated per nuclei surface area (ns) has been developed and compared to global model data. Nucleation experiments on identical droplets have been performed in an X-Ray Diffractometer (XRD) to determine the nature of the phase which formed. β-Nitric Acid Trihydrate (NAT) was observed alongside a mixture of Nitric Acid Dihydrate (NAD) phases. It is not possible to determine whether NAT nucleates directly or is formed by a phase transition from NAD (likely requiring the presence of a mediating liquid phase). Regardless, these results demonstrate the possibility of forming NAT on laboratory timescales. In the polar stratosphere, sulfuric acid (present at several weight percent of the liquid under equilibrium conditions) could provide such a liquid phase. This study therefor provides insight into previous discrepancies between phases formed in the laboratory and those observed in the atmosphere. It also provides a basis for future studies into atmospheric nucleation of solid PSCs.

  18. Insights into the crystallisation process from anhydrous, hydrated and solvated crystal forms of diatrizoic acid.

    PubMed

    Fucke, Katharina; McIntyre, Garry J; Lemée-Cailleau, Marie-Hélène; Wilkinson, Clive; Edwards, Alison J; Howard, Judith A K; Steed, Jonathan W

    2015-01-12

    Diatrizoic acid (DTA), a clinically used X-ray contrast agent, crystallises in two hydrated, three anhydrous and nine solvated solid forms, all of which have been characterised by X-ray crystallography. Single-crystal neutron structures of DTA dihydrate and monosodium DTA tetrahydrate have been determined. All of the solid-state structures have been analysed using partial atomic charges and hardness algorithm (PACHA) calculations. Even though in general all DTA crystal forms reveal similar intermolecular interactions, the overall crystal packing differs considerably from form to form. The water of the dihydrate is encapsulated between a pair of host molecules, which calculations reveal to be an extraordinarily stable motif. DTA presents functionalities that enable hydrogen and halogen bonding, and whilst an extended hydrogen-bonding network is realised in all crystal forms, halogen bonding is not present in the hydrated crystal forms. This is due to the formation of a hydrogen-bonding network based on individual enclosed water squares, which is not amenable to the concomitant formation of halogen bonds. The main interaction in the solvates involves the carboxylic acid, which corroborates the hypothesis that this strong interaction is the last one to be broken during the crystal desolvation and nucleation process.

  19. Determination of pKa and Hydration Constants for a Series of α-Keto-Carboxylic Acids Using Nuclear Magnetic Resonance Spectrometry.

    PubMed

    Lopalco, Antonio; Douglas, Justin; Denora, Nunzio; Stella, Valentino J

    2016-02-01

    The determination of the acid-base dissociation constants, and thus the pKa values, of α-keto acids such as pyruvic acid is complex because of the existence of these acids in their hydrated and nonhydrated or oxo state. Equilibria involved in the hydration and dehydration of the α-keto group of pyruvic acid and three other α-keto acids, 3-methyl-2-oxobutanoic acid, 4-methyl-2-oxopentanoic acid, and 2-oxo-2-phenylacetic acid, were investigated by proton and carbon nuclear magnetic resonance spectrometry, at constant ionic strength, 0.15, and 25 °C. Dissociation constants for the oxo (pKa(oxo)) and hydrated (pKa(hyd)) acids of each compound were estimated from the change in the degree of hydration with changes in pH and directly from the changes in chemical shifts of various hydrogen and carbons nuclei with pH. α-Keto acids showed greater hydration in their acidic forms than their carboxylate forms. The degree of hydration was sensitive to steric and electronic/resonance factors. As expected, the oxo forms of the acids were stronger acids compared with their hydrated analogs, and their dissociation constants were also sensitive to steric and electronic factors.

  20. Structures, Hydration, and Electrical Mobilities of Bisulfate Ion-Sulfuric Acid-Ammonia/Dimethylamine Clusters: A Computational Study.

    PubMed

    Tsona, Narcisse T; Henschel, Henning; Bork, Nicolai; Loukonen, Ville; Vehkamäki, Hanna

    2015-09-17

    Despite the well-established role of small molecular clusters in the very first steps of atmospheric particle formation, their thermochemical data are still not completely available due to limitation of the experimental techniques to treat such small clusters. We have investigated the structures and the thermochemistry of stepwise hydration of clusters containing one bisulfate ion, sulfuric acid, base (ammonia or dimethylamine), and water molecules using quantum chemical methods. We found that water facilitates proton transfer from sulfuric acid or the bisulfate ion to the base or water molecules, and depending on the hydration level, the sulfate ion was formed in most of the base-containing clusters. The calculated hydration energies indicate that water binds more strongly to ammonia-containing clusters than to dimethylamine-containing and base-free clusters, which results in a wider hydrate distribution for ammonia-containing clusters. The electrical mobilities of all clusters were calculated using a particle dynamics model. The results indicate that the effect of humidity is negligible on the electrical mobilities of molecular clusters formed in the very first steps of atmospheric particle formation. The combination of the results of this study with those previously published on the hydration of neutral clusters by our group provides a comprehensive set of thermochemical data on neutral and negatively charged clusters containing sulfuric acid, ammonia, or dimethylamine.

  1. Unmasking the Action of Phosphinous Acid Ligands in Nitrile Hydration Reactions Catalyzed by Arene-Ruthenium(II) Complexes.

    PubMed

    Tomás-Mendivil, Eder; Cadierno, Victorio; Menéndez, María I; López, Ramón

    2015-11-16

    The catalytic hydration of benzonitrile and acetonitrile has been studied by employing different arene-ruthenium(II) complexes with phosphinous (PR2OH) and phosphorous acid (P(OR)2OH) ligands as catalysts. Marked differences in activity were found, depending on the nature of both the P-donor and η(6)-coordinated arene ligand. Faster transformations were always observed with the phosphinous acids. DFT computations unveiled the intriguing mechanism of acetonitrile hydration catalyzed by these arene-ruthenium(II) complexes. The process starts with attack on the nitrile carbon atom of the hydroxyl group of the P-donor ligand instead of on a solvent water molecule, as previously suggested. The experimental results presented herein for acetonitrile and benzonitrile hydration catalyzed by different arene-ruthenium(II) complexes could be rationalized in terms of such a mechanism.

  2. Radiation-sensitive indicator based on radiation-chemical formation of acids in polyvinyl butyral films containing chloral hydrate

    NASA Astrophysics Data System (ADS)

    Abdel-Fattah, Atef A.; El-Kelany, M.

    1998-03-01

    Radiation-sensitive indicators based on dyed polyvinyl butyral (PVB) containing acid-sensitive dye (bromophenol blue, BPB) and chloral hydrate (CCl 3CH(OH) 2, 2,2,2-trichloroethane-1, 1-diol) have been developed. These plastic film dosimeters undergo colour change from blue (the alkaline form of BPB) to yellow (the acidic form of BPB), indicating acid formation. The concentration of radiation-formed acids in the films containing different concentrations of chloral hydrate was calculated at different doses. The kinetics of the acid-formation reaction is discussed, indicating a half-order reaction with respect to chloral hydrate concentration. These films can be used as dosimeters for food irradiation applications where the maxima of the useful dose ranges are between 1 and 4 kGy depending on chloral hydrate concentration in the film. The response of these films depends on temperature during irradiation; therefore a correction should be applied. These films have the advantage of negligible humidity effects on response in the intermediate range of relative humidity from 10 to 70% as well as good post-irradiation stability when stored in the dark at room temperature.

  3. Deciphering the role of charge, hydration, and hydrophobicity for cytotoxic activities and membrane interactions of bile acid based facial amphiphiles.

    PubMed

    Singh, Manish; Singh, Ashima; Kundu, Somanath; Bansal, Sandhya; Bajaj, Avinash

    2013-08-01

    We synthesized four cationic bile acid based facial amphiphiles featuring trimethyl ammonium head groups. We evaluated the role of these amphiphiles for cytotoxic activities against colon cancer cells and their membrane interactions by varying charge, hydration and hydrophobicity. The singly charged cationic Lithocholic acid based amphiphile (LCA-TMA1) is most cytotoxic, whereas the triply charged cationic Cholic acid based amphiphile (CA-TMA3) is least cytotoxic. Light microscopy and Annexin-FITC assay revealed that these facial amphiphiles caused late apoptosis. In addition, we studied the interactions of these amphiphiles with model membrane systems by Prodan-based hydration, DPH-based anisotropy, and differential scanning calorimetry. LCA-TMA1 is most hydrophobic with a hard charge causing efficient dehydration and maximum perturbations of membranes thereby facilitating translocation and high cytotoxicity against colon cancer cells. In contrast, the highly hydrated and multiple charged CA-TMA3 caused least membrane perturbations leading to low translocation and less cytotoxicity. As expected, Chenodeoxycholic acid and Deoxycholic acid based amphiphiles (CDCA-TMA2, DCA-TMA2) featuring two charged head groups showed intermediate behavior. Thus, we deciphered that charge, hydration, and hydrophobicity of these amphiphiles govern membrane interactions, translocation, and resulting cytoxicity against colon cancer cells.

  4. Amino acids generated from hydrated Titan tholins: Comparison with Miller-Urey electric discharge products

    NASA Astrophysics Data System (ADS)

    Cleaves, H. James; Neish, Catherine; Callahan, Michael P.; Parker, Eric; Fernández, Facundo M.; Dworkin, Jason P.

    2014-07-01

    Various analogues of Titan haze particles (termed ‘tholins’) have been made in the laboratory. In certain geologic environments on Titan, these haze particles may come into contact with aqueous ammonia (NH3) solutions, hydrolyzing them into molecules of astrobiological interest. A Titan tholin analogue hydrolyzed in aqueous NH3 at room temperature for 2.5 years was analyzed for amino acids using highly sensitive ultra-high performance liquid chromatography coupled with fluorescence detection and time-of-flight mass spectrometry (UHPLC-FD/ToF-MS) analysis after derivatization with a fluorescent tag. We compare here the amino acids produced from this reaction sequence with those generated from room temperature Miller-Urey (MU) type electric discharge reactions. We find that most of the amino acids detected in low temperature MU CH4/N2/H2O electric discharge reactions are generated in Titan simulation reactions, as well as in previous simulations of Triton chemistry. This argues that many processes provide very similar mixtures of amino acids, and possibly other types of organic compounds, in disparate environments, regardless of the order of hydration. Although it is unknown how life began, it is likely that given reducing conditions, similar materials were available throughout the early Solar System and throughout the universe to facilitate chemical evolution.

  5. Amino Acids Generated from Hydrated Titan Tholins: Comparison with Miller-Urey Electric Discharge Products

    NASA Technical Reports Server (NTRS)

    Cleaves, H. James, II; Neish, Catherine; Callahan, Michael P.; Parker, Eric; Fernandez, Facundo M.; Dworkin, Jason P.

    2014-01-01

    Various analogues of Titan haze particles (termed tholins) have been made in the laboratory. In certain geologic environments on Titan, these haze particles may come into contact with aqueous ammonia (NH3) solutions, hydrolyzing them into molecules of astrobiological interest. A Titan tholin analogue hydrolyzed in aqueous NH3 at room temperature for 2.5 years was analyzed for amino acids using highly sensitive ultra-high performance liquid chromatography coupled with fluorescence detection and time-of-flight mass spectrometry (UHPLC-FDToF-MS) analysis after derivatization with a fluorescent tag. We compare here the amino acids produced from this reaction sequence with those generated from room temperature Miller-Urey (MU) type electric discharge reactions. We find that most of the amino acids detected in low temperature MU CH4N2H2O electric discharge reactions are generated in Titan simulation reactions, as well as in previous simulations of Triton chemistry. This argues that many processes provide very similar mixtures of amino acids, and possibly other types of organic compounds, in disparate environments, regardless of the order of hydration. Although it is unknown how life began, it is likely that given reducing conditions, similar materials were available throughout the early Solar System and throughout the universe to facilitate chemical evolution.

  6. Infrared and density functional theory studies of formic acid hydrate clusters in noble gas matrices

    NASA Astrophysics Data System (ADS)

    Ito, Fumiyuki

    2016-08-01

    Infrared absorption spectra of formic acid hydrate clusters (HCOOH)m(H2O)n have been measured in noble gas matrices (Ar and Kr). The concentration dependence of the spectra and the comparison with a previous experimental study on HCOOH(H2O) and HCOOH(H2O)2 [Geoge et al., Spectrochim. Acta, Part A 60 (2004) 3225] led to the identification of large clusters. Density functional theory calculations at the B3LYP-DCP/6-31+G(2d,2p) level were carried out to determine the anharmonic vibrational properties of the clusters, enabling a consistent assignment of the observed vibrational peaks to specific clusters.

  7. Nature's starships. I. Observed abundances and relative frequencies of amino acids in meteorites

    SciTech Connect

    Cobb, Alyssa K.; Pudritz, Ralph E. E-mail: pudritz@physics.mcmaster.ca

    2014-03-10

    The class of meteorites called carbonaceous chondrites are examples of material from the solar system which have been relatively unchanged from the time of their initial formation. These meteorites have been classified according to the temperatures and physical conditions of their parent planetesimals. We collate available data on amino acid abundance in these meteorites and plot the concentrations of different amino acids for each meteorite within various meteorite subclasses. We plot average concentrations for various amino acids across meteorites separated by subclass and petrologic type. We see a predominance in the abundance and variety of amino acids in CM2 and CR2 meteorites. The range in temperature corresponding to these subclasses indicates high degrees of aqueous alteration, suggesting aqueous synthesis of amino acids. Within the CM2 and CR2 subclasses, we identify trends in relative frequencies of amino acids to investigate how common amino acids are as a function of their chemical complexity. These two trends (total abundance and relative frequencies) can be used to constrain formation parameters of amino acids within planetesimals. Our organization of the data supports an onion shell model for the temperature structure of planetesimals. The least altered meteorites (type 3) and their amino acids originated near cooler surface regions. The most active amino acid synthesis likely took place at intermediate depths (type 2). The most altered materials (type 1) originated furthest toward parent body cores. This region is likely too hot to either favor amino acid synthesis or for amino acids to be retained after synthesis.

  8. Proton transport in triflic acid hydrates studied via path integral car-parrinello molecular dynamics.

    PubMed

    Hayes, Robin L; Paddison, Stephen J; Tuckerman, Mark E

    2009-12-31

    The mono-, di-, and tetrahydrates of trifluoromethanesulfonic acid, which contain characteristic H(3)O(+), H(5)O(2)(+), and H(9)O(4)(+) structures, provide model systems for understanding proton transport in materials with high perfluorosulfonic acid density such as perfluorosulfonic acid membranes commonly employed in hydrogen fuel cells. Ab initio molecular dynamics simulations indicate that protons in these solids are predisposed to transfer to the water most strongly bound to sulfonate groups via a Grotthuss-type mechanism, but quickly return to the most solvated defect structure either due to the lack of a nearby species to stabilize the new defect or a preference for the proton to be maximally hydrated. Path integral molecular dynamics of the mono- and dihydrate reveal significant quantum effects that facilitate proton transfer to the "presolvated" water or SO(3)(-) in the first solvation shell and increase the Zundel character of all the defects. These trends are quantified in free energy profiles for each bonding environment. Hydrogen bonding criteria for HOH-OH(2) and HOH-O(3)S are extracted from the two-dimensional potential of mean force. The quantum radial distribution function, radius of gyration, and root-mean-square displacement position correlation function show that the protonic charge is distributed over two or more water molecules. Metastable structural defects with one excess proton shared between two sulfonate groups and another Zundel or Eigen type cation defect are found for the mono- and dihydrate but not for the tetrahydrate crystal. Results for the tetrahydrate native crystal exhibit minor differences at 210 and 250 K. IR spectra are calculated for all native and stable defect structures. Graph theory techniques are used to characterize the chain lengths and ring sizes in the hydrogen bond network. Low conductivities when limited water is present may be attributable to trapping of protons between SO(3)(-) groups and the increased

  9. Betaine 0.77-perhydrate 0.23-hydrate and common structural motifs in crystals of amino acid perhydrates.

    PubMed

    Minkov, Vasily S; Kapustin, Evgeny A; Boldyreva, Elena V

    2013-04-01

    The title compound, betaine 0.77-perhydrate 0.23-hydrate, (CH3)3N(+)CH2COO(-)·0.77H2O2·0.23H2O, crystallizes in the orthorhombic noncentrosymmetric space group Pca2(1). Chiral molecules of hydrogen peroxide are positionally disordered with water molecules in a ratio of 0.77:0.23. Betaine, 2-(trimethylazaniumyl)acetate, preserves its zwitterionic state, with a positively charged ammonium group and a negatively charged carboxylate group. The molecular conformation of betaine here differs from the conformations of both anhydrous betaine and its hydrate, mainly in the orientation of the carboxylate group with respect to the C-C-N skeleton. Hydrogen peroxide is linked via two hydrogen bonds to carboxylate groups, forming infinite chains along the crystallographic a axis, which are very similar to those in the crystal structure of betaine hydrate. The present work contributes to the understanding of the structure-forming factors for amino acid perhydrates, which are presently attracting much attention. A correlation is suggested between the ratio of amino acid zwitterions and hydrogen peroxide in the unit cell and the structural motifs present in the crystal structures of all currently known amino acids perhydrates. This can help to classify the crystal structures of amino acid perhydrates and to design new crystal structures.

  10. Number of free hydroxyl groups on bile acid phospholipids determines the fluidity and hydration of model membranes.

    PubMed

    Sreekanth, Vedagopuram; Bajaj, Avinash

    2013-10-10

    Interactions of synthetic phospholipids with model membranes determines the drug release capabilities of phospholipid vesicles at diseased sites. We performed 1,6-diphenyl-1,3,5-hexatriene (DPH)-based fluorescence anisotropy, Laurdan-based membrane hydration, and differential scanning calorimetry (DSC) studies to cognize the interactions of three bile acid phospholipids, lithocholic acid-phosphocholine (LCA-PC), deoxycholic acid-phosphocholine (DCA-PC), and cholic acid-phosphocholine (CA-PC) with model membranes. These studies revealed that bile acid phospholipids increases membrane fluidity in DCA-PC > CA-PC > LCA-PC order, indicating that induction of membrane fluidity is contingent on the number and positioning of free hydroxyl groups on bile acids. Similarly, DCA-PC causes maximum membrane perturbations due to the presence of a free hydroxyl group, whereas LCA-PC induces gel phase in membranes due to hydrophobic bile acid acyl chain interactions. These DCA-PC-induced membrane perturbations induce a drastic decrease in phase transition temperature (Tm) as determined by calorimetric studies, whereas doping of LCA-PC causes phase transition broadening without change in Tm. Doping of CA-PC induces membrane perturbations and membrane hydration like DCA-PC but sharpening of phase transition at higher doping suggests self-association of CA-PC molecules. Therefore these differential mode of interactions between bile acid phospholipids and model membranes would help in the future for their use in drug delivery.

  11. Vibrational analysis of amino acids and short peptides in hydrated media. I. L-glycine and L-leucine.

    PubMed

    Derbel, Najoua; Hernández, Belén; Pflüger, Fernando; Liquier, Jean; Geinguenaud, Frédéric; Jaïdane, Nejmeddine; Lakhdar, Zohra Ben; Ghomi, Mahmoud

    2007-02-15

    Raman scattering and Fourier-transform infrared (FT-IR) attenuated transmission reflectance (ATR) spectra of two alpha-amino acids (alpha-AAs), i.e., glycine and leucine, were measured in H2O and D2O (at neutral pH and pD). This series of observed vibrational data gave us the opportunity to analyze vibrational features of both AAs in hydrated media by density functional theory (DFT) calculations at the B3LYP/6-31++G* level. Harmonic vibrational modes calculated after geometry optimization on the clusters containing each AA and 12 surrounding water molecules, which represent primary models for hydration scheme of amino acids, allowed us to assign the main observed peaks.

  12. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    PubMed

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.

  13. 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.

  14. 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.

  15. Combined Effects of Ocean Warming and Acidification on Copepod Abundance, Body Size and Fatty Acid Content.

    PubMed

    Garzke, Jessica; Hansen, Thomas; Ismar, Stefanie M H; Sommer, Ulrich

    2016-01-01

    Concerns about increasing atmospheric CO2 concentrations and global warming have initiated studies on the consequences of multiple-stressor interactions on marine organisms and ecosystems. We present a fully-crossed factorial mesocosm study and assess how warming and acidification affect the abundance, body size, and fatty acid composition of copepods as a measure of nutritional quality. The experimental set-up allowed us to determine whether the effects of warming and acidification act additively, synergistically, or antagonistically on the abundance, body size, and fatty acid content of copepods, a major group of lower level consumers in marine food webs. Copepodite (developmental stages 1-5) and nauplii abundance were antagonistically affected by warming and acidification. Higher temperature decreased copepodite and nauplii abundance, while acidification partially compensated for the temperature effect. The abundance of adult copepods was negatively affected by warming. The prosome length of copepods was significantly reduced by warming, and the interaction of warming and CO2 antagonistically affected prosome length. Fatty acid composition was also significantly affected by warming. The content of saturated fatty acids increased, and the ratios of the polyunsaturated essential fatty acids docosahexaenoic- (DHA) and arachidonic acid (ARA) to total fatty acid content increased with higher temperatures. Additionally, here was a significant additive interaction effect of both parameters on arachidonic acid. Our results indicate that in a future ocean scenario, acidification might partially counteract some observed effects of increased temperature on zooplankton, while adding to others. These may be results of a fertilizing effect on phytoplankton as a copepod food source. In summary, copepod populations will be more strongly affected by warming rather than by acidifying oceans, but ocean acidification effects can modify some temperature impacts.

  16. Combined Effects of Ocean Warming and Acidification on Copepod Abundance, Body Size and Fatty Acid Content

    PubMed Central

    Hansen, Thomas; Ismar, Stefanie M. H.; Sommer, Ulrich

    2016-01-01

    Concerns about increasing atmospheric CO2 concentrations and global warming have initiated studies on the consequences of multiple-stressor interactions on marine organisms and ecosystems. We present a fully-crossed factorial mesocosm study and assess how warming and acidification affect the abundance, body size, and fatty acid composition of copepods as a measure of nutritional quality. The experimental set-up allowed us to determine whether the effects of warming and acidification act additively, synergistically, or antagonistically on the abundance, body size, and fatty acid content of copepods, a major group of lower level consumers in marine food webs. Copepodite (developmental stages 1–5) and nauplii abundance were antagonistically affected by warming and acidification. Higher temperature decreased copepodite and nauplii abundance, while acidification partially compensated for the temperature effect. The abundance of adult copepods was negatively affected by warming. The prosome length of copepods was significantly reduced by warming, and the interaction of warming and CO2 antagonistically affected prosome length. Fatty acid composition was also significantly affected by warming. The content of saturated fatty acids increased, and the ratios of the polyunsaturated essential fatty acids docosahexaenoic- (DHA) and arachidonic acid (ARA) to total fatty acid content increased with higher temperatures. Additionally, here was a significant additive interaction effect of both parameters on arachidonic acid. Our results indicate that in a future ocean scenario, acidification might partially counteract some observed effects of increased temperature on zooplankton, while adding to others. These may be results of a fertilizing effect on phytoplankton as a copepod food source. In summary, copepod populations will be more strongly affected by warming rather than by acidifying oceans, but ocean acidification effects can modify some temperature impacts. PMID:27224476

  17. Olefin hydration

    SciTech Connect

    Butt, M.H.D.; Waller, F.J.

    1993-08-03

    An improved process for the hydration of olefins to alcohols is described wherein the improvement comprises contacting said olefins with the catalytic composition comprising a perfluorinated ion-exchange polymer containing sulfonic acid groups supported on an inert carrier wherein said carrier comprises calcined shot coke with a mean pore diameter of about 1,000 Angstroms in the presence of water at a temperature of from about 180 C to about 250 C.

  18. Acid attack on hydrated cement — Effect of mineral acids on the degradation process

    SciTech Connect

    Gutberlet, T.; Hilbig, H.; Beddoe, R.E.

    2015-08-15

    During acid attack on concrete structural components, a degraded layer develops whose properties as a protective barrier are decisive for durability. {sup 29}Si NMR spectroscopy and {sup 27}Al NMR spectroscopy were used with XRD to investigate the degraded layer on hardened cement paste exposed to HCl and H{sub 2}SO{sub 4}. The layer comprises an amorphous silica gel with framework silicates, geminate and single silanol groups in which Si is substituted by Al. Amorphous Al(OH){sub 3} and Fe(OH){sub 3} are present. The gel forms by polycondensation and cross-linking of C-A-S-H chains at AlO{sub 4} bridging tetrahedra. In the transition zone between the degraded layer and the undamaged material, portlandite dissolves and Ca is removed from the C-A-S-H phases maintaining their polymer structure at first. With HCl, monosulphate in the transition zone is converted into Friedel's salt and ettringite. With H{sub 2}SO{sub 4}, gypsum precipitates near the degradation front reducing the thickness of the transition zone and the rate of degradation.

  19. Reduced nitrification and abundance of ammonia-oxidizing bacteria in acidic soil amended with biochar.

    PubMed

    Wang, Zhenyu; Zong, Haiying; Zheng, Hao; Liu, Guocheng; Chen, Lei; Xing, Baoshan

    2015-11-01

    Adding biochar into soils has potential to manipulate soil nitrification process due to its impacts on nitrogen (N) cycling, however, the exact mechanisms underlying the alteration of nitrification process in soils are still not clear. Nitrification in an acidic orchard soil amended with peanut shell biochar (PBC) produced at 400 °C was investigated. Nitrification was weakened by PBC addition due to the decreased NH4(+)-N content and reduced ammonia-oxidizing bacteria (AOB) abundance in PBC-amended soils. Adding phenolic compounds (PHCs) free biochar (PBC-P) increased the AOB abundance and the DGGE band number, indicating that PHCs remaining in the PBC likely reduced AOB abundance and diversity. However, PBC addition stimulated rape growth and increased N bioavailability. Overall, adding PBC could suppress the nitrification process and improve N bioavailability in the agricultural soils, and thus possibly mitigate the environmental negative impacts and improving N use efficiency in the acidic soils added with N fertilizer.

  20. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    PubMed

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  1. Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-acetic-acid in Organomodified Montmorillonite

    NASA Astrophysics Data System (ADS)

    Tian, Haoting; Gao, Juan; Li, Hui; Boyd, Stephen A.; Gu, Cheng

    2016-09-01

    Here we describe a unique process that achieves complete defluorination and decomposition of perfluorinated compounds (PFCs) which comprise one of the most recalcitrant and widely distributed classes of toxic pollutant chemicals found in natural environments. Photogenerated hydrated electrons derived from 3-indole-acetic-acid within an organomodified clay induce the reductive defluorination of co-sorbed PFCs. The process proceeds to completion within a few hours under mild reaction conditions. The organomontmorillonite clay promotes the formation of highly reactive hydrated electrons by stabilizing indole radical cations formed upon photolysis, and prevents their deactivation by reaction with protons or oxygen. In the constrained interlayer regions of the clay, hydrated electrons and co-sorbed PFCs are brought in close proximity thereby increasing the probability of reaction. This novel green chemistry provides the basis for in situ and ex situ technologies to treat one of the most troublesome, recalcitrant and ubiquitous classes of environmental contaminants, i.e., PFCs, utilizing innocuous reagents, naturally occurring materials and mild reaction conditions.

  2. Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-acetic-acid in Organomodified Montmorillonite

    PubMed Central

    Tian, Haoting; Gao, Juan; Li, Hui; Boyd, Stephen A.; Gu, Cheng

    2016-01-01

    Here we describe a unique process that achieves complete defluorination and decomposition of perfluorinated compounds (PFCs) which comprise one of the most recalcitrant and widely distributed classes of toxic pollutant chemicals found in natural environments. Photogenerated hydrated electrons derived from 3-indole-acetic-acid within an organomodified clay induce the reductive defluorination of co-sorbed PFCs. The process proceeds to completion within a few hours under mild reaction conditions. The organomontmorillonite clay promotes the formation of highly reactive hydrated electrons by stabilizing indole radical cations formed upon photolysis, and prevents their deactivation by reaction with protons or oxygen. In the constrained interlayer regions of the clay, hydrated electrons and co-sorbed PFCs are brought in close proximity thereby increasing the probability of reaction. This novel green chemistry provides the basis for in situ and ex situ technologies to treat one of the most troublesome, recalcitrant and ubiquitous classes of environmental contaminants, i.e., PFCs, utilizing innocuous reagents, naturally occurring materials and mild reaction conditions. PMID:27608658

  3. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-06-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  4. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-01-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  5. Links between Ammonia Oxidizer Community Structure, Abundance, and Nitrification Potential in Acidic Soils ▿ †

    PubMed Central

    Yao, Huaiying; Gao, Yangmei; Nicol, Graeme W.; Campbell, Colin D.; Prosser, James I.; Zhang, Limei; Han, Wenyan; Singh, Brajesh K.

    2011-01-01

    Ammonia oxidation is the first and rate-limiting step of nitrification and is performed by both ammonia-oxidizing archaea (AOA) and bacteria (AOB). However, the environmental drivers controlling the abundance, composition, and activity of AOA and AOB communities are not well characterized, and the relative importance of these two groups in soil nitrification is still debated. Chinese tea orchard soils provide an excellent system for investigating the long-term effects of low pH and nitrogen fertilization strategies. AOA and AOB abundance and community composition were therefore investigated in tea soils and adjacent pine forest soils, using quantitative PCR (qPCR), terminal restriction fragment length polymorphism (T-RFLP) and sequence analysis of respective ammonia monooxygenase (amoA) genes. There was strong evidence that soil pH was an important factor controlling AOB but not AOA abundance, and the ratio of AOA to AOB amoA gene abundance increased with decreasing soil pH in the tea orchard soils. In contrast, T-RFLP analysis suggested that soil pH was a key explanatory variable for both AOA and AOB community structure, but a significant relationship between community abundance and nitrification potential was observed only for AOA. High potential nitrification rates indicated that nitrification was mainly driven by AOA in these acidic soils. Dominant AOA amoA sequences in the highly acidic tea soils were all placed within a specific clade, and one AOA genotype appears to be well adapted to growth in highly acidic soils. Specific AOA and AOB populations dominated in soils at particular pH values and N content, suggesting adaptation to specific niches. PMID:21571885

  6. Biosynthesis of gallic acid in Rhus typhina: discrimination between alternative pathways from natural oxygen isotope abundance.

    PubMed

    Werner, Roland A; Rossmann, Andreas; Schwarz, Christine; Bacher, Adelbert; Schmidt, Hanns-Ludwig; Eisenreich, Wolfgang

    2004-10-01

    The biosynthetic pathway of gallic acid in leaves of Rhus typhina is studied by oxygen isotope ratio mass spectrometry at natural oxygen isotope abundance. The observed delta18O-values of gallic acid indicate an 18O-enrichment of the phenolic oxygen atoms of more than 30 per thousand above that of the leaf water. This enrichment implies biogenetical equivalence with oxygen atoms of carbohydrates but not with oxygen atoms introduced by monooxygenase activation of molecular oxygen. It can be concluded that all phenolic oxygen atoms of gallic acid are retained from the carbohydrate-derived precursor 5-dehydroshikimate. This supports that gallic acid is synthesized entirely or predominantly by dehydrogenation of 5-dehydroshikimate.

  7. Analysis of Carbohydrate and Fatty Acid Marker Abundance in Ricin Toxin Preparations for Forensic Information

    SciTech Connect

    Colburn, Heather A.; Wunschel, David S.; Kreuzer-Martin, Helen W.; Moran, James J.; Antolick, Kathryn C.; Melville, Angela M.

    2010-07-15

    One challenge in the forensic analysis of ricin samples is determining the method and extent of sample preparation. Ricin purification from the source castor seeds is essentially a protein purification through removal of the non-protein fractions of the seed. Two major, non-protein constituents in the seed are the castor oil and carbohydrates. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil, which comprises roughly half the seed weight. The carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. We used derivatization of carbohydrate and fatty acid markers followed by identification and quantification using gas chromatography/mass spectrometry (GC/MS) to assess compositional changes in ricin samples purified by different methods. The loss of ricinoleic acid indicated steps for oil removal had occurred. Changes to the carbohydrate content of the sample were also observed following protein precipitation. The differential loss of arabinose relative to mannose indicated removal of the major carbohydrate fraction of the seed and enrichment of the protein content. Taken together, these changes in fatty acid and carbohydrate abundance are indicative of the preparation method used for each sample.

  8. CO2-Selective Absorbents in Air: Reverse Lipid Bilayer Structure Forming Neutral Carbamic Acid in Water without Hydration.

    PubMed

    Inagaki, Fuyuhiko; Matsumoto, Chiaki; Iwata, Takashi; Mukai, Chisato

    2017-04-05

    Emission gas and air contain not only CO2 but also plentiful moisture, making it difficult to achieve selective CO2 absorption without hydration. To generate absorbed CO2 (wet CO2) under heating, the need for external energy to release the absorbed water has been among the most serious problems in the fields of carbon dioxide capture and storage (CCS) and direct air capture (DAC). We found that the introduction of the hydrophobic phenyl group into alkylamines of CO2 absorbents improved the absorption selectivity between CO2 and water. Furthermore, ortho-, meta-, and para-xylylenediamines (OXDA, MXDA, PXDA, respectively) absorbed only CO2 in air without any hydration. Notably, MXDA·CO2 was formed as an anhydrous carbamic acid even in water, presumably because it was covered with hydrophobic phenyl groups, which induces a reverse lipid bilayer structure. Dry CO2 was obtained from heating MXDA·CO2 at 103-120 °C, which was revealed to involve chemically the Grignard reaction to form the resulting carboxylic acids in high yields.

  9. [Seasonality and contribution to acid rain of the carbon abundance in rainwater].

    PubMed

    Xu, Tao; Song, Zhi-guang; Liu, Jun-feng; Wang, Cui-ping

    2008-02-01

    This paper reports the results from a study of the carbon abundance in rainwater of Guangzhou city, China. The determination of TOC, DOC, POC and PEC helps to study the seasonality of carbon abundance and its contribution to the acid rain. The results display the fact that the average contents of TOC, DOC, POC and PEC are 7.10 mg/L, 3.58 mg/L, 3.60 mg/L and 0.72 mg/L, respectively. These results confirm the deep effect of the organic pollutant to the rain. The seasonality exists in the carbon abundance of rainwater. The contents of TOC and DOC are up to the maximum in spring and the minimum in summer; the contribution of POC to TOC in summer is obviously higher than that in other seasons; and the relative content of POC is clearly higher in dry season than that in wet season. The seasonality reflects the more emission of the total pollutant in spring and the solid particle pollutant in summer than those in other seasons. Moreover, the emission of the organic pollutant from the mobile vehicles is more obvious in dry season than that in wet season. The contents of TOC and DOC have the negative correlation to the pH values, which confirms the contribution effect of the organic pollutant, such as vehicle emission, to the acid rain.

  10. In vivo oocyte hydration in Atlantic halibut (Hippoglossus hippoglossus); proteolytic liberation of free amino acids, and ion transport, are driving forces for osmotic water influx.

    PubMed

    Finn, Roderick Nigel; Østby, Gunn C; Norberg, Birgitta; Fyhn, Hans Jørgen

    2002-01-01

    The in vivo swelling and hydration of maturing oocytes of Atlantic halibut Hippoglossus hippoglossus were studied in order to characterise the osmotic mechanism underlying oocyte hydration in oviparous marine teleosts that spawn pelagic eggs. Sequential biopsies from two females, spanning four hydration cycles, were examined by osmometry, solute analysis and electrophoresis of dissected hydrating oocytes and ovulated eggs. The hydration cycle of the biopsied halibuts lasted 33-54 h. The majority of ovarian oocytes existed in a pre-hydrated condition (individual wet mass approx. 3.7 mg, diameter approx. 1.87 mm, 63 % H(2)O) with easily visible, non-coalesced, yolk platelets. Group-synchronous batches of the pre-hydrated oocytes increased in individual wet mass, diameter and water content to reach the ovulated egg stage of approximately 15 mg, 3.0 mm and 90 % H(2)O, respectively. The yolk osmolality of the hydrating oocytes was transiently hyperosmotic to the ovarian fluid (range 305-350 mOsmol l(-1)) with a peak osmolality of about 450 mOsmol l(-1) in oocytes of 6-8 mg individual wet mass. The transient hyperosmolality was well accounted for by the increase in oocyte content of free amino acids (FAAs; approx. 2300 nmol oocyte(-1)), K(+) (approx. 750 nmol oocyte(-1)), Cl(-) (approx. 900 nmol oocyte(-1)), total ammonium (approx. 300 nmol oocyte(-1)) and inorganic phosphate (P(i); approx. 200 nmol oocyte(-1)) when relating to the increase in cellular water. The oocyte content of Na(+) did not increase during the hydration phase. Extensive proteolysis of yolk proteins, in particular a 110 kDa protein, correlated with the increase in the FAA pool, although the latter increased by approx. 20 % more than could be accounted for by the decrease in the oocyte protein content. Both indispensable and dispensable amino acids increased in the FAA pool, and particularly serine, alanine, leucine, lysine, glutamine and glutamate. Taurine content remained stable at approx. 70 nmol

  11. A toy model of prebiotic peptide evolution: the possible role of relative amino acid abundances.

    PubMed

    Polanco, Carlos; Buhse, Thomas; Samaniego, José Lino; Castañón González, Jorge Alberto

    2013-01-01

    This paper presents a mathematical-computational toy model based on the assumed dynamic principles of prebiotic peptide evolution. Starting from a pool of amino acid monomers, the model describes in a generalized manner the generation of peptides and their sequential information. The model integrates the intrinsic and dynamic key elements of the initiation of biopolymerization, such as the relative amino acid abundances and polarities, as well as the oligomer reversibility, i.e. fragmentation and recombination, and peptide self-replication. Our modeling results suggest that the relative amino acid abundances, as indicated by Miller-Urey type electric discharge experiments, played a principal role in the early sequential information of peptide profiles. Moreover, the computed profiles display an astonishing similarity to peptide profiles observed in so-called biological common ancestors found in the following three microorganisms; E. coli, M. jannaschii, and S. cereviasiae. The prebiotic peptide fingerprint was obtained by the so-called polarity index method that was earlier reported as a tool for the identification of cationic amphipathic antibacterial short peptides.

  12. Distinctive lipid composition of the copepod Limnocalanus macrurus with a high abundance of polyunsaturated fatty acids.

    PubMed

    Hiltunen, Minna; Strandberg, Ursula; Keinänen, Markku; Taipale, Sami; Kankaala, Paula

    2014-09-01

    We studied the copepod Limnocalanus macrurus for seasonal variation in the composition of fatty acids, wax esters and sterols in large boreal lakes, where it occurs as a glacial-relict. Vast wax ester reserves of Limnocalanus were accumulated in a period of only two months, and comprised mono- and polyunsaturated fatty acids (PUFA) and saturated fatty alcohols. In winter, the mobilization of wax esters was selective, and the proportion of long-chain polyunsaturated wax esters declined first. PUFA accounted for >50% of all fatty acids throughout the year reaching up to ca. 65% during late summer and fall. Long-chain PUFA 20:5n-3 and 22:6n-3 together comprised 17-40% of all fatty acids. The rarely reported C24 and C26 very-long-chain PUFA (VLC-PUFA) comprised 6.2 ± 3.4 % of all fatty acids in August and 2.1 ± 1.7% in September. The VLC-PUFA are presumably synthesized by Limnocalanus from shorter chain-length precursors because they were not found in the potential food sources. We hypothesize that these VLC-PUFA help Limnocalanus to maximize lipid reserves when food is abundant. Sterol content of Limnocalanus, consisting ca. 90% of cholesterol, did not show great seasonal variation. As a lipid-rich copepod with high abundance of PUFA, Limnocalanus is excellent quality food for fish. The VLC-PUFA were also detected in planktivorous fish, suggesting that these compounds can be used as a trophic marker indicating feeding on Limnocalanus.

  13. Molecular structures of N-ethylpiperidine betaine hydrate and its 1:1 complex with squaric acid

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Dutkiewicz, G.; Kosturkiewicz, Z.; Szafran, M.

    2013-12-01

    N-ethylpiperidine betaine, (N-carboxymethyl-N-ethylpiperidinium inner salt, EtPB) crystallizes as a hydrate. EtPB and water molecules are bonded by intermolecular OH⋯O hydrogen bonds of 2.817(1) and 2.863(1) Å, into a centrosymmetric dimer, in which only one carboxylate oxygen atom is involved in H-bonds formation. In the complex of EtPB with squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione, H2SQ) both carboxylate oxygen atoms are engaged in the hydrogen bonds which links molecules through two short, non-symmetric OH⋯O hydrogen bonds of 2.489(1) and 2.500(1) Å. The preferences of the conformation of the EtPB unit in the hydrogen bond formation have been studied by X-ray diffraction, FTIR and NMR spectroscopy and the results are supported by DFT calculations. EtPB, in hydrate and in the complex, has a chair conformation with the CH3CH2 group in the axial position and the CH2COO substituent in the equatorial position.

  14. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

    SciTech Connect

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.

    2009-12-01

    This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate components can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development, one

  15. Aerosol silica as a possible candidate for the heterogeneous formation of nitric acid hydrates in the stratosphere

    NASA Astrophysics Data System (ADS)

    Bogdan, A.; Kulmala, M.

    The liquid-solid phase transitions in nanometersize HNO3/H2O solution droplets obtained on fumed silica (a counterpart of aerosol silica) have been studied with differential scanning calorimetry (DSC). “Soft” transitions, reduction in the freezing and melting temperatures, Tf and Tm, and enthalpies, ΔHf and ΔHm, are interpreted to be caused by very small size of droplets. The observed difference between ΔHf and ΔHm can serve as an evidence of temperature dependence of the enthalpy of fusion for hydrates. Freezing of droplets with stoichiometry close to nitric acid trihydrate (NAT) at temperature 4 K warmer than the ice frost point indicates that, in the stratosphere, silica particles can serve as nuclei for heterogeneous freezing of NAT.

  16. Laboratory Investigation of the Growth and Crystal Structure of Nitric Acid Hydrates by Transmission Electron Microscopy (TEM)

    NASA Technical Reports Server (NTRS)

    Blake, David F.; Chang, Sherwood (Technical Monitor)

    1994-01-01

    A great deal of recent laboratory work has focussed on the characterization of the nitric acid hydrates, thought to be present in type I Polar Stratospheric Clouds (PSCs). Phase relationships and vapor pressure measurements (1-3) and infrared characterizations (4-5) have been made. However, the observed properties of crystalline solids (composition, melting point, vapor pressure, surface reactivity, thermodynamic stability, extent of solid solution with other components, etc.) are controlled by their crystal structure. The only means of unequivocal structural identification for crystalline solids is diffraction (using electrons, X-rays, neutrons, etc.). Other observed properties of crystalline solids, such as their infrared spectra, their vapor pressure as a function of temperature, etc. yield only indirect information about what phases are present, their relative proportions, or whether they are crystalline or amorphous.

  17. 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…

  18. A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers

    SciTech Connect

    Clark II, Jeffrey K.; Paddison, Stephen J.; Eikerling, Michael; Dupuis, Michel; Zawodzinski, Jr., Thomas A.

    2012-03-29

    We compare the role of neighboring group substitutions on proton dissociation of hydrated acidic moieties suitable for proton exchange membranes through electronic structure calculations. Three pairs of ionomers containing similar electron withdrawing groups within the pair were chosen for the study: two fully fluorinated sulfonyl imides (CF3SO2NHSO2CF3 and CF3CF2SO2NHSO2CF3), two partially fluorinated sulfonyl imides (CH3SO2NHSO2CF3 and C6H5SO2NHSO2CF2CF3), and two aromatic sulfonic acid based material s (CH3C6H4SO3H and CH3 OC6 - H3OCH3C6H4SO3H). Fully optimized counterpoise (CP) corrected geometries were obtained for each ionomer fragment with the inclusion of water molecules at the B3LYP/6-311G** level of density functional theory. Spontaneous proton dissociation was observed upon addition of three water molecules in each system, and the transition to a solvent-separated ion pair occurred when four water molecules were introduced. No considerable quantitative or qualitative differences in proton dissociation, hydrogen bond networks formed, or water binding energies were found between systems containing similar electron withdrawing groups. Each of the sulfonyl imide ionomers exhibited qualitatively similar results regarding proton dissociation and separation. The fully fluorinated sulfonyl imides, however, showed a greater propensity to exist in dissociated and ion-pair separated states at low degrees of hydration than the partially fluorinated sulfonyl imides. This effect is due to the additional electron withdrawing groups providing charge stabilization as the dissociated proton migrates away from the imide anion.

  19. A theoretical investigation of the relative stability of hydrated glycine and methylcarbamic acid--from water clusters to interstellar ices.

    PubMed

    Kayi, Hakan; Kaiser, Ralf I; Head, John D

    2012-04-14

    We have theoretically investigated how the low-energy conformers of the neutral and the zwitterionic forms of glycine as well as methylcarbamic acid are stabilized by the presence water. The MP2/6-311++G(d,p) method was utilized to conduct calculations on glycine and methylcarbamic acid in both isolated clusters and in clusters embedded in the conductor-like polarizable continuum model (C-PCM), where the clusters explicitly contain between one and ten water molecules. The neutral forms of glycine and methylcarbamic acid were found to have similar hydration energies, whereas the neutral methylcarbamic acid was determined to be approximately 32 kJ mol(-1) more stable than the neutral glycine in the isolated clusters and 30 kJ mol(-1) more stable in the C-PCM embedded clusters. Both the number and strength of the hydrogen bonding interactions between water and the zwitterions drive the stability. This lowers the relative energy of the glycine zwitterion from 50 kJ mol(-1) above neutral glycine, when there are two water molecules in the clusters to 11 kJ mol(-1) below for the clusters containing ten water molecules. For the methylcarbamic acid clusters with two water molecules, the zwitterion is 51 kJ mol(-1) higher in energy than the neutral form, but it remains 13 kJ mol(-1) above the neutral methylcarbamic acid in the clusters containing ten water molecules. When the bulk water environment is simulated by the C-PCM calculations, we find both the methylcarbamic acid and glycine zwitterionic forms have similar energies at 20 kJ mol(-1) above the neutral methylcarbamic acid energy and 10 kJ mol(-1) lower than the neutral glycine energy. Although neither methylcarbamic acid nor glycine have been detected in the interstellar medium yet, our findings indicate that methylcarbamic acid is the more stable product from methylamine and carbon dioxide reactions in a water ice. This suggests that methylcarbamic acid likely plays a role in the intermediate steps if glycine is

  20. The earthworm Aporrectodea caliginosa stimulates abundance and activity of phenoxyalkanoic acid herbicide degraders

    PubMed Central

    Liu, Ya-Jun; Zaprasis, Adrienne; Liu, Shuang-Jiang; Drake, Harold L; Horn, Marcus A

    2011-01-01

    2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a widely used phenoxyalkanoic acid (PAA) herbicide. Earthworms represent the dominant macrofauna and enhance microbial activities in many soils. Thus, the effect of the model earthworm Aporrectodea caliginosa (Oligochaeta, Lumbricidae) on microbial MCPA degradation was assessed in soil columns with agricultural soil. MCPA degradation was quicker in soil with earthworms than without earthworms. Quantitative PCR was inhibition-corrected per nucleic acid extract and indicated that copy numbers of tfdA-like and cadA genes (both encoding oxygenases initiating aerobic PAA degradation) in soil with earthworms were up to three and four times higher than without earthworms, respectively. tfdA-like and 16S rRNA gene transcript copy numbers in soil with earthworms were two and six times higher than without earthworms, respectively. Most probable numbers (MPNs) of MCPA degraders approximated 4 × 105 gdw−1 in soil before incubation and in soil treated without earthworms, whereas MPNs of earthworm-treated soils were approximately 150 × higher. The aerobic capacity of soil to degrade MCPA was higher in earthworm-treated soils than in earthworm-untreated soils. Burrow walls and 0–5 cm depth bulk soil displayed higher capacities to degrade MCPA than did soil from 5–10 cm depth bulk soil, expression of tfdA-like genes in burrow walls was five times higher than in bulk soil and MCPA degraders were abundant in burrow walls (MPNs of 5 × 107 gdw−1). The collective data indicate that earthworms stimulate abundance and activity of MCPA degraders endogenous to soil by their burrowing activities and might thus be advantageous for enhancing PAA degradation in soil. PMID:20740027

  1. Synthesis, characterization, solubility and stability studies of hydrate cocrystal of antitubercular Isoniazid with antioxidant and anti-bacterial Protocatechuic acid

    NASA Astrophysics Data System (ADS)

    Mashhadi, Syed Muddassir Ali; Yunus, Uzma; Bhatti, Moazzam Hussain; Ahmed, Imtiaz; Tahir, Muhammad Nawaz

    2016-08-01

    Isoniazid is an important component used in "triple therapy" to combat tuberculosis. It has reduced Tabletting formulations stability. Anti-oxidants are obligatory to counter oxidative stress, pulmonary inflammation, and free radical burst from macrophages caused in tuberculosis and other diseases. In the present study a hydrate cocrystal of Isoniazid with anti-oxidant and anti-inflammatory and anti-bacterial Protocatechuic acid (3,4-dihydroxybenzoic acid) in 1:1 is reported. This Cocrystal may have improved tabletting stability and anti-oxidant properties. Cocrystal structure analysis confirmed the existence of pyridine-carboxylic acid synthon in the Cocrystal. Other synthons of different graph sets involving Nsbnd H···O and Osbnd H···N bonds are formed between hydrazide group of isoniazid and coformer. Solubility studies revealed that cocrystal is less soluble as compared to isoniazid in buffer at pH 7.4 at 22 °C while stability studies at 80 °C for 24 h period disclosed the fact that cocrystal has higher stability than that of isoniazid.

  2. Synthon preference in a hydrated β-resorcylic acid structure and its cocrystal with thymine.

    PubMed

    Sridhar, Balasubramanian

    2015-12-01

    Multicomponent crystals or cocrystals play a significant role in crystal engineering, the main objective of which is to understand the role of intermolecular interactions and to utilize such understanding in the design of novel crystal structures. Molecules possessing carboxylic acid and amide functional groups are good candidates for forming cocrystals. β-Resorcylic acid monohydrate, C7H6O4·H2O, (I), crystallizes in the triclinic space group P-1 with one β-resorcylic acid molecule and one water molecule in the asymmetric unit. The cocrystal thymine-β-resorcylic acid-water (1/1/1), C5H6N2O2·C7H6O4·H2O, (II), crystallizes in the orthorhombic space group Pca21, with one molecule each of thymine, β-resorcylic acid and water in the asymmetric unit. All available donor and acceptor atoms in (I) and (II) are utilized for hydrogen bonding. The acid and amide functional groups are well known for the formation of self-complementary acid-acid and amide-amide homosynthons. In (I), an acid-acid homosynthon is observed, while in (II), an amide-acid heterosynthon is present. In (I), the β-resorcylic acid molecule exhibits the expected intramolecular S(6) motif between the hydroxy and carbonyl O atoms, and an intermolecular R2(2)(8) dimer motif between the carboxylic acid groups; only the former motif is observed in (II). The water solvent molecule in (I) propagates the discrete dimers into two-dimensional hydrogen-bonded sheets. In (II), thymine and β-resorcylic acid molecules do not form self-complementary amide-amide and acid-acid homosynthons; instead, a thymine-β-resorcylic acid heterosynthon is observed. With the help of the water molecule, this heterosynthon is aggregated into a three-dimensional hydrogen-bonded network. The absence of thymine base pairing in (II) might be linked to the availability of additional functional groups and the preference of the donor and acceptor hydrogen-bond combinations.

  3. Arachidonic acid mediates the formation of abundant alpha-helical multimers of alpha-synuclein

    NASA Astrophysics Data System (ADS)

    Iljina, Marija; Tosatto, Laura; Choi, Minee L.; Sang, Jason C.; Ye, Yu; Hughes, Craig D.; Bryant, Clare E.; Gandhi, Sonia; Klenerman, David

    2016-09-01

    The protein alpha-synuclein (αS) self-assembles into toxic beta-sheet aggregates in Parkinson’s disease, while it is proposed that αS forms soluble alpha-helical multimers in healthy neurons. Here, we have made αS multimers in vitro using arachidonic acid (ARA), one of the most abundant fatty acids in the brain, and characterized them by a combination of bulk experiments and single-molecule Fӧrster resonance energy transfer (sm-FRET) measurements. The data suggest that ARA-induced oligomers are alpha-helical, resistant to fibril formation, more prone to disaggregation, enzymatic digestion and degradation by the 26S proteasome, and lead to lower neuronal damage and reduced activation of microglia compared to the oligomers formed in the absence of ARA. These multimers can be formed at physiologically-relevant concentrations, and pathological mutants of αS form less multimers than wild-type αS. Our work provides strong biophysical evidence for the formation of alpha-helical multimers of αS in the presence of a biologically relevant fatty acid, which may have a protective role with respect to the generation of beta-sheet toxic structures during αS fibrillation.

  4. 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.

  5. On the factors governing the abundance of oxalic acid in tropospheric aerosol particles

    NASA Astrophysics Data System (ADS)

    van Pinxteren, D.; Neusuess, C.; Brüggemann, E.; Gnauk, T.; Müller, K.; Herrmann, H.

    2010-12-01

    Oxalic acid is frequently observed as one of the most abundant single organic compounds in tropospheric particles. Its sources are commonly believed to be of secondary nature. In state-of-the-art multiphase chemistry models, different pathways exist, which can lead to oxalic acid as final product. Anthropogenic hydrocarbon emissions can be photochemically degraded to glyoxal and methyglyoxal, which - after partitioning into deliquescent particles or cloud droplets - are further oxidized via glyoxylic acid to oxalic acid [Herrmann et al., 2005]. A biogenic oxidation pathway starts with isoprene or monoterpene emissions and leads to glycolaldehyde and methylglyoxal via methacrolein and methylvinylketone, followed by aqueous phase oxalic acid formation [Lim et al., 2005]. As suggested by Warneck, 2003, a marine pathway might exist, starting from marine ethene emissions and leading via glycolaldehyde to oxalic acid. The aim of this study was to elucidate from field measurements the importance of each of these pathways. To this aim, oxalic acid concentrations from 144 size-resolved particle samples (5-stage Berner impactor) from different continental and coastal European sampling sites were statistically analyzed using principal component analysis (PCA). Hourly back trajectories were calculated for each sampling interval using the HYSPLIT model [Draxler and Rolph, 2003] and combined in a novel way with global land cover data to yield “residence times” of the sampled air masses above urban, agricultural, forested, and oceanic areas. These residence times served as quantitative proxies for different emission regimes (anthropogenic, biogenic, marine) in the statistical analysis. Additionally, meteorological parameters such as sunflux along the trajectories or mixing layer depth at the sampling site were retrieved from the HYSPLIT output. PCA of the continental dataset retrieved two factors that were connected to the oxalic acid concentrations. A first one showed high

  6. Pressure-dependent studies on hydration of the C-H group in formic acid

    NASA Astrophysics Data System (ADS)

    Chang, Hai-Chou; Jiang, Jyh-Chiang; Chao, Ming-Chi; Lin, Ming-Shan; Lin, Sheng Hsien; Chen, Hsin-Yen; Hsueh, Hung-Chung

    2001-11-01

    The infrared spectroscopic profiles of HCOOD/D2O mixtures were measured as a function of pressure and concentration. The C-H bond of HCOOD shortens as the pressure is elevated, while the increase in C-H bond length upon diluting HCOOD with D2O was observed. Based on the experimental results, the shift in frequency of C-H stretching band is concluded to relate to the mechanism of the hydration of the C-H group and the water structure in the vicinity of the C-H group. The pressure-dependent results can be attributed to the strengthening of C-H---O electrostatic/dispersion interaction upon increasing pressure. The observations are in accord with ab initio calculation forecasting a blueshift of the C-H stretching mode via C-H---O interaction in HCOOD-water/(HCOOD)2-(D2O) complexes relative to the noninteracting monomer/dimer. Hydrogen-bonding nonadditivity and the size of water clusters are suggested to be responsible to cause the redshift in C-H stretching mode upon dilution HCOOD with D2O.

  7. Application of hydrated and anhydrous fluroantimonic acids in the polymerization of epoxidized soybean oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polymerizations of epoxidized soybean oil (ESO) were catalyzed by the superacids, fluroantimonic acid hexahydrate (HSbF6•6H2O) and anhydrous fluroantimonic acid (HSbF6) using ethyl acetate solvent. This work was conducted in an effort to develop useful biodegradable polymers from renewable resources...

  8. Catalyzed ring-opening polymerization of epoxidized soybean oil by hydrated and anhydrous fluoroantimonic acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by the super acid, fluroantimonic acid hexahydrate (HSbF6-6H2O), and the anhydrous form (HSbF6) in ethyl acetate was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (SA-RPESO and SAA-...

  9. Squaraines: crystal structures and spectroscopic analysis of hydrated and anhydrous forms of squaric acid-isoniazid species.

    PubMed

    dos Reis, Felipe D; Gatti, Isabela C; Garcia, Humberto C; de Oliveira, Vanessa E; de Oliveira, Luiz F C

    2014-12-11

    The crystal structures, synthesis procedure, thermal behavior, and spectroscopic properties of a new squaraine SqINH·H2O and its anhydrous arrangement are described. This squaraine is obtained through an acid-base reaction using squaric acid (H2Sq) and isoniazid (INH) as precursors. Both squaraines crystallize in the monoclinic system, but in different space groups: the hydrated and anhydrous arrangement crystallizes in the P2₁ and P2₁/c space group, respectively. The crystallographic data strongly suggest that the structures present an expressive increase in their electronic delocalization all over the molecular structure of both compounds, when compared with the reagents. The bond distances for both structures present an average value intermediate between a single and double character (1.463(3) Å for SqINH·H2O and 1.4959(3) Å for SqINH). The vibrational and electronic data also corroborate with this proposal, since the band shifts indicate that the conjugation over the system is increased, as indicated by the blue shift observed for the carbonyl stretching bands for both compounds. The presence of the water molecule is responsible for a decrease in fluorescence emission, as determined by the emission spectra recorded for both compounds.

  10. Effects of short-chain fatty acid-supplemented total parenteral nutrition on intestinal pro-inflammatory cytokine abundance.

    PubMed

    Milo, L A; Reardon, K A; Tappenden, K A

    2002-09-01

    We examined the effect of short-chain fatty acid-supplemented total parenteral nutrition on proinflammatory cytokine levels in piglets. Piglets (N = 22) received either standard total parenteral nutrition or total parenteral nutrition supplemented with short-chain fatty acids. After seven days of continuous nutrient infusion, proinflammatory cytokine (TNF-alpha, IL-1beta, IL-6) abundance in plasma, jejunal, and ileal samples and small intestinal myeloperoxidase was determined using western blotting. No differences were seen in TNF-alpha small intestinal abundance. IL-1beta was higher in the small intestine of the short-chain fatty acid group (P < 0.05). IL-6 was higher in intestinal samples of the short-chain fatty acid group (P = 0.05), with the ileum having a greater abundance of IL-6 than the jejunum (P < 0.005). No differences in proinflammatory cytokine abundance in the plasma or tissue myeloperoxidase were seen. These results indicate short-chain fatty acids beneficially increase small intestinal abundance of IL-1beta and IL-6 during total parenteral nutrition administration, while not affecting systemic production of these cytokines or intestinal inflammation.

  11. The effect of sample hydration on 13C CPMAS NMR spectra of fulvic acids

    USGS Publications Warehouse

    Hatcher, P.G.; Wilson, M.A.

    1991-01-01

    Three fulvic acids, two of which have been well studied by a number of other groups (Armadale and Suwannee river fulvic acids) have been examined by high resolution solid-state 13C-NMR techniques to delineate the effect of absorbed water. Two main effects of absorbed water were observed: (1) changes in spin lattice relaxation times in the rotating frame and cross polarization times and (2) total loss of signal so that some fulvic acid is effectively in solution. These results suggest that discrepancies in the literature concerning observed relative signal intensities from different structural groups are due to absorbed water and emphasize the necessity for proper precautionary drying before spectroscopic analysis. ?? 1991.

  12. Reaction of cis-3-chloroacrylic acid dehalogenase with an allene substrate, 2,3-butadienoate: hydration via an enamine.

    PubMed

    Schroeder, Gottfried K; Johnson, William H; Huddleston, Jamison P; Serrano, Hector; Johnson, Kenneth A; Whitman, Christian P

    2012-01-11

    cis-3-Chloroacrylic acid dehalogenase (cis-CaaD) catalyzes the hydrolytic dehalogenation of cis-3-haloacrylates to yield malonate semialdehyde. The enzyme processes other substrates including an allene (2,3-butadienoate) to produce acetoacetate. In the course of a stereochemical analysis of the cis-CaaD-catalyzed reaction using this allene, the enzyme was unexpectedly inactivated in the presence of NaBH(4) by the reduction of a covalent enzyme-substrate bond. Covalent modification was surprising because the accumulated evidence for cis-CaaD dehalogenation favored a mechanism involving direct substrate hydration mediated by Pro-1. However, the results of subsequent mechanistic, pre-steady state and full progress kinetic experiments are consistent with a mechanism in which an enamine forms between Pro-1 and the allene. Hydrolysis of the enamine or an imine tautomer produces acetoacetate. Reduction of the imine species is likely responsible for the observed enzyme inactivation. This is the first reported observation of a tautomerase superfamily member functioning by covalent catalysis. The results may suggest that some fraction of the cis-CaaD-catalyzed dehalogenation of cis-3-haloacrylates also proceeds by covalent catalysis.

  13. Muonium reactions with chloroacetic acid in water: Contrasts with H atoms and hydrated electrons

    NASA Astrophysics Data System (ADS)

    Stadlbauer, John M.; Venkateswaran, Krishnan; Walker, David C.

    1997-09-01

    Muonium atoms react with chloroacetic acid and chloroacetate ions in dilute aqueous solution with rate constants of 2.3 × 10 6 and 9.1 × 10 5 dm 3 mol -1 s -1 respectively. These are compared with the reactions of 1H atoms (and e aq-) and discussed in terms of a pair of competing kinetic isotope effects. Muonium reacts at least eight times faster than H overall, and probably 28 times faster in forming Cl -. It behaves as a nucleophile, thus resembling e aq- more than H, in reacting faster with the acid than the anion. Muonium's reactions must be governed to a considerable extent by quantum-mechanical effects arising from its very small mass.

  14. Variations of the abundance and nucleic acid content of heterotrophic bacteria in Beaufort Shelf waters during winter and spring

    NASA Astrophysics Data System (ADS)

    Belzile, Claude; Brugel, Sonia; Nozais, Christian; Gratton, Yves; Demers, Serge

    2008-12-01

    Depth profiles of heterotrophic bacteria abundance were measured weekly over a 6-month period from December to May in Franklin Bay, a 230 m-deep coastal Arctic Ocean site of the southeastern Beaufort Sea. Total bacteria, low nucleic acid (LNA) and high nucleic acid (HNA) bacteria abundances were measured using flow cytometry after SYBR Green I staining. The HNA bacteria abundance in surface waters started to increase 5-6 weeks after phytoplankton growth resumed in spring, increasing from 1 × 10 5 to 3 × 10 5 cells mL - 1 over an 8-week period, with a net growth rate of 0.018 d - 1 . LNA bacteria response was delayed by more than two months relative to the beginning of the phytoplankton biomass accumulation and had a lower net growth rate of 0.013 d - 1 . The marked increase in bacterial abundance occurred before any significant increase in organic matter input from river discharge (as indicated by the unchanged surface water salinity and DOC concentrations), and in the absence of water temperature increase. The abundance of bacteria below the halocline was relatively high until January (up to 5 × 10 5 cells mL - 1 ) but then decreased to values close to 2 × 10 5 cells mL - 1 . The three-fold bacterial abundance increase observed in surface waters in spring was mostly due to HNA bacteria, supporting the idea that these cells are the most active.

  15. In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

    PubMed

    Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

    2017-05-01

    Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants.

  16. Use of sequential sampling of amphipod abundance to classify the biotic integrity of acid-sensitive lakes

    NASA Astrophysics Data System (ADS)

    France, Robert

    1992-03-01

    A sequential sampling program using previously published zoobenthos data is described for ubiquitous, cost-effective biomonitoring of the effects of lake acidification. Spring densities of the littoral amphipod Hyalella azteca are quantitatively sorted into five abundance catagories. An essential step in the a priori definition of decision criteria is the stratification of proportional densities per unit macrophyte biomass in relation to aqueous total phosphorus concentrations. Density rankings were related to lake acidity and to detailed lake-specific information on patterns of Hyalella life history and acid tolerance. Incorporation of Hyalella abundance as a potential metric for the assessment of the biological integrity of acid-sensitive waters is recommended. The temporal integration of transient changes in spring meltwater chemistry is an important rationale for the development of such biomonitoring procedures.

  17. The microstructure of the stratum corneum lipid barrier: mid-infrared spectroscopic studies of hydrated ceramide:palmitic acid:cholesterol model systems.

    PubMed

    Garidel, Patrick; Fölting, Bettina; Schaller, Ingrid; Kerth, Andreas

    2010-08-01

    The current mid-infrared spectroscopic study is a systematic investigation of hydrated stratum corneum lipid barrier model systems composed of an equimolar mixture of a ceramide, free palmitic acid and cholesterol. Four different ceramide molecules (CER NS, CER NP, CER NP-18:1, CER AS) were investigated with regard to their microstructure arrangement in a stratum corneum lipid barrier model system. Ceramide molecules were chosen from the sphingosine and phytosphingosine groups. The main differences in the used ceramide molecules result from their polar head group architecture as well as hydrocarbon chain properties. The mixing properties with cholesterol and palmitic acid are considered. This is feasible by using perdeuterated palmitic acid and proteated ceramides. Both molecules can be monitored separately, within the same experiment, using mid-infrared spectroscopy; no external label is necessary. At physiological relevant temperatures, between 30 and 35 degrees C, orthorhombic as well as hexagonal chain packing of the ceramide molecules is observed. The formation of these chain packings are extremely dependent on lipid hydration, with a decrease in ceramide hydration favouring the formation of orthorhombic hydrocarbon chain packing, as well as temperature. The presented data suggest in specific cases phase segregation in ceramide and palmitic acid rich phases. However, other ceramides like CER NP-18:1 show a rather high miscibility with palmitic acid and cholesterol. For all investigated ternary systems, more or less mixing of palmitic acid with cholesterol is observed. The investigated stratum corneum mixtures exhibit a rich polymorphism from crystalline domains with heterogeneous lipid composition to a "fluid" homogeneous phase. Thus, a single gel phase is not evident for the presented stratum corneum model systems. The study shows, that under skin physiological conditions (pH 5.5, hydrated, 30-35 degrees C) ternary systems composed of an equimolar ratio of

  18. Lack of formic acid production in rat hepatocytes and human renal proximal tubule cells exposed to chloral hydrate or trichloroacetic acid.

    PubMed

    Lock, Edward A; Reed, Celia J; McMillan, Joellyn M; Oatis, John E; Schnellmann, Rick G

    2007-02-12

    The industrial solvent trichloroethylene (TCE) and its major metabolites have been shown to cause formic aciduria in male rats. We have examined whether chloral hydrate (CH) and trichloroacetic acid (TCA), known metabolites of TCE, produce an increase in formic acid in vitro in cultures of rat hepatocytes or human renal proximal tubule cells (HRPTC). The metabolism and cytotoxicity of CH was also examined to establish that the cells were metabolically active and not compromised by toxicity. Rat hepatocytes and HRPTC were cultured in serum-free medium and then treated with 0.3-3mM CH for 3 days or 0.03-3mM CH for 10 days, respectively and formic acid production, metabolism to trichloroethanol (TCE-OH) and TCA and cytotoxicity determined. No increase in formic acid production in rat hepatocytes or HRPTC exposed to CH was observed over and above that due to chemical degradation, neither was formic acid production observed in rat hepatocytes exposed to TCA. HRPTC metabolized CH to TCE-OH and TCA with a 12-fold greater capacity to form TCE-OH versus TCA. Rat hepatocytes exhibited a 1.6-fold and three-fold greater capacity than HRPTC to form TCE-OH and TCA, respectively. CH and TCA were not cytotoxic to rat hepatocytes at concentrations up to 3mM/day for 3 days. With HRPTC, one sample showed no cytotoxicity to CH at concentrations up to 3mM/day for 10 days, while in another cytotoxicity was seen at 1mM/day for 3 days. In summary, increased formic acid production was not observed in rat hepatocytes or HRPTC exposed to TCE metabolites, suggesting that the in vivo response cannot be modelled in vitro. CH was toxic to HRPTC at millimolar concentrations/day over 10 days, while glutathione derived metabolites of TCE were toxic at micromolar concentrations/day over 10 days [Lock, E.A., Reed, C.J., 2006. Trichloroethylene: mechanisms of renal toxicity and renal cancer and relevance to risk assessment. Toxicol. Sci. 19, 313-331] supporting the view that glutathione derived

  19. On the Hydration State of Amino Acids and Their Derivatives at Different Ionization States: A Comparative Multinuclear NMR and Crystallographic Investigation

    PubMed Central

    Pappas, Charalampos G.; Tzakos, Andreas G.; Gerothanassis, Ioannis P.

    2012-01-01

    2D, 13C, 14N, and 17O NMR and crystallographic data from the literature were critically evaluated in order to provide a coherent hydration model of amino acids and selected derivatives at different ionization states. 17O shielding variations, longitudinal relaxation times (T1) of 2D and 13C and line widths (Δν1/2) of 14N and 17O, may be interpreted with the hypothesis that the cationic form of amino acids is more hydrated by 1 to 3 molecules of water than the zwitterionic form. Similar behaviour was also observed for N-acetylated derivatives of amino acids. An exhaustive search in crystal structure databases demonstrates the importance of six-membered hydrogen-bonded conjugated rings of both oxygens of the α-carboxylate group with a molecule of water in the vicinity. This type of hydrogen bond mode is absent in the case of the carboxylic groups. Moreover, a considerable number of structures was identified with the propensity to form intramolecular hydrogen bond both in the carboxylic acid (NH⋯O=C) and in the carboxylate (NH ⋯ O−) ionization state. In the presence of bound molecules of water this interaction is significantly reduced in the case of the carboxylate group whereas it is statistically negligible in the carboxylic group. PMID:22675607

  20. The effects of parent-body hydrothermal heating on amino acid abundances in CI-like chondrites

    NASA Astrophysics Data System (ADS)

    Burton, Aaron S.; Grunsfeld, Sarah; Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2014-09-01

    We determined the amino acid abundances and enantiomeric compositions of the Antarctic CI1 carbonaceous chondrites Yamato (Y)-86029 and Y-980115, as well as the Ivuna and Orgueil CI1 carbonaceous chondrites by liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Y-86029 and Y-980115 both show evidence of parent-body heating (500-600 °C) in addition to aqueous alteration, while Ivuna and Orgueil only show evidence for aqueous alteration. In contrast to Ivuna and Orgueil, which each contain ˜70 nmol/g of amino acids in acid-hydrolyzed, water extracts, both heated Yamato CI meteorites contain only low levels of amino acids that were primarily L-enantiomers of proteinogenic amino acids, indicating that they are likely to be terrestrial in origin. Because indigenous amino acids have been found in meteorites that have experienced metamorphic temperatures of >1000 °C with only minimal aqueous alteration, heating alone is not sufficient to explain the lack of amino acids in Y-86029 and Y-980115. Rather, our data suggest that the combination of heating and aqueous alteration has a profound destructive effect on amino acids in meteorites. This finding has implications for the origins of amino acids and other molecules in the early evolution of our solar system.

  1. Gas hydrates in the ocean environment

    USGS Publications Warehouse

    Dillon, William P.

    2002-01-01

    A GAS HYDRATE, also known as a gas clathrate, is a gas-bearing, icelike material. It occurs in abundance in marine sediments and stores immense amounts of methane, with major implications for future energy resources and global climate change. Furthermore, gas hydrate controls some of the physical properties of sedimentary deposits and thereby influences seafloor stability.

  2. 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.

  3. Endospore abundance and D:L-amino acid modeling of bacterial turnover in holocene marine sediment (Aarhus Bay)

    NASA Astrophysics Data System (ADS)

    Langerhuus, Alice T.; Røy, Hans; Lever, Mark A.; Morono, Yuki; Inagaki, Fumio; Jørgensen, Bo B.; Lomstein, Bente Aa.

    2012-12-01

    In order to study bacterial activity, and turnover times of bacterial necromass and biomass in marine sediment, two stations from the Aarhus Bay, Denmark were analyzed. Sediment cores were up to 11 m deep and covered a timescale from the present to ˜11,000 years ago. Sediment was analyzed for total hydrolysable amino acids (THAA), total hydrolysable amino sugars, the bacterial endospore marker dipicolinic acid (DPA), and amino acid enantiomers (L- and D-form) of aspartic acid. Turnover times of bacterial necromass and vegetative cells, as well as carbon oxidation rates were estimated by use of the D:L-amino acid racemization model. Diagenetic indicators were applied to evaluate the diagenetic state of the sedimentary organic matter. The contribution of amino acids to total organic carbon, and the ratio between the amino acids aspartic acid and glutamic acid, and their respective non protein degradation products, β-alanine and γ-amino butyric acid, all indicated increasing degradation state of the organic matter with sediment depth and age. Quantification of DPA showed that endospores were abundant, and increased with depth relative to vegetative cells. Most of the amino acids (97%) could be ascribed to microbial necromass, i.e. the remains of dead bacterial cells. Model estimates showed that the turnover times of microbial necromass were in the range of 0.5-1 × 105 years, while turnover times of vegetative cells were in the range of tens to hundreds of years. The turnover time of the TOC pool increased with depth in the sediment, indicating that the TOC pool became progressively more refractory and unavailable to microorganisms with depth and age of the organic matter.

  4. Chloral hydrate

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 00 / 006 TOXICOLOGICAL REVIEW OF CHLORAL HYDRATE ( CAS No . 302 - 17 - 0 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) August 2000 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been reviewed in accordance w

  5. Metabolic potential of fatty acid oxidation and anaerobic respiration by abundant members of Thaumarchaeota and Thermoplasmata in deep anoxic peat

    DOE PAGES

    Lin, Xueju; Handley, Kim M.; Gilbert, Jack A.; ...

    2015-12-01

    To probe the metabolic potential of abundant Archaea in boreal peats, we reconstructed two near-complete archaeal genomes, affiliated with Thaumarchaeota group 1.1c (bin Fn1, 8% abundance), which was a genomically unrepresented group, and Thermoplasmata (bin Bg1, 26% abundance), from metagenomic data acquired from deep anoxic peat layers. Each of the near-complete genomes encodes the potential to degrade long-chain fatty acids (LCFA) via β-oxidation. Fn1 has the potential to oxidize LCFA either by syntrophic interaction with methanogens or by coupling oxidation with anaerobic respiration using fumarate as a terminal electron acceptor (TEA). Fn1 is the first Thaumarchaeota genome without an identifiablemore » carbon fixation pathway, indicating that this mesophilic phylum encompasses more diverse metabolisms than previously thought. Furthermore, we report genetic evidence suggestive of sulfite and/or organosulfonate reduction by Thermoplasmata Bg1. In deep peat, inorganic TEAs are often depleted to extremely low levels, yet the anaerobic respiration predicted for two abundant archaeal members suggests organic electron acceptors such as fumarate and organosulfonate (enriched in humic substances) may be important for respiration and C mineralization in peatlands.« less

  6. Metabolic potential of fatty acid oxidation and anaerobic respiration by abundant members of Thaumarchaeota and Thermoplasmata in deep anoxic peat

    SciTech Connect

    Lin, Xueju; Handley, Kim M.; Gilbert, Jack A.; Kostka, Joel E.

    2015-12-01

    To probe the metabolic potential of abundant Archaea in boreal peats, we reconstructed two near-complete archaeal genomes, affiliated with Thaumarchaeota group 1.1c (bin Fn1, 8% abundance), which was a genomically unrepresented group, and Thermoplasmata (bin Bg1, 26% abundance), from metagenomic data acquired from deep anoxic peat layers. Each of the near-complete genomes encodes the potential to degrade long-chain fatty acids (LCFA) via β-oxidation. Fn1 has the potential to oxidize LCFA either by syntrophic interaction with methanogens or by coupling oxidation with anaerobic respiration using fumarate as a terminal electron acceptor (TEA). Fn1 is the first Thaumarchaeota genome without an identifiable carbon fixation pathway, indicating that this mesophilic phylum encompasses more diverse metabolisms than previously thought. Furthermore, we report genetic evidence suggestive of sulfite and/or organosulfonate reduction by Thermoplasmata Bg1. In deep peat, inorganic TEAs are often depleted to extremely low levels, yet the anaerobic respiration predicted for two abundant archaeal members suggests organic electron acceptors such as fumarate and organosulfonate (enriched in humic substances) may be important for respiration and C mineralization in peatlands.

  7. Metabolic potential of fatty acid oxidation and anaerobic respiration by abundant members of Thaumarchaeota and Thermoplasmata in deep anoxic peat.

    PubMed

    Lin, Xueju; Handley, Kim M; Gilbert, Jack A; Kostka, Joel E

    2015-12-01

    To probe the metabolic potential of abundant Archaea in boreal peats, we reconstructed two near-complete archaeal genomes, affiliated with Thaumarchaeota group 1.1c (bin Fn1, 8% abundance), which was a genomically unrepresented group, and Thermoplasmata (bin Bg1, 26% abundance), from metagenomic data acquired from deep anoxic peat layers. Each of the near-complete genomes encodes the potential to degrade long-chain fatty acids (LCFA) via β-oxidation. Fn1 has the potential to oxidize LCFA either by syntrophic interaction with methanogens or by coupling oxidation with anaerobic respiration using fumarate as a terminal electron acceptor (TEA). Fn1 is the first Thaumarchaeota genome without an identifiable carbon fixation pathway, indicating that this mesophilic phylum encompasses more diverse metabolisms than previously thought. Furthermore, we report genetic evidence suggestive of sulfite and/or organosulfonate reduction by Thermoplasmata Bg1. In deep peat, inorganic TEAs are often depleted to extremely low levels, yet the anaerobic respiration predicted for two abundant archaeal members suggests organic electron acceptors such as fumarate and organosulfonate (enriched in humic substances) may be important for respiration and C mineralization in peatlands.

  8. Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data.

    PubMed

    Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel

    2016-05-25

    Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

  9. 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.

  10. Crystal structure of 4-(3-carb-oxy-pro-pan-amido)-2-hy-droxy-benzoic acid mono-hydrate.

    PubMed

    Tahir, Muhammad Nawaz; Ahmed, Muhammad Naeem; Butt, Arshad Farooq; Shad, Hazoor Ahmad

    2014-12-01

    In the title hydrate, C11H11NO6·H2O, the organic mol-ecule is approximately planar (r.m.s. deviation for the non-H atoms = 0.129 Å) and an intra-molecular O-H⋯O hydrogen bond closes an S(6) ring. In the crystal, the benzoic acid group participates in an O-H⋯O hydrogen bond to the water mol-ecule and accepts a similar bond from another water mol-ecule. The other -CO2H group forms a carb-oxy-lic acid inversion dimer, thereby forming an R 2 (2)(8) loop. These bonds, along with N-H⋯O and C-H⋯O inter-actions, generate a three-dimensional network.

  11. Structural characterization of hydrated poly(aspartic acid) sodium and poly(aspartic acid) sodium/poly(vinyl alcohol) blends by high-resolution solid-state 23Na NMR

    NASA Astrophysics Data System (ADS)

    Wang, P.; Ando, I.

    1999-09-01

    The structure of hydrated poly(aspartic acid) sodium (PAANa) and in blended PAANa, which was blended with poly(vinyl alcohol) (PVA), is characterized by means of high-resolution solid-state 23Na NMR. There are two peaks in dried pure PAANa, which are assigned to associated ions (about -16 ppm) and isolated ions or end group ions of PAANa (7.2 ppm), respectively. With an increase in hydration, the 23Na chemical shifts of these two peaks are changed to tend toward 0 ppm, and the line width at half the height of the 23Na resonance decreases. In contrast, in the blended samples, the 23Na resonance shapes and chemical shift values are significantly changed depending on the ratio of the PAANa/PVA blends and the temperature. On the basis of these experimental results, the structure of the blends was elucidated.

  12. Competitive sorption of Pb(II) and Zn(II) on polyacrylic acid-coated hydrated aluminum-oxide surfaces.

    PubMed

    Wang, Yingge; Michel, F Marc; Levard, Clement; Choi, Yong; Eng, Peter J; Brown, Gordon E

    2013-01-01

    Natural organic matter (NOM) often forms coatings on minerals. Such coatings are expected to affect metal-ion sorption due to abundant sorption sites in NOM and potential modifications to mineral surfaces, but such effects are poorly understood in complex multicomponent systems. Using poly(acrylic acid) (PAA), a simplified analog of NOM containing only carboxylic groups, Pb(II) and Zn(II) partitioning between PAA coatings and α-Al2O3 (1-102) and (0001) surfaces was investigated using long-period X-ray standing wave-florescence yield spectroscopy. In the single-metal-ion systems, PAA was the dominant sink for Pb(II) and Zn(II) for α-Al2O3(1-102) (63% and 69%, respectively, at 0.5 μM metal ions and pH 6.0). In equi-molar mixed-Pb(II)-Zn(II) systems, partitioning of both ions onto α-Al2O3(1-102) decreased compared with the single-metal-ion systems; however, Zn(II) decreased Pb(II) sorption to a greater extent than vice versa, suggesting that Zn(II) outcompeted Pb(II) for α-Al2O3(1-102) sorption sites. In contrast, >99% of both metal ions sorbed to PAA when equi-molar Pb(II) and Zn(II) were added simultaneously to PAA/α-Al2O3(0001). PAA outcompeted both α-Al2O3 surfaces for metal sorption but did not alter their intrinsic order of reactivity. This study suggests that single-metal-ion sorption results cannot be used to predict multimetal-ion sorption at NOM/metal-oxide interfaces when NOM is dominated by carboxylic groups.

  13. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  14. Effects of inorganic acids and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process.

    PubMed

    Zhang, Jian; Xia, Yuguo; Zhang, Li; Chen, Dairong; Jiao, Xiuling

    2015-11-07

    In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

  15. Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction.

    PubMed

    Kibsgaard, Jakob; Jaramillo, Thomas F

    2014-12-22

    Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells.

  16. Tracing the source of cooking oils with an integrated approach of using stable carbon isotope and fatty acid abundance.

    PubMed

    Liu, Weiguo; Yang, Hong; Wang, Zheng; Liu, Jinzhao

    2012-08-15

    We report a new approach to identify swill-cooked oils that are recycled from tainted food and livestock waste from commercial vegetable and animal oils by means of carbon isotope values and relative abundance of fatty acids. We test this method using 40 cooking oil samples of different types with known sources. We found significant differences in both total organic carbon isotope as well as compound-specific isotope values and fatty acid C(14)/C(18) ratios between commercial vegetable oils refined from C(3) plants (from -35.7 to -27.0‰ and from 0 to 0.15) and animal oils (from -28.3 to -14.3‰ and from 0.1 to 0.6). Tested swill-cooked oils, which were generally refined by mixing with animal waste illegally, fall into a narrow δ(13)C/fatty acid ratio distribution: from -25.9 to -24.1‰ and from 0.1 to 0.2. Our data demonstrate that the index of a cross-plotting between fatty acid δ(13)C values and C(14)/C(18) ratios can be used to distinguish clean commercial cooking oils from illegal swill-cooked oils.

  17. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    Whoever said there is nothing new under the sun did not delve deeply enough to the bottom of the ocean. There in the Gulf of Mexico, about 150 miles south of New Orleans, scientists have just discovered what could be a new species of centipede—like worms living on or within gas hydrates— mounds of methane ice— rising from the ocean floor.Scientists have previously recognized an association between some bacteria and these hydrates. However, this is the first discovery of a higher life form there.

  18. c-Myc Programs Fatty Acid Metabolism and Dictates Acetyl-CoA Abundance and Fate*

    PubMed Central

    Edmunds, Lia R.; Sharma, Lokendra; Kang, Audry; Lu, Jie; Vockley, Jerry; Basu, Shrabani; Uppala, Radha; Goetzman, Eric S.; Beck, Megan E.; Scott, Donald; Prochownik, Edward V.

    2014-01-01

    myc−/− rat fibroblasts (KO cells) differ from myc+/+ (WT) cells and KO cells with enforced Myc re-expression (KO-Myc cells) with respect to mitochondrial structure and function, utilization of glucose and glutamine as energy-generating substrates, and ATP levels. Specifically, KO cells demonstrate low levels of glycolysis and oxidative phosphorylation, dysfunctional mitochondria and electron transport chain complexes, and depleted ATP stores. We examined here how these cells adapt to their energy-deficient state and how they differ in their uptake and utilization of long- and medium-chain fatty acids such as palmitate and octanoate, respectively. Metabolic tracing of these molecules showed that KO cells preferentially utilize them as β-oxidation substrates and that, rather than directing them into phospholipids, preferentially store them as neutral lipids. KO cell transcriptional profiling and functional assays revealed a generalized up-regulation of pathways involved in fatty acid transport and catabolism as well as evidence that these cells attempt to direct acetyl-CoA into the tricarboxylic acid (TCA) cycle for ATP production rather than utilizing it for anabolic purposes. Additional evidence to support this idea included the finding that AMP-dependent protein kinase was constitutively activated in KO cells. The complex control of pyruvate dehydrogenase, which links glycolysis to the TCA cycle, was also maximized to ensure the conversion of pyruvate to acetyl-CoA. Despite these efforts to maximize acetyl-CoA for energy-generating purposes, its levels remained chronically low in KO cells. This suggests that tumor cells with Myc deregulation might be susceptible to novel therapies that limit acetyl-CoA availability. PMID:25053415

  19. Growth and spectral characterization of ethylene diamine tetra acetic acid (EDTA) doped zinc sulphate hepta hydrate - a semi organic NLO material.

    PubMed

    Ramachandra Raja, C; Ramamurthi, K; Manimekalai, R

    2012-12-01

    Semi-organic non-linear optical single crystals of ethylene diamine tetra acetic acid (EDTA) doped zinc sulphate hepta hydrate crystals were grown by slow evaporation solution growth technique, at room temperature, using de-ionized water as solvent. The modes of vibrations of different molecular groups present in the grown crystal were identified by FT-IR technique. The optical absorbance/transmittance was recorded in the wavelength range of 190-1100 nm. Thermal properties of the grown crystal were studied by thermo gravimetric analysis and differential thermal analysis. The melting point of the grown crystal was estimated by differential scanning calorimetric analysis. The inclusion of the dopant (EDTA) was confirmed by colorimetric estimation method. The second harmonic generation efficiency is about 30% of potassium dihydrogen orthophosphate.

  20. Acidic α-galactosidase is the most abundant nectarin in floral nectar of common tobacco (Nicotiana tabacum)

    PubMed Central

    Zha, Hong-Guang; Flowers, V. Lynn; Yang, Min; Chen, Ling-Yang; Sun, Hang

    2012-01-01

    Background and Aims To date, most floral nectarins (nectar proteins) are reported to function in nectar defence, particularly for insect-pollinated outcrossing species. We compared nectarin composition and abundance in selfing common tobacco (Nicotiana tobaccum) with outcrossing ornamental tobacco plants to elucidate the functional difference of nectarins in different reproductive systems. Methods Common tobacco (CT) nectarins were separated by SDS-PAGE and the N terminus of the most abundant nectarin was sequenced via Edman degradation. The full-length nectarin gene was amplified and cloned from genomic DNA and mRNA with hiTail-PCR and RACE (rapid amplification of cDNA ends), and expression patterns were then investigated in different tissues using semi-quantitative reverse transcriptase PCR. Additionally, high-performance liquid chromatography and enzymatic analyses of nectar sugar composition, and other biochemical traits and functions of the novel nectarin were studied. Key Results The most abundant nectarin in CT nectar is an acidic α-galactosidase, here designated NTα-Gal. This compound has a molecular mass of 40 013 Da and a theoretical pI of 5·33. NTα-Gal has a conserved α-Gal characteristic signature, encodes a mature protein of 364 amino acids and is expressed in different organs. Compared with 27 other melliferous plant species from different families, CT floral nectar demonstrated the highest α-Gal activity, which is inhibited by d-galactose. Raffinose family oligosaccharides were not detected in CT nectar, indicating that NTα-Gal does not function in post-secretory hydrolysis. Moreover, tobacco plant fruits did not develop intact skin with galactose inhibition of NTα-Gal activity in nectar, suggesting that NTα-Gal induces cell-wall surface restructuring during the initial stages of fruit development. Conclusions α-Gal was the most abundant nectarin in selfing CT plants, but was not detected in the nectar of strictly outcrossing sister tobacco

  1. Reactions of Cg10062, a cis-3-Chloroacrylic Acid Dehalogenase Homologue, with Acetylene and Allene Substrates: Evidence for a Hydration-Dependent Decarboxylation.

    PubMed

    Huddleston, Jamison P; Johnson, William H; Schroeder, Gottfried K; Whitman, Christian P

    2015-05-19

    Cg10062 is a cis-3-chloroacrylic acid dehalogenase (cis-CaaD) homologue from Corynebacterium glutamicum with an unknown function and an uninformative genomic context. It shares 53% pairwise sequence similarity with cis-CaaD including the six active site amino acids (Pro-1, His-28, Arg-70, Arg-73, Tyr-103, and Glu-114) that are critical for cis-CaaD activity. However, Cg10062 is a poor cis-CaaD: it lacks catalytic efficiency and isomer specificity. Two acetylene compounds (propiolate and 2-butynoate) and an allene compound, 2,3-butadienoate, were investigated as potential substrates. Cg10062 functions as a hydratase/decarboxylase using propiolate as well as the cis-3-chloro- and 3-bromoacrylates, generating mixtures of malonate semialdehyde and acetaldehyde. The two activities occur sequentially at the active site using the initial substrate. With 2,3-butadienoate and 2-butynoate, Cg10062 functions as a hydratase and converts both to acetoacetate. Mutations of the proposed water-activating residues (E114Q, E114D, and Y103F) have a range of consequences from a reduction in wild type activity to a switch of activities (i.e., hydratase into a hydratase/decarboxylase or vice versa). The intermediates for the hydration and decarboxylation products can be trapped as covalent adducts to Pro-1 when NaCNBH3 is incubated with the E114D mutant and 2,3-butadienoate or 2-butynoate, and the Y103F mutant and 2-butynoate. Three mechanisms are presented to explain these findings. One mechanism involves the direct attack of water on the substrate, whereas the other two mechanisms use covalent catalysis in which a covalent bond forms between Pro-1 and the hydration product or the substrate. The strengths and weaknesses of the mechanisms and the implications for Cg10062 function are discussed.

  2. The highly abundant urinary metabolite urobilin interferes with the bicinchoninic acid assay.

    PubMed

    Sampson, D L; Chng, Y L; Upton, Z; Hurst, C P; Parker, A W; Parker, T J

    2013-11-01

    Estimation of total protein concentration is an essential step in any protein- or peptide-centric analysis pipeline. This study demonstrates that urobilin, a breakdown product of heme and a major constituent of urine, interferes considerably with the bicinchoninic acid (BCA) assay. This interference is probably due to the propensity of urobilin to reduce cupric ions (Cu(2+)) to cuprous ions (Cu(1+)), thus mimicking the reduction of copper by proteins, which the assay was designed to do. In addition, it is demonstrated that the Bradford assay is more resistant to the influence of urobilin and other small molecules. As such, urobilin has a strong confounding effect on the estimate of total protein concentrations obtained by BCA assay and thus this assay should not be used for urinary protein quantification. It is recommended that the Bradford assay be used instead.

  3. Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

    NASA Astrophysics Data System (ADS)

    Kürten, Andreas; Bianchi, Federico; Almeida, Joao; Kupiainen-Määttä, Oona; Dunne, Eimear M.; Duplissy, Jonathan; Williamson, Christina; Barmet, Peter; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Flagan, Richard C.; Franchin, Alessandro; Gordon, Hamish; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Ickes, Luisa; Jokinen, Tuija; Kangasluoma, Juha; Kim, Jaeseok; Kirkby, Jasper; Kupc, Agnieszka; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Onnela, Antti; Ortega, Ismael K.; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schnitzhofer, Ralf; Schobesberger, Siegfried; Smith, James N.; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Paul E.; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Ken; Kulmala, Markku; Curtius, Joachim

    2016-10-01

    Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109 cm-3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of 1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm-3 s-1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.

  4. Ontogenetic change in the abundance of mycosporine-like amino acids in non-zooxanthellate coral larvae

    NASA Astrophysics Data System (ADS)

    Yakovleva, Irina M.; Baird, Andrew H.

    2005-11-01

    Although mycosporine-like amino acids (MAAs) have been extensively investigated in reef-building corals, the sources of these MAAs and the process of their interconversion remain a topic of interest. Here we examined ontogenetic change in the abundance of MAAs in planula larvae of the spawning scleractinian coral Goniastrea retiformis in the absence of zooxanthellae and other dietary input. In order to examine the potential contribution of prokaryotes in the synthesis of MAAs in animal tissue, one group of larvae were treated with the antibiotic rifampicin. High concentrations of MAAs (mycosporine-glycine, shinorine, palythinol, asterina-330), were present in the asymbiotic eggs and adults; however, no MAAs were present in the endosymbiotic zooxanthellae. We documented a steady decline in the total MAA concentrations through time in larvae treated with rifampicin; however, in the absence of antibiotic there was a significant increase in the concentration of MAAs, driven by a sharp increase in the abundance of shinorine and palythinol between day 3 and 7. Our results suggest that MAA synthesis and conversion in G. retiformis larvae occurred in the absence of symbiotic zooxanthellae, and indicate a possible contribution of prokaryotes associated with the animal tissue to these processes.

  5. High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Okuzawa, K.; Aggarwal, S. G.; Kanaya, Y.; Wang, Z. F.

    2013-08-01

    Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N, 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low-molecular-weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Molecular distributions of dicarboxylic acids (C2-C11, 220-6070 ng m-3) were characterized by a predominance of oxalic (C2) acid (105-3920 ng m-3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acids, were also detected together with aromatic diacids (phthalic, isophthalic and terephthalic acids). ω-oxocarboxylic acids (C2-C9, 24-610 ng m-3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11-360 ng m-3), followed by α-ketoacid (pyruvic acid, 3-140 ng m-3) and α-dicarbonyls (glyoxal, 1-230 ng m-3 and methylglyoxal, 2-120 ng m-3). We found that these levels (>6000 ng m-3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June, showing a maximum on 7 June, and then significantly decreased during the period 8-11 June, when the wind direction shifted from southerly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of

  6. Modifying the OPLS-AA force field to improve hydration free energies for several amino acid side chains using new atomic charges and an off-plane charge model for aromatic residues.

    PubMed

    Xu, Zhitao; Luo, Harry H; Tieleman, D Peter

    2007-02-01

    The hydration free energies of amino acid side chains are an important determinant of processes that involve partitioning between different environments, including protein folding, protein complex formation, and protein-membrane interactions. Several recent papers have shown that calculated hydration free energies for polar and aromatic residues (Trp, His, Tyr, Asn, Gln, Asp, Glu) in several common molecular dynamics force fields differ significantly from experimentally measured values. We have attempted to improve the hydration energies for these residues by modifying the partial charges of the OPLS-AA force field based on natural population analysis of density functional theory calculations. The resulting differences between calculated hydration free energies and experimental results for the seven side chain analogs are less than 0.1 kcal/mol. Simulations of the synthetic Trp-rich peptide Trpzip2 show that the new charges lead to significantly improved geometries for interacting Trp-side chains. We also investigated an off-plane charge model for aromatic rings that more closely mimics their electronic configuration. This model results in an improved free energy of hydration for Trp and a somewhat altered benzene-sodium potential of mean force with a more favorable energy for direct benzene-sodium contact.

  7. Gas origin of hydrate in the Qilian Mountain permafrost, Qinghai

    NASA Astrophysics Data System (ADS)

    Lu, Z.; Zhu, Y.; Liu, H.; Zhang, Y.; Sun, Z.

    2012-12-01

    Gas origin of hydrate is not clear yet in the Muli of Qilian mountain permafrost, which will obviously affect its further exploration direction. A case is illustrated in the hole of DK-2 during gas hydrate drilling; gas composition and isotopes of gas hydrate and its associated gases are analyzed; organic geochemistry on mudstone, oily shale, coal, oil & gas indications are correlated within the interval of gas hydrate occurrences; the aim is to discuss the source of gases from gas hydrate and its implication to gas hydrate exploration in the study area. Results from gas composition and isotopes of gas hydrate and its associated gases reveal that the origin of gases from gas hydrate is mainly concomitant with deep oil or crude oil in the study area. Parameters for the abundance, type and thermal evolution of organic matter in mudstone, oil shale, coal in the same interval of gas hydrate occurrence suggest that these strata, especially within gas hydrate stability zone, play little role in gas sources for gas hydrate. Reservoir pyrolysis results for oil & gas indication-bearing cores reveal that oil & gas indications are closely associated with gas hydrate within its interval, indicating that they may serve as a sign of gas hydrate in the study area.

  8. Clathrate hydrates in nature.

    PubMed

    Hester, Keith C; Brewer, Peter G

    2009-01-01

    Scientific knowledge of natural clathrate hydrates has grown enormously over the past decade, with spectacular new findings of large exposures of complex hydrates on the sea floor, the development of new tools for examining the solid phase in situ, significant progress in modeling natural hydrate systems, and the discovery of exotic hydrates associated with sea floor venting of liquid CO2. Major unresolved questions remain about the role of hydrates in response to climate change today, and correlations between the hydrate reservoir of Earth and the stable isotopic evidence of massive hydrate dissociation in the geologic past. The examination of hydrates as a possible energy resource is proceeding apace for the subpermafrost accumulations in the Arctic, but serious questions remain about the viability of marine hydrates as an economic resource. New and energetic explorations by nations such as India and China are quickly uncovering large hydrate findings on their continental shelves.

  9. Hydrogen bonding and molecular association in 2-(quinuclidinium)-butyric acid bromide hydrate studied by X-ray diffraction, DFT calculations, FTIR and NMR spectroscopy, and potentiometric titration

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.; Barczyński, P.

    2010-06-01

    The structure of 2-(quinuclidinium)-butyric acid bromide hydrate (QNBu·H 2O·HBr, 3) has been determined by X-ray diffraction, DFT calculations and characterized by FTIR and NMR spectroscopy. Crystals of 3 are monoclinic, space group P2 1. The water molecule interacts with the carboxylic group of 2-(quinuclidinium)-butyric acid and with the bromide anion by the COOH⋯OH 2 and HOH⋯Br hydrogen bonds of 2.575(3) and 3.293(2) Å, respectively. The structures of monomer ( 4) and dimeric cation ( 5) of the title complex have been optimized by the B3LYP/6-31G(d,p) approach, yielding conformations consistent with this in the crystal. The solid-state FTIR spectra of 3 and its deuterated analogue have been measured and compared with the theoretical spectrum of 4. The assignments of the observed and predicted bands have been proposed. The molecule of 3 has a chiral center at the C(9) atom, which is responsible for the non-magnetically equivalence of the α-ring and C(11)H 2 methylene protons in 1H NMR spectrum. The values of p Ka of quinuclidinium-acetate (quinuclidine betaine), 2-(quinuclidinium)-propionate and 2-(quinuclidinium)-butyrate have been determined by the potentiometric titration of their hydrohalides.

  10. Bio-inspired nitrile hydration by peptidic ligands based on L-cysteine, L-methionine or L-penicillamine and pyridine-2,6-dicarboxylic acid.

    PubMed

    Byrne, Cillian; Houlihan, Kate M; Devi, Prarthana; Jensen, Paul; Rutledge, Peter J

    2014-12-12

    Nitrile hydratase (NHase, EC 4.2.1.84) is a metalloenzyme which catalyses the conversion of nitriles to amides. The high efficiency and broad substrate range of NHase have led to the successful application of this enzyme as a biocatalyst in the industrial syntheses of acrylamide and nicotinamide and in the bioremediation of nitrile waste. Crystal structures of both cobalt(III)- and iron(III)-dependent NHases reveal an unusual metal binding motif made up from six sequential amino acids and comprising two amide nitrogens from the peptide backbone and three cysteine-derived sulfur ligands, each at a different oxidation state (thiolate, sulfenate and sulfinate). Based on the active site geometry revealed by these crystal structures, we have designed a series of small-molecule ligands which integrate essential features of the NHase metal binding motif into a readily accessible peptide environment. We report the synthesis of ligands based on a pyridine-2,6-dicarboxylic acid scaffold and L-cysteine, L-S-methylcysteine, L-methionine or L-penicillamine. These ligands have been combined with cobalt(III) and iron(III) and tested as catalysts for biomimetic nitrile hydration. The highest levels of activity are observed with the L-penicillamine ligand which, in combination with cobalt(III), converts acetonitrile to acetamide at 1.25 turnovers and benzonitrile to benzamide at 1.20 turnovers.

  11. Acyl homoserine lactone changes the abundance of proteins and the levels of organic acids associated with stationary phase in Salmonella Enteritidis.

    PubMed

    de Almeida, Felipe Alves; Pimentel-Filho, Natan de Jesus; Carrijo, Lanna Clícia; Bento, Cláudia Braga Pereira; Baracat-Pereira, Maria Cristina; Pinto, Uelinton Manoel; de Oliveira, Leandro Licursi; Vanetti, Maria Cristina Dantas

    2017-01-01

    Quorum sensing (QS) is cell-cell communication mechanism mediated by signaling molecules known as autoinducers (AIs) that lead to differential gene expression. Salmonella is unable to synthesize the AI-1 acyl homoserine lactone (AHL), but is able to recognize AHLs produced by other microorganisms through SdiA protein. Our study aimed to evaluate the influence of AI-1 on the abundance of proteins and the levels of organic acids of Salmonella Enteritidis. The presence of N-dodecyl-homoserine lactone (C12-HSL) did not interfere on the growth or the total amount of extracted proteins of Salmonella. However, the abundance of the proteins PheT, HtpG, PtsI, Adi, TalB, PmgI (or GpmI), Eno, and PykF enhanced while the abundance of the proteins RplB, RplE, RpsB, Tsf, OmpA, OmpC, OmpD, and GapA decreased when Salmonella Enteritidis was anaerobically cultivated in the presence of C12-HSL. Additionally, the bacterium produced less succinic, lactic, and acetic acids in the presence of C12-HSL. However, the concentration of extracellular formic acid reached 20.46 mM after 24 h and was not detected when the growth was in the absence of AI-1. Considering the cultivation period for protein extraction, their abundance, process and function, as well as the levels of organic acids, we observed in cells cultivated in presence of C12-HSL a correlation with what is described in the literature as entry into the stationary phase of growth, mainly related to nitrogen and amino acid starvation and acid stress. Further studies are needed in order to determine the specific role of the differentially abundant proteins and extracellular organic acids secreted by Salmonella in the presence of quorum sensing signaling molecules.

  12. The comparison of p Ka determination between carbonic acid and formic acid and its application to prediction of the hydration numbers

    NASA Astrophysics Data System (ADS)

    Wang, Xiang-xiang; Fu, Hui; Du, Dong-mei; Zhou, Zheng-yu; Zhang, An-guo; Su, Chun-fang; Ma, Ke-sheng

    2008-07-01

    The p Ka for H 2CO 3 have been calculated using the combination of the extended clusters-continuum model (ECM) with the polarizable continuum solvation model (PCM) and a comparison has been carried on with the p Ka prediction of HCOOH. Our results show that the calculated and experimental p Ka of HCOOH are in good agreement as two water molecules are added, the best agreement of p Ka 1 for H 2CO 3 is for n = 3 (the number of water molecules) and the closest agreement of p Ka 2 is for n = 4 at B3LYP/6-311++G(d, p) level. On the base of the results, attempts have been made to evaluate the hydration numbers.

  13. High abundances of oxalic, azelaic, and glyoxylic acids and methylglyoxal in the open ocean with high biological activity: Implication for secondary OA formation from isoprene

    NASA Astrophysics Data System (ADS)

    Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo; Fu, Pingqing

    2014-05-01

    Atmospheric dicarboxylic acids (DCA) are a ubiquitous water-soluble component of secondary organic aerosols (SOA), which can act as cloud condensation nuclei (CCN), affecting the Earth's climate. Despite the high abundances of oxalic acid and related compounds in the marine aerosols, there is no consensus on what controls their distributions over the open ocean. Marine biological productivity could play a role in the production of DCA, but there is no substantial evidence to support this hypothesis. Here we present latitudinal distributions of DCA, oxoacids and α-dicarbonyls in the marine aerosols from the remote Pacific. Their concentrations were found several times higher in more biologically influenced aerosols (MBA) than less biologically influenced aerosols. We propose isoprene and unsaturated fatty acids as sources of DCA as inferred from significantly higher abundances of isoprene-SOA tracers and azelaic acid in MBA. These results have implications toward the reassessment of climate forcing feedbacks of marine-derived SOA.

  14. High-throughput quantification of the levels and labeling abundance of free amino acids by liquid chromatography tandem mass spectrometry.

    PubMed

    Cocuron, Jean-Christophe; Tsogtbaatar, Enkhtuul; Alonso, Ana P

    2017-03-24

    Accurate assessment of mass isotopomer distributions (MIDs) of intracellular metabolites, such as free amino acids (AAs), is crucial for quantifying in vivo fluxes. To date, the majority of studies that measured AA MIDs have relied on the analysis of proteinogenic rather than free AAs by: i) GC-MS, which involved cumbersome process of derivatization, or ii) NMR, which requires large quantities of biological sample. In this work, the development and validation of a high-throughput LC-MS/MS method allowing the quantification of the levels and labeling of free AAs is described. Sensitivity in the order of the femtomol was achieved using multiple reaction monitoring mode (MRM). The MIDs of all free AAs were assessed without the need of derivatization, and were validated (except for Trp) on a mixture of unlabeled AA standards. Finally, this method was applied to the determination of the (13)C-labeling abundance in free AAs extracted from maize embryos cultured with (13)C-glutamine or (13)C-glucose. Although Cys was below the limit of detection in these biological samples, the MIDs of a total of 18 free AAs were successfully determined. Due to the increased application of tandem mass spectrometry for (13)C-Metabolic Flux Analysis, this novel method will enable the assessment of more complete and accurate labeling information of intracellular AAs, and therefore a better definition of the fluxes.

  15. Activation and attenuation of apoptosis of CD4+ T cells following in vivo exposure to two common environmental toxicants, trichloroacetaldehyde hydrate and trichloroacetic acid.

    PubMed

    Blossom, Sarah J; Pumford, Neil R; Gilbert, Kathleen M

    2004-11-01

    Exposure to occupationally relevant concentrations of the environmental pollutant, trichloroethylene (TCE), in the drinking water of autoimmune-prone MRL+/+ mice has been shown to promote the generation of lupus and autoimmune hepatitis in association with the activation of Interferon-gamma (IFN-gamma)-producing CD4+ T cells. Since blocking TCE metabolism suppressed the TCE-induced alteration in immune function, the present study was initiated to determine whether the major metabolites of TCE, trichloroacetaldehyde hydrate (TCAH) and trichloroacetic acid (TCA) could also mediate these immunoregulatory affects in vivo. TCAH and TCA were administered to the drinking water of MRL+/+ mice for 4 weeks. CD4+ T cells from TCAH and TCA-treated MRL+/+ mice, unlike CD4+ T cells from control mice, demonstrated functional and phenotypic signs of activation, as evidenced by increased IFN-gamma production in association with the increased percentage of CD62L(lo) CD4+ T cells. Interestingly, it was also found that the CD4+ T cells from the TCAH and TCA-treated mice showed a decreased susceptibility to the activation-induced cell death (AICD) form of apoptosis following re-stimulation in vitro. By demonstrating that TCAH and TCA can activate CD4+ T cells and inhibit their apoptosis following in vivo exposure represents a mechanism by which environmental toxicants may induce or accelerate the development of autoimmune disease.

  16. Hydrated and anhydrous forms of copper(II) complex of 3-methylpicolinic acid, and spectroscopic studies of their ROS-inducing and proteasome inhibition

    NASA Astrophysics Data System (ADS)

    Lai, Jing Wei; Chan, Cheang Wei; Ng, Chew Hee; Ooi, Ing Hong; Tan, Kong Wai; Maah, Mohd Jamil; Ng, Seik Weng

    2016-02-01

    The hydrated and anhydrous forms of the copper(II) complex of 3-methylpicolinic acid, monomeric [Cu(3Me-pic)2(H2O)]·H2O 1 and polymeric [Cu(3Me-pic)2]n2, were synthesized and characterized by FTIR, UV-visible spectroscopy, conductivity measurement, magnetic susceptibility determination, electron paramagnetic resonance (EPR) and light scattering. Crystal structure analysis of 2 shows that it has a doubly-bridged polymeric structure, involving diagonally stacked Cu(3Me-pic)2 units which are linked via carbonyl oxygen atoms of the 3Me-pic moieties. Analysis of EPR spectra at 133 K and 293 K suggests isotropic intermolecular spin interaction only in 2. Complex 2 dissolved in DMF and DMSO solvents to yield nano-size particles. Solution studies show aqueous solutions of 1 and 2 contain the same neutral Cu(3Me-pic)2 species, which generates less hydroxyl radicals from the reaction with hydrogen peroxide than their precursor CuCl2. The Cu(3Me-pic)2 species exhibit more selective inhibition of the β2 site of the 20S proteasome, among the three proteolytic sites.

  17. Surfactant adsorption and interfacial tension investigations on cyclopentane hydrate.

    PubMed

    Aman, Zachary M; Olcott, Kyle; Pfeiffer, Kristopher; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

    2013-02-26

    Gas hydrates represent an unconventional methane resource and a production/safety risk to traditional oil and gas flowlines. In both systems, hydrate may share interfaces with both aqueous and hydrocarbon fluids. To accurately model macroscopic properties, such as relative permeability in unconventional systems or dispersion viscosity in traditional systems, knowledge of hydrate interfacial properties is required. This work presents hydrate cohesive force results measured on a micromechanical force apparatus, and complementary water-hydrocarbon interfacial tension data. By combining a revised cohesive force model with experimental data, two interfacial properties of cyclopentane hydrate were estimated: hydrate-water and hydrate-cyclopentane interfacial tension values at 0.32 ± 0.05 mN/m and 47 ± 5 mN/m, respectively. These fundamental physiochemical properties have not been estimated or measured for cyclopentane hydrate to date. The addition of surfactants in the cyclopentane phase significantly reduced the cyclopentane hydrate cohesive force; we hypothesize this behavior to be the result of surfactant adsorption on the hydrate-oil interface. Surface excess quantities were estimated for hydrate-oil and water-oil interfaces using four carboxylic and sulfonic acids. The results suggest the density of adsorbed surfactant may be 2× larger for the hydrate-oil interface than the water-oil interface. Additionally, hydrate-oil interfacial tension was observed to begin decreasing from the baseline value at significantly lower surfactant concentrations (1-3 orders of magnitude) than those for the water-oil interfacial tension.

  18. Factors governing abundance of hydrolyzable amino acids in the sediments from the N.W. European Continental Margin (47 50°N)

    NASA Astrophysics Data System (ADS)

    Boski, T.; Pessoa, J.; Pedro, P.; Thorez, J.; Dias, J. M. A.; Hall, I. R.

    1998-12-01

    Fifty-six samples representing 6 sediment cores taken along the N.W. European Continental Margin from the shelf, slope and abyssal plain of the Goban Spur and Meriadzek Terrace were quantitatively analysed for total hydrolyzable amino acids (THAA) and clay minerals. In descending order, the five most abundant amino acids making up more than 70% of the total were: aspartic acid, glycine, serine, alanine and glutamic acid. Clay mineral proportions were typical for the N.E. Atlantic, in order of descending abundance: illite, kaolinite, chlorite, smectite and mixed layers. The Meriadzek Terrace area is characterised by fine grain suspension sedimentation with a low pelagic carbonate input and the lowest content of THAA. In contrast, the Goban Spur transect is characterised by much higher carbonate inputs and more vigorous hydrodynamics as judged from granulometry and the high abundance of minerals of shelf and continental origin and a generally higher THAA content. The pelagic portion of THAA deposited at the sea floor is more readily mineralised during early diagenesis than the more `refractory', clay mineral-associated continental portion. Along this margin the average mineralization of THAA down to 25 cm in the sediment is about 54%. There is a significant affinity between chlorites and amino acids which we suggest may involve the formation of ionic bonds between the octahedral layers of the clay and the amino acids.

  19. Metabolomic profiling in Selaginella lepidophylla at various hydration states provides new insights into the mechanistic basis of desiccation tolerance.

    PubMed

    Yobi, Abou; Wone, Bernard W M; Xu, Wenxin; Alexander, Danny C; Guo, Lining; Ryals, John A; Oliver, Melvin J; Cushman, John C

    2013-03-01

    Selaginella lepidophylla is one of only a few species of spike mosses (Selaginellaceae) that have evolved desiccation tolerance (DT) or the ability to 'resurrect' from an air-dried state. In order to understand the metabolic basis of DT, S. lepidophylla was subjected to a five-stage, rehydration/dehydration cycle, then analyzed using non-biased, global metabolomics profiling technology based on GC/MS and UHLC/MS/MS(2) platforms. A total of 251 metabolites including 167 named (66.5%) and 84 (33.4%) unnamed compounds were characterized. Only 42 (16.7%) and 74 (29.5%) of compounds showed significantly increased or decreased abundance, respectively, indicating that most compounds were produced constitutively, including highly abundant trehalose, sucrose, and glucose. Several glycolysis/gluconeogenesis and tricarboxylic acid (TCA) cycle intermediates showed increased abundance at 100% relative water content (RWC) and 50% RWC. Vanillate, a potent antioxidant, was also more abundant in the hydrated state. Many different sugar alcohols and sugar acids were more abundant in the hydrated state. These polyols likely decelerate the rate of water loss during the drying process as well as slow water absorption during rehydration, stabilize proteins, and scavenge reactive oxygen species (ROS). In contrast, nitrogen-rich and γ-glutamyl amino acids, citrulline, and nucleotide catabolism products (e.g. allantoin) were more abundant in the dry states, suggesting that these compounds might play important roles in nitrogen remobilization during rehydration or in ROS scavenging. UV-protective compounds such as 3-(3-hydroxyphenyl)propionate, apigenin, and naringenin, were more abundant in the dry states. Most lipids were produced constitutively, with the exception of choline phosphate, which was more abundant in dry states and likely plays a role in membrane hydration and stabilization. In contrast, several polyunsaturated fatty acids were more abundant in the hydrated states

  20. In-situ characterization of gas hydrates

    NASA Astrophysics Data System (ADS)

    Moerz, T.; Brueckmann, W.; Linke, P.; Tuerkay, M.

    2003-04-01

    Gas hydrates are a dynamic reservoir in the marine carbon cycle and a periodically large and focussed source of methane probably constituting the largest carbon reservoir on earth. Therefore an important issue in gas hydrate research is the need for better tools to remotely estimate the volume and stability conditions of marine gas hydrate in the near sub-surface. It is also crucial to precisely determine the hydrate stability conditions in the near sub-surface, where gas hydrates are most susceptible to dissolution under changing P/T conditions. Our knowledge about the occurrence, spatial distribution, and life-cycle of gas hydrates in marine sediments is mainly derived from indirect geophysical and geochemical evidence. In a few instances gas hydrates have also been directly observed and sampled at the sea floor. For regional or global estimates of hydrate volumes and stability conditions however, new techniques for ground-truthing and calibration of geophysical, biological and geochemical methods are needed. During the OTEGA cruise with RV SONNE to Hydrate Ridge off Oregon a new device for in-situ characterization of gas hydrates was deployed and tested for the first time. The tool, HDSD (Hydrate Detection and Stability Determination) is being developed as part of Cooperative Research Center (SFB) 574 "Volatiles and Fluids in Subduction Zones". It is designed to identify and quantify small volumes of near-surface gas hydrate through continuous in-situ thermal and resistivity monitoring in a defined volume of sediment while it is slowly heated to destabilize gas hydrates embedded in it. In its current configuration HDSD is delivered to the seafloor by a video-guided GEOMAR BC Lander system. The sediment volume to be tested for the presence and abundance of gas hydrates is first isolated by a rectangular experiment chamber that is pushed into the upper 30cm of sediment. A "stinger", centrally mounted in the chamber and equipped with two arrays of sensors, provides

  1. Dietary sunflower oil modulates milk fatty acid composition without major changes in adipose and mammary tissue fatty acid profile or related gene mRNA abundance in sheep.

    PubMed

    Castro-Carrera, T; Frutos, P; Leroux, C; Chilliard, Y; Hervás, G; Belenguer, A; Bernard, L; Toral, P G

    2015-04-01

    There are very few studies in ruminants characterizing mammary and adipose tissue (AT) expression of genes and gene networks for diets causing variations in milk fatty acid (FA) composition without altering milk fat secretion, and even less complementing this information with data on tissue FA profiles. This work was conducted in sheep in order to investigate the response of the mammary gland and the subcutaneous and perirenal AT, in terms of FA profile and mRNA abundance of genes involved in lipid metabolism, to a diet known to modify milk FA composition. Ten lactating Assaf ewes were randomly assigned to two treatments consisting of a total mixed ration based on alfalfa hay and a concentrate (60 : 40) supplemented with 0 (control diet) or 25 (SO diet) g of sunflower oil/kg of diet dry matter for 7 weeks. Milk composition, including FA profile, was analysed after 48 days on treatments. On day 49, the animals were euthanized and tissue samples were collected to analyse FA and mRNA abundance of 16 candidate genes. Feeding SO did not affect animal performance but modified milk FA composition. Major changes included decreases in the concentration of FA derived from de novo synthesis (e.g. 12:0, 14:0 and 16:0) and increases in that of long-chain FA (e.g. 18:0, c9-18:1, trans-18:1 isomers and c9,t11-CLA); however, they were not accompanied by significant variations in the mRNA abundance of the studied lipogenic genes (i.e. ACACA, FASN, LPL, CD36, FABP3, SCD1 and SCD5) and transcription factors (SREBF1 and PPARG), or in the constituent FA of mammary tissue. Regarding the FA composition of AT, the little influence of SO did not appear to be linked to changes in gene mRNA abundance (decreases of GPAM and SREBF1 in both tissues, and of PPARG in the subcutaneous depot). Similarly, the great variation between AT (higher contents of saturated FA and trans-18:1 isomers in the perirenal, and of cis-18:1, c9,t11-CLA and n-3 PUFA in the subcutaneous AT) could not be related to

  2. Molecular structure of hydrated complex of 1,4-dimethylpiperazine di-betaine with L-tartaric acid

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2008-12-01

    1,4-Dimethylpiperazine di-betaine (DBPZ) forms a crystalline complex with L-tartaric acid (TA) and two and a half water molecules. The crystals are monoclinic, space group P2 1. The piperazine has a chair conformation with the methyl groups in the equatorial positions and the axial CH 2COO substituents. One of the CH 2COO group is protonated and forms with the neighboring DBPZ molecule the COO sbnd H⋯OOC hydrogen bond of the length 2.476(3) Å, which links them into a chain. The semi-tartrate anions, form a chain through the symmetrical, short COO⋯H⋯OOC hydrogen bond of 2.464(3) Å. The crystals have a layer structure, where hydrogen-bonded sheets of TA and water molecules are separated by the chains of DBPZ; no H-bonds between water and DBPZ are present. In the optimized molecules in the B3LYP/6-31G(d,p) approach, the tartaric acid interacts with the tartrate di-anions through the COO sbnd H⋯OOC hydrogen bonds of 2.506 Å, while the DBPZ has the same conformation as in the crystals. The FTIR spectrum of the solid complex is consistent with the X-ray results.

  3. Use of an amorphous iron oxide hydrated as catalyst for hydrogen peroxide oxidation of ferulic acid in water.

    PubMed

    Andreozzi, Roberto; Canterino, Marisa; Caprio, Vincenzo; Di Somma, Ilaria; Marotta, Raffaele

    2008-04-01

    The abatement of ferulic acid (FA), a polyphenolic constituent of olive mill wastewater, is studied in the pH range 5.0-7.0 by using hydrogen peroxide and an amorphous iron oxide as catalyst. The effect of pH, catalyst load, hydrogen peroxide and substrate starting concentrations is assessed during the investigation. A suitable reaction scheme is developed and used to build a mathematical model which satisfactorily describes the system's behavior. Kinetic constants for the proposed scheme as well as the total active site concentration of the catalyst in the studied pH range are estimated. The occurrence of internal mass-transfer limitation for the adopted granulometric fraction of the catalyst is demonstrated.

  4. Intermolecular momentum transfer in poly(perfluorosulfonic acid) membrane hydrated by aqueous solution of methanol: A molecular dynamics simulation study.

    PubMed

    Shao, Changle; Yan, Liuming; Ji, Xiaobo; Zhu, Suhua

    2009-12-14

    Intermolecular momentum transfer in methanol-water mixture solvated poly(perfluoro-sulfonic acid) membrane is studied in terms of center of mass velocity cross-correlation functions between molecular mass centers in their first coordination shells based on molecular dynamics simulations. Moreover, the center of mass velocity cross-correlation functions are also decomposed into longitudinal and transversal contributions. The fastest momentum transfer is observed between hydronium cation and water molecule due to the strong hydrogen bond interaction. The center of mass velocity cross-correlation functions reach peak value in about 36 fs, corresponding to a single collision with a neighboring molecule. For the momentum transfer between the water molecule and methanol molecule, the peaking time is 70 fs or about twice of that between hydronium cation and water molecule. Oscillation of the center of mass velocity cross-correlation functions between hydronium cation and water molecule is also observed due to the cage effect in their equilibrium positions.

  5. Three-dimensional hydrogen-bonded structures in the hydrated proton-transfer salts of isonipecotamide with the dicarboxylic oxalic and adipic acid homologues.

    PubMed

    Smith, Graham; Wermuth, Urs D

    2013-10-01

    The structures of the 1:1 hydrated proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with oxalic acid, 4-carbamoylpiperidinium hydrogen oxalate dihydrate, C6H13N2O(+)·C2HO4(-)·2H2O, (I), and with adipic acid, bis(4-carbamoylpiperidinium) adipate dihydrate, 2C6H13N2O(+)·C6H8O4(2-)·2H2O, (II), are three-dimensional hydrogen-bonded constructs involving several different types of enlarged water-bridged cyclic associations. In the structure of (I), the oxalate monoanions give head-to-tail carboxylic acid O-H···O(carboxyl) hydrogen-bonding interactions, forming C(5) chain substructures which extend along a. The isonipecotamide cations also give parallel chain substructures through amide N-H···O hydrogen bonds, the chains being linked across b and down c by alternating water bridges involving both carboxyl and amide O-atom acceptors and amide and piperidinium N-H···O(carboxyl) hydrogen bonds, generating cyclic R4(3)(10) and R3(2)(11) motifs. In the structure of (II), the asymmetric unit comprises a piperidinium cation, half an adipate dianion, which lies across a crystallographic inversion centre, and a solvent water molecule. In the crystal structure, the two inversion-related cations are interlinked through the two water molecules, which act as acceptors in dual amide N-H···O(water) hydrogen bonds, to give a cyclic R4(2)(8) association which is conjoined with an R4(4)(12) motif. Further N-H···O(water), water O-H···O(amide) and piperidinium N-H···O(carboxyl) hydrogen bonds give the overall three-dimensional structure. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. The presence of solvent water molecules in these structures is largely responsible for the non-occurrence of the common hydrogen-bonded amide-amide dimer, promoting instead various expanded cyclic hydrogen-bonding motifs.

  6. Heat stress, hydration and uric acid: a cross-sectional study in workers of three occupations in a hotspot of Mesoamerican nephropathy in Nicaragua

    PubMed Central

    Aragón, Aurora; González, Marvin; Weiss, Ilana; Glaser, Jason; Rivard, Christopher J; Roncal-Jiménez, Carlos; Correa-Rotter, Ricardo; Johnson, Richard J

    2016-01-01

    Objectives To study Mesoamerican nephropathy (MeN) and its risk factors in three hot occupations. Design Cross-sectional. Setting Chinandega and León municipalities, a MeN hotspot on the Nicaraguan Pacific coast, January–February 2013. Participants 194 male workers aged 17–39 years: 86 sugarcane cutters, 56 construction workers, 52 small-scale farmers. Outcome measures (1) Differences between the three occupational groups in prevalences/levels of socioeconomic, occupational, lifestyle and health risk factors for chronic kidney disease (CKD) and in biomarkers of kidney function and hydration; (2) differences in prevalences/levels of CKD risk factors between workers with reduced estimated glomerular filtration rate (eGFRCKD-EPI <80 mL/min/1.73 m2) and workers with normal kidney function (eGFRCKD-EPI ≥80 mL/min/1.73 m2). Results Sugarcane cutters were more exposed to heat and consumed more fluid on workdays and had less obesity, lower blood sugar, lower blood pressure and a better lipid profile. Reduced eGFR occurred in 16%, 9% and 2% of sugarcane cutters, construction workers and farmers, respectively (trend cane > construction > farming, p=0.003). Significant trends (cane > construction > farming) were also observed for high serum urea nitrogen (blood urea nitrogen (BUN) >20 mg/dL), high serum creatinine (SCr >1.2 mg/dL), low urinary pH (≤5.5) and high BUN/SCr ratio (>20) but not for high urinary specific gravity (≥1.030). Sugarcane cutters also more often had proteinuria and blood and leucocytes in the urine. Workers with eGFR <80 mL/min/1.73 m2 reported a higher intake of water and lower intake of sugary beverages. Serum uric acid levels related strongly and inversely to eGFR levels (adj β −10.4 mL/min/1.73 m2, 95% CI −12.2 to −8.5, p<0.001). No associations were observed for other metabolic risk factors, pesticides, non-steroidal anti-inflammatory drugs or alcohol. Among cane cutters, consumption of electrolyte hydration

  7. 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.

  8. Gas Hydrate Nucleation Processes

    NASA Astrophysics Data System (ADS)

    David, R. E.; Zatsepina, O.; Phelps, T. J.

    2003-12-01

    The onset of gas hydrate nucleation is greatly affected by the thermal history of the water that forms its lattice structure. Hydrate formation experiments were performed in a 72 liter pressure vessel by bubbling carbon dioxide through a 1 liter column at hydrate formation pressures (1.4 to 3.7 MPa) and temperatures (275.0 to 278.0 K) to quantify this effect. They show that when even a fraction ( e. g. 20 %) of the water in which hydrate has formed was recently frozen and thawed, the overpressurization for nucleation was reduced by an average of 50 % versus experiments performed in distilled water. In those experiments where a lower overpressure is present when hydrate nucleated, they tended to form on the surface of bubbles, whereas when a higher amount of overpressure was necessary for hydrate to nucleate, they appeared to form abruptly on bubble surfaces as well as from the bulk liquid phase. In approximation of classical nucleation, hydrate formation could be described as occurring by the spontaneous joining together of arising components of the hydrate lattice. In water that was frozen, and kept at a low temperature (< 275 K), molecular simulation models predict the predominance of water molecules organized as penatmeters, a possible subunit of the hydrate lattice. Our results suggest that in nature, initiation of hydrate formation may be strongly influenced by temperature dependant pre-structuring of water molecules prior to their contact with gas.

  9. Origins of hydration lubrication.

    PubMed

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-14

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

  10. Hydrate-phobic surfaces: fundamental studies in clathrate hydrate adhesion reduction.

    PubMed

    Smith, J David; Meuler, Adam J; Bralower, Harrison L; Venkatesan, Rama; Subramanian, Sivakumar; Cohen, Robert E; McKinley, Gareth H; Varanasi, Kripa K

    2012-05-07

    Clathrate hydrate formation and subsequent plugging of deep-sea oil and gas pipelines represent a significant bottleneck for deep-sea oil and gas operations. Current methods for hydrate mitigation are expensive and energy intensive, comprising chemical, thermal, or flow management techniques. In this paper, we present an alternate approach of using functionalized coatings to reduce hydrate adhesion to surfaces, ideally to a low enough level that hydrodynamic shear stresses can detach deposits and prevent plug formation. Systematic and quantitative studies of hydrate adhesion on smooth substrates with varying solid surface energies reveal a linear trend between hydrate adhesion strength and the practical work of adhesion (γ(total)[1 + cos θ(rec)]) of a suitable probe liquid, that is, one with similar surface energy properties to those of the hydrate. A reduction in hydrate adhesion strength by more than a factor of four when compared to bare steel is achieved on surfaces characterized by low Lewis acid, Lewis base, and van der Waals contributions to surface free energy such that the practical work of adhesion is minimized. These fundamental studies provide a framework for the development of hydrate-phobic surfaces, and could lead to passive enhancement of flow assurance and prevention of blockages in deep-sea oil and gas operations.

  11. Strong anion exchange liquid chromatographic separation of protein amino acids for natural 13C-abundance determination by isotope ratio mass spectrometry.

    PubMed

    Abaye, Daniel A; Morrison, Douglas J; Preston, Tom

    2011-02-15

    Amino acids are the building blocks of proteins and the analysis of their (13)C abundances is greatly simplified by the use of liquid chromatography (LC) systems coupled with isotope ratio mass spectrometry (IRMS) compared with gas chromatography (GC)-based methods. To date, various cation exchange chromatography columns have been employed for amino acid separation. Here, we report strong anion exchange chromatography (SAX) coupled to IRMS with a Liquiface interface for amino acid δ(13)C determination. Mixtures of underivatised amino acids (0.1-0.5 mM) and hydrolysates of representative proteins (prawns and bovine serum albumin) were resolved by LC/IRMS using a SAX column and inorganic eluents. Background inorganic carbon content was minimised through careful preparation of alkaline reagents and use of a pre-injector on-line carbonate removal device. SAX chromatography completely resolved 11 of the 16 expected protein amino acids following acid hydrolysis in underivatised form. Basic and neutral amino acids were resolved with 35 mM NaOH in isocratic mode. Elution of the aromatic and acidic amino acids required a higher hydroxide concentration (180 mM) and a counterion (NO 3-, 5-25 mM). The total run time was 70 min. The average δ(13)C precision of baseline-resolved peaks was 0.75‰ (range 0.04 to 1.06‰). SAX is a viable alternative to cation chromatography, especially where analysis of basic amino acids is important. The technology shows promise for (13)C amino acid analysis in ecology, archaeology, forensic science, nutrition and protein metabolism.

  12. Noble gas encapsulation: clathrate hydrates and their HF doped analogues.

    PubMed

    Mondal, Sukanta; Chattaraj, Pratim Kumar

    2014-09-07

    The significance of clathrate hydrates lies in their ability to encapsulate a vast range of inert gases. Although the natural abundance of a few noble gases (Kr and Xe) is poor their hydrates are generally abundant. It has already been reported that HF doping enhances the stability of hydrogen hydrates and methane hydrates, which prompted us to perform a model study on helium, neon and argon hydrates with their HF doped analogues. For this purpose 5(12), 5(12)6(8) and their HF doped analogues are taken as the model clathrate hydrates, which are among the building blocks of sI, sII and sH types of clathrate hydrate crystals. We use the dispersion corrected and gradient corrected hybrid density functional theory for the calculation of thermodynamic parameters as well as conceptual density functional theory based reactivity descriptors. The method of the ab initio molecular dynamics (AIMD) simulation is used through atom centered density matrix propagation (ADMP) techniques to envisage the structural behaviour of different noble gas hydrates on a 500 fs timescale. Electron density analysis is carried out to understand the nature of Ng-OH2, Ng-FH and Ng-Ng interactions. The current results noticeably demonstrate that the noble gas (He, Ne, and Ar) encapsulation ability of 5(12), 5(12)6(8) and their HF doped analogues is thermodynamically favourable.

  13. Bacterial Growth, Necromass Turnover, And Endospore Abundance In The Deep Subseafloor Sediments Of The Greenland Shelf Using D:L Amino Acid Model.

    NASA Astrophysics Data System (ADS)

    Mhatre, S. S.; Braun, S.; Jaussi, M.; Røy, H.; Jørgensen, B. B.; Lomstein, B. A.

    2015-12-01

    The subsurface realm is colonized by a large number of microorganisms- about 3 × 1029. Microbial cells in these very stable and oligotrophic settings catabolize at a much slower rate than model organisms in nutrient rich cultures. The aim of this work was to use recently developed D:L-amino acid racemization model for studying the turnover times of microbial biomass and microbial necromass in a ~12,000 years old Greenland shelf marine sediment samples. Sediments were analyzed for total hydrolysable amino acids (THAA), the bacterial endospore marker dipicolinic acid (DPA), and amino acid enantiomers of aspartic acid. The percentage amino acid carbon content (%TAAC) and the percentage amino acid nitrogen content (%TAAN) were used for determining the degradation state of the organic matter. Endospores quantified using DPA quantification method were found to be as abundant as vegetative cells. The microbial necromass turnover times were thousand years, and biomass turnover times were in the range of tens to hundred years. Studies with deeper sediment cores will further improve our understanding of the energetic limits of life in the deep biosphere.

  14. Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

    NASA Technical Reports Server (NTRS)

    Jenkins, J. M.; Steffes, P. G.

    1992-01-01

    Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued

  15. Single-step analysis of low abundance phosphoamino acids via on-line sample preconcentration with chemical derivatization by capillary electrophoresis.

    PubMed

    Ptolemy, Adam S; Britz-McKibbin, Philip

    2005-09-01

    New strategies for rapid, sensitive and high-throughput analysis of low abundance metabolites in biological samples are required for future metabolomic research. In this report, a direct method for sub-micromolar analyses of phosphoamino acids was developed using on-line sample preconcentration with 9-fluorenylmethyloxycarbonyl chloride (FMOC) derivatization by capillary electrophoresis (CE) and UV detection. Analyte focusing by dynamic pH junction and FMOC labeling efficiency were influenced by several experimental factors including buffer pH, ionic strength, sample injection length and FMOC concentration. About a 200-fold enhancement in concentration sensitivity was achieved under optimal conditions relative to conventional off-line derivatization, as reflected by a detection limit (S/N approximately 3) of 0.1 microM. In-capillary sample preconcentration with chemical labeling by CE offers a unique single-step analytical platform for high-throughput screening of low abundance metabolites without intrinsic chromophores.

  16. Fragmentation and hydration of tektites and microtektites

    USGS Publications Warehouse

    Glass, B.P.; Muenow, D.W.; Bohor, B.F.; Meeker, G.P.

    1997-01-01

    An examination of data collected over the last 30 years indicates that the percent of glass fragments vs. whole splash forms in the Cenozoic microtektite strewn fields increases towards the source crater (or source region). We propose that this is due to thermal stress produced when tektites and larger microtektites fall into water near the source crater while still relatively hot (>1150 ??C). We also find evidence (low major oxide totals, frothing when melted) for hydration of most of the North American tektite fragments and microtektites found in marine sediments. High-temperature mass spectrometry indicates that these tektite fragments and microtektites contain up to 3.8 wt% H2O. The H2O-release behavior during the high-temperature mass-spectrometric analysis, plus high Cl abundances (???0.05 wt%), indicate that the North. American tektite fragments and microtektites were hydrated in the marine environment (i.e., the H2O was not trapped solely on quenching from a melt). The younger Ivory Coast and Australasian microtektites do not exhibit much evidence of hydration (at least not in excess of 0.5 wt% H2O); this suggests that the degree of hydration increases with age. In addition, we find that some glass spherules (with 65 wt% SiO2 can undergo simple hydration in the marine environment, while impact glasses (with <65 wt% SiO2) can also undergo palagonitization.

  17. Effect of ribonucleic acid (RNA) isolation methods on putative reference genes messenger RNA abundance in human spermatozoa.

    PubMed

    Barragán, M; Martínez, A; Llonch, S; Pujol, A; Vernaeve, V; Vassena, R

    2015-07-01

    Although the male gamete participates in a significant proportion of infertility cases, there are currently no proven molecular markers of sperm quality. The search for significant gene expression markers is partially hindered by the lack of a recognized set of reference genes (RGs) to normalize reverse transcription quantitative PCR (RT-qPCR) data across studies. The aim of this study is to define a set of RGs in assisted reproduction patients undergoing different sample collection and RNA isolation methods. Twenty-two normozoospermic men were included in the study. From each man, semen was either cryopreserved by slow freezing or analyzed fresh, and, for each, RNA was extracted with either phenol-free or phenol-based methods. In two cases, both methods were used to isolate RNA. Twenty putative RGs were analyzed and their mRNA abundance across samples was estimated by RT-qPCR. To determine the genes whose steady-state mRNA abundance remains unchanged, three different algorithms (geNorm, BestKeeper and NormFinder) were applied to the qPCR data. We found that RGs such as GAPDH or ACTB, useful in other biological contexts, cannot be used as reference for human spermatozoa. It is possible to compare gene expression from fresh and cryopreserved sperm samples using the same isolation method, while the mRNA abundance of expressed genes becomes different depending on the RNA isolation technique employed. In our conditions, the most appropriate RGs for RT-qPCR analysis were RPLP1, RPL13A, and RPLP2. Published discrepancies in gene expression studies in human spermatozoa may be due in part to inappropriate RGs selection, suggesting a possible different interpretation of PCR data in several reports, which were normalized using unstable RGs.

  18. The use of amino acid indices for assessing organic matter quality and microbial abundance in deep-sea Antarctic sediments of IODP Expedition 318

    USGS Publications Warehouse

    Carr, Stephanie A; Mills, Christopher; Mandernack, Kevin W

    2016-01-01

    The Adélie Basin, located offshore of the Wilkes Land margin, experiences unusually high sedimentation rates (~ 2 cm yr− 1) for the Antarctic coast. This study sought to compare depthwise changes in organic matter (OM) quantity and quality with changes in microbial biomass with depth at this high-deposition site and an offshore continental margin site. Sediments from both sites were collected during the International Ocean Drilling (IODP) Program Expedition 318. Viable microbial biomass was estimated from concentrations of bacterial-derived phospholipid fatty acids, while OM quality was assessed using four different amino acid degradation proxies. Concentrations of total hydrolysable amino acids (THAA) measured from the continental margin suggest an oligotrophic environment, with THAA concentrations representing only 2% of total organic carbon with relative proportions of non-protein amino acids β-alanine and γ-aminobutyric acid as high as 40%. In contrast, THAA concentrations from the near-shore Adélie Basin represent 40%–60% of total organic carbon. Concentrations of β-alanine and γ-aminobutyric acid were often below the detection limit and suggest that the OM of the basin as labile. DI values in surface sediments at the Adélie and margin sites were measured to be + 0.78 and − 0.76, reflecting labile and more recalcitrant OM, respectively. Greater DI values in deeper and more anoxic portions of both cores correlated positively with increased relative concentrations of phenylalanine plus tyrosine and may represent a change of redox conditions, rather than OM quality. This suggests that DI values calculated along chemical profiles should be interpreted with caution. THAA concentrations, the percentage of organic carbon (CAA%) and total nitrogen (NAA%) represented by amino acids at both sites demonstrated a significant positive correlation with bacterial abundance estimates. These data suggest that the selective degradation of amino acids, as

  19. Hydration rate of obsidian.

    PubMed

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

  20. Sulfuric acid vapor and other cloud-related gases in the Venus atmosphere - Abundances inferred from observed radio opacity

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.; Eshleman, V. R.

    1982-01-01

    It is suggested that the absorbing characteristics of sulfuric acid vapor appear to reconcile what had been thought to be an inconsistency among measurements and deductions regarding the constituents of the Venus atmosphere and radio occultation, radar reflection, and radio emission measurements of its opacity. Laboratory measurements of sulfuric acid, sulfur dioxide, water vapor, and carbon dioxide are used to model relative contributions to opacity as a function of height in a way that is consistent with observations of the constituents and absorbing properties of the atmosphere. It is concluded that sulfuric acid vapor is likely to be the principal microwave absorber in the 30-50 km altitude range of the middle atmosphere of Venus.

  1. Sulfuric acid on Europa and the radiolytic sulfur cycle

    NASA Technical Reports Server (NTRS)

    Carlson, R. W.; Johnson, R. E.; Anderson, M. S.

    1999-01-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  2. Sulfuric acid on Europa and the radiolytic sulfur cycle.

    PubMed

    Carlson, R W; Johnson, R E; Anderson, M S

    1999-10-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  3. 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

  4. 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

  5. Effects of ruminal infusion of garlic oil on fermentation dynamics, Fatty Acid profile and abundance of bacteria involved in biohydrogenation in rumen of goats.

    PubMed

    Zhu, Zhi; Mao, Shengyong; Zhu, Weiyun

    2012-07-01

    This study aimed to investigate the effects of ruminal infusion of garlic oil (GO) on fermentation dynamics, fatty acid (FA) profile, and abundance of bacteria involved in biohydrogenation in the rumen. Six wethers fitted with ruminal fistula were assigned to two groups for cross-over design with a 14-d interval. Each 30-d experimental period consisted of a 27-d adaptation and a 3-d sample collection. Goats were fed a basal diet without (control) or with GO ruminal infusion (0.8 g/d). Ruminal contents collected before (0 h) and at 2, 4, 6, 8, and 10 h after morning feeding were used for fermentation analysis, and 0 h samples were further used for FA determination and DNA extraction. Garlic oil had no influence on dry matter intakes of concentrate and hay. During ruminal fermentation, GO had no effects on total VFA concentration and individual VFA molar proportions, whereas GO increased the concentrations of ammonia nitrogen and microbial crude protein (p<0.05). Compared with control, GO group took a longer time for total VFA concentration and propionate molar proportion to reach their respective maxima after morning feeding. The ratio of acetate to propionate in control reduced sharply after morning feeding, whereas it remained relatively stable in GO group. Fatty acid analysis showed that GO reduced saturated FA proportion (p<0.05), while increasing the proportions of C18, t11-18:1 (TVA), c9,t11-conjugated linoleic acid (c9,t11-CLA), t10,c12-CLA, and polyunsaturated FA (p<0.05). The values of TVA/(c9,t11-CLA+TVA) and C18:0/(TVA+ C18:0) were reduced by GO (p<0.05). Real-time PCR showed that GO tended to reduce Butyrivibrio proteoclasticus abundance (p = 0.058), whereas GO had no effect on total abundance of the Butyrivibrio group bacteria. A low correlation was found between B. proteoclasticus abundance and C18:0/(TVA+C18:0) (p = 0.910). The changes of fermentation over time suggested a role of GO in delaying the fermentation process and maintaining a relatively

  6. Gold(III)-Catalyzed Hydration of Phenylacetylene

    ERIC Educational Resources Information Center

    Leslie, J. Michelle; Tzeel, Benjamin A.

    2016-01-01

    A guided inquiry-based experiment exploring the regioselectivity of the hydration of phenylacetylene is described. The experiment uses an acidic gold(III) catalyst in a benign methanol/water solvent system to introduce students to alkyne chemistry and key principles of green chemistry. The experiment can be easily completed in approximately 2 h,…

  7. Slowly digestible starch influences mRNA abundance of glucose and short-chain fatty acid transporters in the porcine distal intestinal tract.

    PubMed

    Woodward, A D; Regmi, P R; Gänzle, M G; van Kempen, T A T G; Zijlstra, R T

    2012-12-01

    The relationship between starch chemistry and intestinal nutrient transporters is not well characterized. We hypothesized that inclusion of slowly instead of rapidly digestible starch in pig diets will decrease glucose and increase short-chain fatty acid (SCFA) transporter expression in the distal gut. Weaned barrows (n = 32) were fed 4 diets containing 70% starch [ranging from 0 to 63% amylose and from 1.06 (rapidly) to 0.22%/min (slowly) rate of in vitro digestion] at 3 × maintenance energy requirement in a complete randomized block design. Ileal and colon mucosa was collected on day 21 to quantify mRNA abundance of Na(+)-dependent glucose transporter 1 (SGLT1), monocarboxylic acid transporter 1 (MCT1), and Na(+)-coupled monocarboxylate transporter (SMCT). Messenger RNA was extracted and cDNA manufactured prior to relative quantitative reverse transcription PCR. Data were analyzed using the 2(-Δ ΔC)(T) method, with β-actin and glyceraldehyde-3-phosphate dehydrogenase as reference genes, and regression analysis was performed. As in vitro rate of digestion decreased, SGLT1 linearly increased (P < 0.05) in the ileum. Contrary to SGLT1, MCT1 tended to linearly decrease (P = 0.08) in the ileum and increased quadratically (P < 0.001) in the colon with decreasing rate of digestion. Starch digestion rate did not affect SMCT in the ileum; however, colonic SMCT quadratically decreased (P < 0.01) with decreasing rate of digestion. In conclusion, in contrast to our hypothesis, slowly digestible starch increased ileal glucose and decreased ileal SCFA transporter mRNA abundance, possibly due to an increased glucose in the luminal ileum. Effects of starch on colonic SCFA transporter mRNA abundance were inconsistent.

  8. Transformations in methane hydrates

    USGS Publications Warehouse

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

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

  9. 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.

  10. Impact of improving dietary amino acid balance for lactating sows on efficiency of dietary amino acid utilization and transcript abundance of genes encoding lysine transporters in mammary tissue.

    PubMed

    Huber, L; de Lange, C F M; Ernst, C W; Krogh, U; Trottier, N L

    2016-11-01

    Lactating multiparous Yorkshire sows ( = 64) were used in 2 experiments to test the hypothesis that reducing dietary CP intake and improving AA balance through crystalline AA (CAA) supplementation improves apparent dietary AA utilization efficiency for milk production and increases transcript abundance of genes encoding Lys transporter proteins in mammary tissue. In Exp. 1, 40 sows were assigned to 1 of 4 diets: 1) high CP (HCP; 16.0% CP, as-fed basis; analyzed concentration), 2) medium-high CP (MHCP; 15.7% CP), 3) medium-low CP (MLCP; 14.3% CP), and 4) low CP (LCP; 13.2% CP). The HCP diet was formulated using soybean meal and corn as the only Lys sources. The reduced-CP diets contained CAA to meet estimated requirements for essential AA that became progressively limiting with reduction in CP concentration, that is, Lys, Ile, Met + Cys, Thr, Trp, and Val. Dietary standardized ileal digestible (SID) Lys concentration was 80% of the estimated requirement. In Exp. 2, 24 sows were assigned to the HCP or LCP diets. In Exp. 1, blood samples were postprandially collected 15 h on d 3, 7, 14, and 18 of lactation and utilization efficiency of dietary AA for milk production was calculated during early (d 3 to 7) and peak (d 14 to 18) lactation. Efficiency values were estimated from daily SID AA intakes and milk AA yield, with corrections for maternal AA requirement for maintenance and AA contribution from body protein losses. In Exp. 2, mammary tissue was biopsied on d 4 and 14 of lactation to determine the mRNA abundance of genes encoding Lys transporter proteins. In peak lactation, Lys, Thr, Trp, and Val utilization efficiency increased with decreasing dietary CP (linear for Trp and Val, < 0.05; in sows fed the MHCP diet vs. sows fed the HCP diet for Lys and Thr, < 0.05). Total essential and nonessential 15-h postprandial serum AA concentrations increased with decreasing dietary CP (linear, = 0.09 and < 0.05, respectively), suggesting increased maternal body protein

  11. Natural (15)N Abundance in Key Amino Acids from Lamb Muscle: Exploring a New Horizon in Diet Authentication and Assessment of Feed Efficiency in Ruminants.

    PubMed

    Cantalapiedra-Hijar, Gonzalo; Ortigues-Marty, Isabelle; Schiphorst, Anne-Marie; Robins, Richard J; Tea, Illa; Prache, Sophie

    2016-05-25

    Natural (15)N abundance (δ(15)N) varies between individual amino acids (AAs). We hypothesized that δ(15)N of nontransaminating and essential AAs ("source" AAs, such as phenylalanine) present in animal tissues could be used as a marker of dietary origin, whereas δ(15)N of transaminating AAs ("trophic" AAs, such as glutamic acid) could give more detailed insights into animal feed efficiency. Two diets based on dehydrated Lucerne pellets were tested in growing lambs, which promoted different feed efficiencies. No dietary effects were noted on δ(15)N of any AAs analyzed in lamb muscle. In addition, δ(15)N of phenylalanine was unexpectedly similar to that of glutamic acid, suggesting that δ(15)N of AAs is significantly derived from the metabolism of the rumen microbiota and, thus, are not suited for diet authentication in ruminants. In contrast, the δ(15)N of transaminating AAs facilitates an improved prediction of animal feed efficiency compared to the classical isotopic bulk N analysis.

  12. Changes in abundance of an abscisic acid-responsive, early cysteine-labeled metallothionein transcript during pollen embryogenesis in bread wheat (Triticum aestivum).

    PubMed

    Reynolds, T L; Crawford, R L

    1996-12-01

    A clone for an embryoid-abundant, early cysteine-labeled metallothionein (EcMt) gene has been isolated from a wheat pollen embryoid cDNA library. The transcript of this gene was only expressed in embryogenic microspores, pollen embryoids, and developing zygotic embryos of wheat. Accumulation of the EcMt mRNA showed a direct and positive correlation with an increase of the plant hormone, abscisic acid (ABA) in developing pollen embryoids. Treating cultures with an inhibitor of ABA biosynthesis, fluridone, suppressed not only ABA accumulation but also the appearance of the EcMt gene transcript and the ability of microspores to form embryoids. These results suggest that the EcMt gene may act as a molecular marker for pollen embryogenesis because ABA biosynthesis is accompanied by the increased expression of the EcMt transcript that coincides with the differentiation of pollen embryoids in wheat anther cultures.

  13. Purification, properties and amino acid sequence of a low-Mr abundant seed protein from pea (Pisum sativum L.).

    PubMed

    Gatehouse, J A; Gilroy, J; Hoque, M S; Croy, R R

    1985-01-01

    The seeds of pea (Pisum sativum L.) contain several proteins in the albumin solubility fraction that are significant components of total cotyledonary protein (5-10%) and are accumulated in developing seeds concurrently with storage-protein synthesis. One of these proteins, of low Mr and designated 'Psa LA', has been purified, characterized and sequenced. Psa LA has an Mr of 11000 and contains polypeptides of Mr 6000, suggesting that the protein molecules are dimeric. The amino acid sequence contains 54 residues, with a high content (10/54) of asparagine/aspartate. It has no inhibitory action towards trypsin or chymotrypsin, and is distinct from the inhibitors of those enzymes found in pea seeds, nor does it inhibit hog pancreatic alpha-amylase. The protein contains no methionine, but significant amounts of cysteine (four residues per polypeptide), suggesting a possible role as a sulphur storage protein. However, its sequence is not homologous with low-Mr (2S) storage proteins from castor bean (Ricinus communis) or rape (Brassica napus). Psa LA therefore represents a new type of low-Mr seed protein.

  14. Picoliter droplet-based digital peptide nucleic acid clamp PCR and dielectric sorting for low abundant K-ras mutations

    NASA Astrophysics Data System (ADS)

    Zhang, Huidan; Sperling, Ralph; Rotem, Assaf; Shan, Lianfeng; Heyman, John; Zhang, Yizhe; Weitz, David

    2012-02-01

    Colorectal cancer (CRC) remains the second leading cause of cancer-related mortality in the US, and the 5-year survival of metastatic CRC (mCRC) is less than 10%. Although monoclonal antibodies against epidermal growth factor receptor (EGFR) provide incremental improvements in survival, approximately 40% of mCRC patients with activating KRAS mutations won't benefit from this therapy. Peptide nucleic acid (PNA), a synthetic non-extendable oligonucleotides, can bind strongly to completely complementary wild-type KRAS by Watson-Crick base pairing and suppress its amplification during PCR, while any mutant allele will show unhindered amplification. The method is particularly suitable for the simultaneously detection of several adjoining mutant sites, just as mutations of codons 12 and 13 of KRAS gene where there are totally 12 possible mutation types. In this work, we describe the development and validation of this method, based on the droplet-based digital PCR. Using a microfluidic system, single target DNA molecule is compartmentalized in microdroplets together with PNA specific for wild-type KRAS, thermocycled and the fluorescence of each droplet was detected, followed by sorting and sequencing. It enables the precise determination of all possible mutant KRAS simultaneously, and the precise quantification of a single mutated KRAS in excess background unmutated KRAS.

  15. Synthesis and characterization of a new structure of gas hydrate

    SciTech Connect

    Tulk, Christopher A; Chakoumakos, Bryan C; Ehm, Lars; Klug, Dennis D; Parise, John B; Yang, Ling; Martin, Dave; Ripmeester, John; Moudrakovski, Igor; Ratcliffe, Chris

    2009-01-01

    Atoms and molecules 0.4 0.9 nm in diameter can be incorporated in the cages formed by hydrogen-bonded water molecules making up the crystalline solid clathrate hydrates. There are three structural families of these hydrates , known as sI, sII and sH, and the structure usually depends on the largest guest molecule in the hydrate. Species such as Ar, Kr, Xe and methane form sI or sII hydrate, sH is unique in that it requires both small and large cage guests for stability. All three structures, containing methane, other hydrocarbons, H2S and CO2, O2 and N2 have been found in the geosphere, with sI methane hydrate by far the most abundant. At high pressures (P > 0.7 kbar) small guests (Ar, Kr, Xe, methane) are also known to form sH hydrate with multiple occupancy of the largest cage in the hydrate. The high-pressure methane hydrate of sH has been proposed as playing a role in the outer solar system, including formation models for Titan , and yet another high pressure phase of methane has been reported , although its structure remains unknown. In this study, we report a new and unique hydrate structure that is derived from the high pressure sH hydrate of xenon. After quench recovery at ambient pressure and 77 K it shows considerable stability at low temperatures (T < 160 K) and is compositionally similar to the sI Xe clathrate starting material. This evidence of structural complexity in compositionally similar clathrate compounds indicates that thermodynamic pressure temperature conditions may not be the only important factor in structure determination, but also the reaction path may have an important effect.

  16. 15N natural abundance during early and late succession in a middle-European dry acidic grassland.

    PubMed

    Beyschlag, W; Hanisch, S; Friedrich, S; Jentsch, A; Werner, C

    2009-09-01

    delta(15)N and total nitrogen content of above- and belowground tissues of 13 plant species from two successional stages (open pioneer community and ruderal grass stage) of a dry acidic grassland in Southern Germany were analysed, in order to evaluate whether resource use partitioning by niche separation and N input by N(2)-fixing legumes are potential determinants for species coexistence and successional changes. Within each stage, plants from plots with different legume cover were compared. Soil inorganic N content, total plant biomass and delta(15)N values of bulk plant material were significantly lower in the pioneer stage than in the ruderal grass community. The observed delta(15)N differences were rather species- than site-specific. Within both stages, there were also species-specific differences in isotopic composition between above- and belowground plant dry matter. Species-specific delta(15)N signatures may theoretically be explained by (i) isotopic fractionation during microbial-mediated soil N transformations; (ii) isotopic fractionation during plant N uptake or fractionation during plant-mycorrhiza transfer processes; (iii) differences in metabolic pathways and isotopic fractionation within the plant; or (iv) partitioning of available N resources (or pools) among plant groups or differential use of the same resources by different species, which seems to be the most probable route in the present case. A significant influence of N(2)-fixing legumes on the N balance of the surrounding plant community was not detectable. This was confirmed by the results of an independent in situ removal experiment, showing that after 3 years there were no measurable differences in the frequency distribution between plots with and without N(2)-fixing legumes.

  17. HYDRATE CORE DRILLING TESTS

    SciTech Connect

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

    2002-11-01

    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate formation comprised of coarse, large

  18. The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

    NASA Astrophysics Data System (ADS)

    Guan, Jinan; Liang, Deqing; Wu, Nengyou; Fan, Shuanshi

    2009-10-01

    It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m -2 a -1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10 9 m 3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

  19. Dynamics of protein hydration water.

    PubMed

    Wolf, M; Emmert, S; Gulich, R; Lunkenheimer, P; Loidl, A

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  20. [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.

  1. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  2. 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.

  3. Colorado Plateau Uplift Through Deep Crustal Hydration?

    NASA Astrophysics Data System (ADS)

    Butcher, L. A.; Mahan, K. H.; Jones, C. H.; Farmer, G.

    2013-12-01

    The conventional view of plate tectonics restricts deformation to plate boundaries and does not account for regionally elevated topography in continental interiors. Thermal, mechanical or chemical alteration of ancient continental lithosphere is a mechanism sometimes invoked to explain intracratonic uplift in the western U.S. although the timing, extent and effects of this modification are poorly understood. Here we present new petrological and in situ geochronological data for a hydrated deep crustal xenolith from the Colorado Plateau and investigate the effects of deep crustal hydration on topography. Two distinct mineral assemblages recorded in a garnet biotite schist xenolith from the Navajo Volcanic Field, Four Corners region document hydration subsequent to peak metamorphism in the deep crust whereby the primary metamorphic assemblage (Gt + Bt + Ms + Pl + Kfs + Qtz) is variably replaced by a lower-density, hydrated assemblage (Ab + Ph + Cc + Rt). Results from forward petrological modeling constrain hydration at ≥ 20 km (0.65 GPa, 450 °C) prior to exhumation in the ˜20 Ma volcanic host. In situ Th/Pb dating of secondary monazite grains spatially associated with fluid-related plagioclase and allanite breakdown reveals a significant majority of Late Cretaceous dates from 91 to 58 Ma. These dates are interpreted to reflect a finite period of deep crustal hydration, possibly by fluids sourced from a shallowly subducting Farallon slab. Xenolith data additionally supports crustal hydration as a mechanism for producing regionally elevated topography. Fluid-related reactions in the deep crust may lead to a net density decrease as low-density hydrous phases (e.g. Ms + Amp + Cc) replace high-density, anhydrous minerals (e.g. Gt + Fsp + Opx + Cpx) abundant in high-pressure, high-temperature assemblages preserved in Proterozoic North American lithosphere. If these reactions are sufficiently pervasive and widespread, reductions in lower crustal density would provide a

  4. Perturbations of amino acid metabolism associated with glyphosate-dependent inhibition of shikimic acid metabolism affect cellular redox homeostasis and alter the abundance of proteins involved in photosynthesis and photorespiration.

    PubMed

    Vivancos, Pedro Diaz; Driscoll, Simon P; Bulman, Christopher A; Ying, Liu; Emami, Kaveh; Treumann, Achim; Mauve, Caroline; Noctor, Graham; Foyer, Christine H

    2011-09-01

    The herbicide glyphosate inhibits the shikimate pathway of the synthesis of amino acids such as phenylalanine, tyrosine, and tryptophan. However, much uncertainty remains concerning precisely how glyphosate kills plants or affects cellular redox homeostasis and related processes in glyphosate-sensitive and glyphosate-resistant crop plants. To address this issue, we performed an integrated study of photosynthesis, leaf proteomes, amino acid profiles, and redox profiles in the glyphosate-sensitive soybean (Glycine max) genotype PAN809 and glyphosate-resistant Roundup Ready Soybean (RRS). RRS leaves accumulated much more glyphosate than the sensitive line but showed relatively few changes in amino acid metabolism. Photosynthesis was unaffected by glyphosate in RRS leaves, but decreased abundance of photosynthesis/photorespiratory pathway proteins was observed together with oxidation of major redox pools. While treatment of a sensitive genotype with glyphosate rapidly inhibited photosynthesis and triggered the appearance of a nitrogen-rich amino acid profile, there was no evidence of oxidation of the redox pools. There was, however, an increase in starvation-associated and defense proteins. We conclude that glyphosate-dependent inhibition of soybean leaf metabolism leads to the induction of defense proteins without sustained oxidation. Conversely, the accumulation of high levels of glyphosate in RRS enhances cellular oxidation, possibly through mechanisms involving stimulation of the photorespiratory pathway.

  5. Perturbations of Amino Acid Metabolism Associated with Glyphosate-Dependent Inhibition of Shikimic Acid Metabolism Affect Cellular Redox Homeostasis and Alter the Abundance of Proteins Involved in Photosynthesis and Photorespiration1[W][OA

    PubMed Central

    Vivancos, Pedro Diaz; Driscoll, Simon P.; Bulman, Christopher A.; Ying, Liu; Emami, Kaveh; Treumann, Achim; Mauve, Caroline; Noctor, Graham; Foyer, Christine H.

    2011-01-01

    The herbicide glyphosate inhibits the shikimate pathway of the synthesis of amino acids such as phenylalanine, tyrosine, and tryptophan. However, much uncertainty remains concerning precisely how glyphosate kills plants or affects cellular redox homeostasis and related processes in glyphosate-sensitive and glyphosate-resistant crop plants. To address this issue, we performed an integrated study of photosynthesis, leaf proteomes, amino acid profiles, and redox profiles in the glyphosate-sensitive soybean (Glycine max) genotype PAN809 and glyphosate-resistant Roundup Ready Soybean (RRS). RRS leaves accumulated much more glyphosate than the sensitive line but showed relatively few changes in amino acid metabolism. Photosynthesis was unaffected by glyphosate in RRS leaves, but decreased abundance of photosynthesis/photorespiratory pathway proteins was observed together with oxidation of major redox pools. While treatment of a sensitive genotype with glyphosate rapidly inhibited photosynthesis and triggered the appearance of a nitrogen-rich amino acid profile, there was no evidence of oxidation of the redox pools. There was, however, an increase in starvation-associated and defense proteins. We conclude that glyphosate-dependent inhibition of soybean leaf metabolism leads to the induction of defense proteins without sustained oxidation. Conversely, the accumulation of high levels of glyphosate in RRS enhances cellular oxidation, possibly through mechanisms involving stimulation of the photorespiratory pathway. PMID:21757634

  6. The effectiveness of organic PCM based on lauric acid from coconut oil and inorganic PCM based on salt hydrate CaCl2.6H2o as latent heat energy storage system in Indonesia

    NASA Astrophysics Data System (ADS)

    U, Sri Rahayu A.; Putri, Widya A.; Sutjahja, I. M.; Kurnia, D.; Wonorahardjo, S.

    2016-08-01

    A latent heat energy storage system utilizing phase change materials (PCM) is an alternative strategy to reduce the use of Air Conditioning (AC) system in big cities in Indonesia in order for energy conservation in the future. In this research we used two kinds of materials, namely organic PCM based on lauric acid from coconut oil (CO) and inorganic PCM based on salt hydrate CaCl2.6H2O, because they have thermophysical parameters suitable for human's thermal comfort application in the building. The CO which contained more than 50% lauric acid has the melting temperature (Tm ) of about 26 °C and heat entalphy (ΔH) around 103 kJ/kg, while CaCl2.6H2O has the melting point of 29 °C and heat entalphy of 190 kJ/kg. In this paper we report the effectiveness of those two kinds of PCM in reducing the air temperature as one of some criteria for human's thermal comfort. The experiments were performed in a close and adiabatic room and the time-temperature measurements were done automatically using Arduino microcontroller and LM35 temperature sensor connected to the PC.

  7. Hydration dynamics near a model protein surface

    SciTech Connect

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-09-01

    The evolution of water dynamics from dilute to very high concentration solutions of a prototypical hydrophobic amino acid with its polar backbone, N-acetyl-leucine-methylamide (NALMA), is studied by quasi-elastic neutron scattering and molecular dynamics simulation for both the completely deuterated and completely hydrogenated leucine monomer. We observe several unexpected features in the dynamics of these biological solutions under ambient conditions. The NALMA dynamics shows evidence of de Gennes narrowing, an indication of coherent long timescale structural relaxation dynamics. The translational water dynamics are analyzed in a first approximation with a jump diffusion model. At the highest solute concentrations, the hydration water dynamics is significantly suppressed and characterized by a long residential time and a slow diffusion coefficient. The analysis of the more dilute concentration solutions takes into account the results of the 2.0M solution as a model of the first hydration shell. Subtracting the first hydration layer based on the 2.0M spectra, the translational diffusion dynamics is still suppressed, although the rotational relaxation time and residential time are converged to bulk-water values. Molecular dynamics analysis shows spatially heterogeneous dynamics at high concentration that becomes homogeneous at more dilute concentrations. We discuss the hydration dynamics results of this model protein system in the context of glassy systems, protein function, and protein-protein interfaces.

  8. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  9. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  10. FcLDP1, a Gene Encoding a Late Embryogenesis Abundant (LEA) Domain Protein, Responds to Brassinosteroids and Abscisic Acid during the Development of Fruits in Fragaria chiloensis

    PubMed Central

    Espinoza, Analía; Contreras, Rodrigo; Zúñiga, Gustavo E.; Herrera, Raúl; Moya-León, María Alejandra; Norambuena, Lorena; Handford, Michael

    2016-01-01

    White Chilean strawberries (Fragaria chiloensis) are non-climacteric fruits, with an exotic color and aroma. In order to discover genes involved in the development of these fruits, we identified a fragment of a gene encoding a late embryogenesis abundant domain protein, FcLDP1, that was expressed in early stages of fruit development, particularly in receptacles. Hormones play key roles in regulating the development of non-climacteric fruits. We show that the brassinosteroid content of the white strawberry varies during development. Additionally, FcLDP1 as well as the closest ortholog in the woodland strawberry, F. vesca (FvLDP1) possess multiple brassinosteroid, as well as abscisic acid (ABA) response motifs in the promoter region, consistent with the response of transiently expressed FcLDP1 promoter-GFP fusions to these hormones, and the rise in FcLDP1 transcript levels in white strawberry fruits treated with brassinosteroids or ABA. These findings suggest that both hormones regulate FcLDP1 expression during the development of white strawberries. PMID:27379111

  11. Uses of phage display in agriculture: sequence analysis and comparative modeling of late embryogenesis abundant client proteins suggest protein-nucleic acid binding functionality.

    PubMed

    Kushwaha, Rekha; Downie, A Bruce; Payne, Christina M

    2013-01-01

    A group of intrinsically disordered, hydrophilic proteins-Late Embryogenesis Abundant (LEA) proteins-has been linked to survival in plants and animals in periods of stress, putatively through safeguarding enzymatic function and prevention of aggregation in times of dehydration/heat. Yet despite decades of effort, the molecular-level mechanisms defining this protective function remain unknown. A recent effort to understand LEA functionality began with the unique application of phage display, wherein phage display and biopanning over recombinant Seed Maturation Protein homologs from Arabidopsis thaliana and Glycine max were used to retrieve client proteins at two different temperatures, with one intended to represent heat stress. From this previous study, we identified 21 client proteins for which clones were recovered, sometimes repeatedly. Here, we use sequence analysis and homology modeling of the client proteins to ascertain common sequence and structural properties that may contribute to binding affinity with the protective LEA protein. Our methods uncover what appears to be a predilection for protein-nucleic acid interactions among LEA client proteins, which is suggestive of subcellular residence. The results from this initial computational study will guide future efforts to uncover the protein protective mechanisms during heat stress, potentially leading to phage-display-directed evolution of synthetic LEA molecules.

  12. Computational and Statistical Analyses of Amino Acid Usage and Physico-Chemical Properties of the Twelve Late Embryogenesis Abundant Protein Classes

    PubMed Central

    Jaspard, Emmanuel; Macherel, David; Hunault, Gilles

    2012-01-01

    Late Embryogenesis Abundant Proteins (LEAPs) are ubiquitous proteins expected to play major roles in desiccation tolerance. Little is known about their structure - function relationships because of the scarcity of 3-D structures for LEAPs. The previous building of LEAPdb, a database dedicated to LEAPs from plants and other organisms, led to the classification of 710 LEAPs into 12 non-overlapping classes with distinct properties. Using this resource, numerous physico-chemical properties of LEAPs and amino acid usage by LEAPs have been computed and statistically analyzed, revealing distinctive features for each class. This unprecedented analysis allowed a rigorous characterization of the 12 LEAP classes, which differed also in multiple structural and physico-chemical features. Although most LEAPs can be predicted as intrinsically disordered proteins, the analysis indicates that LEAP class 7 (PF03168) and probably LEAP class 11 (PF04927) are natively folded proteins. This study thus provides a detailed description of the structural properties of this protein family opening the path toward further LEAP structure - function analysis. Finally, since each LEAP class can be clearly characterized by a unique set of physico-chemical properties, this will allow development of software to predict proteins as LEAPs. PMID:22615859

  13. FcLDP1, a Gene Encoding a Late Embryogenesis Abundant (LEA) Domain Protein, Responds to Brassinosteroids and Abscisic Acid during the Development of Fruits in Fragaria chiloensis.

    PubMed

    Espinoza, Analía; Contreras, Rodrigo; Zúñiga, Gustavo E; Herrera, Raúl; Moya-León, María Alejandra; Norambuena, Lorena; Handford, Michael

    2016-01-01

    White Chilean strawberries (Fragaria chiloensis) are non-climacteric fruits, with an exotic color and aroma. In order to discover genes involved in the development of these fruits, we identified a fragment of a gene encoding a late embryogenesis abundant domain protein, FcLDP1, that was expressed in early stages of fruit development, particularly in receptacles. Hormones play key roles in regulating the development of non-climacteric fruits. We show that the brassinosteroid content of the white strawberry varies during development. Additionally, FcLDP1 as well as the closest ortholog in the woodland strawberry, F. vesca (FvLDP1) possess multiple brassinosteroid, as well as abscisic acid (ABA) response motifs in the promoter region, consistent with the response of transiently expressed FcLDP1 promoter-GFP fusions to these hormones, and the rise in FcLDP1 transcript levels in white strawberry fruits treated with brassinosteroids or ABA. These findings suggest that both hormones regulate FcLDP1 expression during the development of white strawberries.

  14. Effects of clofibric acid alone and in combination with 17β-estradiol on mRNA abundance in primary hepatocytes isolated from rainbow trout.

    PubMed

    Sovadinová, I; Liedtke, A; Schirmer, K

    2014-09-01

    Clofibric acid (CA) is the active substance of lipid lowering drugs. It is resistant to degradation, polar in nature, and has been found ubiquitously in the aquatic environment. Though CA is classified as a peroxisomal proliferator in rodents and is considered as a potential endocrine disruptor, little information exists on the effects of CA in aquatic organisms, such as fish. In the present study, we examined the mRNA levels of peroxisome proliferator- and estrogen-sensitive genes on the exposure of primary rainbow trout (Oncorhynchus mykiss) hepatocytes to CA alone and in combination with the natural female sex hormone, 17β-estradiol (E2). Our results demonstrate that rainbow trout hepatocytes are relatively refractory to the effects of CA on the PPAR signaling pathway and lipid metabolism. Moreover, CA did not show recognizable estrogenic activity, but after the induction of vitellogenesis by E2, CA significantly reduced vitellogenin (VTG) mRNA abundance. Apparently, the indirect repression of VTG transcription, independent of estrogen receptors, occurred. The mechanism is not yet clearly understood but may involve disruption of the stabilization of VTG mRNA known to be induced by E2.

  15. 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.

  16. Methane Hydrates inventory for a warm Paleogene Ocean

    NASA Astrophysics Data System (ADS)

    Kahana, R.; Ridgwell, A. J.

    2010-12-01

    A large and instantaneous release of methane from hydrate deposits beneath the ocean floor is often considered to be the main trigger for the Paleocene-Eocene Thermal Maximum (PETM) at 55 Ma BP and for other hyperthermal events during the warm Paleogene. About 2000 GtC of methane hydrates are required to explain the observed negative carbon excursion at the onset of the PETM. This amount is comparable to the entire modern-day global ocean inventory. However, the Paleogene bottom ocean temperatures were about 10 C warmer. Higher temperatures increase the depth of methane hydrates stability to about 1000 m. This reduces the area available for methanogenesis and hydrates production, and confines it to regions of the continental slope, further away from sources of particulate organic carbon. On the other hand higher water and sediment temperatures and possibly increased productivity might increase hydrate abundance by speeding up methanogenesis process and lowering deep sea oxygen levels, which results in a better preservation of particulate organic carbon available for methanogenesis. It is therefore difficult to estimate the methane hydrates inventory for the Paleogene and determine its spatial distribution without modelling it explicitly. To improve our understanding of these processes we have applied the methodology used by Archer et al., (2009) for estimating modern inventory of methane hydrates, to predict methane hydrates abundance in the warm Palaeogene ocean and its sensitivity to changes in temperatures and productivity: The Paleogene bathymetry and bottom water chemistry (seafloor temperature and oxygen levels) simulated by GENIE-1, an intermediate complexity Earth System Model is fed into David Archer’s early sedimentary diagenesis model (MUDS). MUDS simulates the fraction of organic carbon which is buried below one meter of the sediment column and is available for methanogenesis, and the total burial rate at this depth. These are then fed into a steady

  17. 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.

  18. Rapid gas hydrate formation process

    DOEpatents

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  19. Gas hydrate cool storage system

    DOEpatents

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  20. Chemical characteristics of mineral trioxide aggregate and its hydration reaction

    PubMed Central

    2012-01-01

    Mineral trioxide aggregate (MTA) was developed in early 1990s and has been successfully used for root perforation repair, root end filling, and one-visit apexification. MTA is composed mainly of tricalcium silicate and dicalcium silicate. When MTA is hydrated, calcium silicate hydrate (CSH) and calcium hydroxide is formed. Formed calcium hydroxide interacts with the phosphate ion in body fluid and form amorphous calcium phosphate (ACP) which finally transforms into calcium deficient hydroxyapatite (CDHA). These mineral precipitate were reported to form the MTA-dentin interfacial layer which enhances the sealing ability of MTA. Clinically, the use of zinc oxide euginol (ZOE) based materials may retard the setting of MTA. Also, the use of acids or contact with excessive blood should be avoided before complete set of MTA, because these conditions could adversely affect the hydration reaction of MTA. Further studies on the chemical nature of MTA hydration reaction are needed. PMID:23429542

  1. Red light-regulated growth. I. Changes in the abundance of indoleacetic acid and a 22-kilodalton auxin-binding protein in the maize mesocotyl.

    PubMed

    Jones, A M; Cochran, D S; Lamerson, P M; Evans, M L; Cohen, J D

    1991-01-01

    We examined the changes in the levels of indoleacetic acid (IAA), IAA esters, and a 22-kilodalton subunit auxin-binding protein (ABP1) in apical mesocotyl tissue of maize (Zea mays L.) during continuous red light (R) irradiation. These changes were compared with the kinetics of R-induced growth inhibition in the same tissue. Upon the onset of continuous irradiation, growth decreased in a continuous manner following a brief lag period. The decrease in growth continued for 5 hours, then remained constant at 25% of the dark rate. The abundance of ABP1 and the level of free IAA both decreased in the mesocotyl. Only the kinetics of the decrease in IAA within the apical mesocotyl correlated with the initial change in growth, although growth continued to decrease even after IAA content reached its final level, 50% of the dark control. This decrease in IAA within the mesocotyl probably occurs primarily by a change in its transport within the shoot since auxin applied as a pulse move basipetally in R-irradiated tissue at the same rate but with half the area as dark control tissue. In situ localization of auxin in etiolated maize shoots revealed that R-irradiated shoots contained less auxin in the epidermis than the dark controls. Irradiated mesocotyl grew 50% less than the dark controls even when incubated in an optimal level of auxin. However, irradiated and dark tissue contained essentially the same amount of radioactivity after incubation in [14C]IAA indicating that the light treatment does not affect the uptake into the tissue through the cut end, although it is possible that a small subset of cells within the mesocotyl is affected. These observations support the hypothesis that R causes a decrease in the level of auxin in epidermal cells of the mesocotyl, consequently constraining the growth of the entire mesocotyl.

  2. Carbon-13 natural abundance signatures of long-chain fatty acids to determinate sediment origin: A case study in northeast Austria

    NASA Astrophysics Data System (ADS)

    Mabit, Lionel; Gibbs, Max; Meusburger, Katrin; Toloza, Arsenio; Resch, Christian; Klik, Andreas; Swales, Andrew; Alewell, Christine

    2016-04-01

    - Several recently published information from scientific research have highlighted that compound-specific stable isotope (CSSI) signatures of fatty acids (FAs) based on the measurement of carbon-13 natural abundance signatures showed great promises to identify sediment origin. The authors have used this innovative isotopic approach to investigate the sources of sediment in a three hectares Austrian sub-watershed (i.e. Mistelbach). Through a previous study using the Cs-137 technique, Mabit et al. (Geoderma, 2009) reported a local maximum sedimentation rate reaching 20 to 50 t/ha/yr in the lowest part of this watershed. However, this study did not identify the sources. Subsequently, the deposited sediment at its outlet (i.e. the sediment mixture) and representative soil samples from the four main agricultural fields - expected to be the source soils - of the site were investigated. The bulk delta carbon-13 of the samples and two long-chain FAs (i.e. C22:0 and C24:0) allowed the best statistical discrimination. Using two different mixing models (i.e. IsoSource and CSSIAR v1.00) and the organic carbon content of the soil sources and sediment mixture, the contribution of each source has been established. Results suggested that the grassed waterway contributed to at least 50% of the sediment deposited at the watershed outlet. This study, that will require further validation, highlights that CSSI and Cs-137 techniques are complementary as fingerprints and tracers for establishing land sediment redistribution and could provide meaningful information for optimized decision-making by land managers.

  3. Red light-regulated growth. I. Changes in the abundance of indoleacetic acid and a 22-kilodalton auxin-binding protein in the maize mesocotyl

    NASA Technical Reports Server (NTRS)

    Jones, A. M.; Cochran, D. S.; Lamerson, P. M.; Evans, M. L.; Cohen, J. D.

    1991-01-01

    We examined the changes in the levels of indoleacetic acid (IAA), IAA esters, and a 22-kilodalton subunit auxin-binding protein (ABP1) in apical mesocotyl tissue of maize (Zea mays L.) during continuous red light (R) irradiation. These changes were compared with the kinetics of R-induced growth inhibition in the same tissue. Upon the onset of continuous irradiation, growth decreased in a continuous manner following a brief lag period. The decrease in growth continued for 5 hours, then remained constant at 25% of the dark rate. The abundance of ABP1 and the level of free IAA both decreased in the mesocotyl. Only the kinetics of the decrease in IAA within the apical mesocotyl correlated with the initial change in growth, although growth continued to decrease even after IAA content reached its final level, 50% of the dark control. This decrease in IAA within the mesocotyl probably occurs primarily by a change in its transport within the shoot since auxin applied as a pulse move basipetally in R-irradiated tissue at the same rate but with half the area as dark control tissue. In situ localization of auxin in etiolated maize shoots revealed that R-irradiated shoots contained less auxin in the epidermis than the dark controls. Irradiated mesocotyl grew 50% less than the dark controls even when incubated in an optimal level of auxin. However, irradiated and dark tissue contained essentially the same amount of radioactivity after incubation in [14C]IAA indicating that the light treatment does not affect the uptake into the tissue through the cut end, although it is possible that a small subset of cells within the mesocotyl is affected. These observations support the hypothesis that R causes a decrease in the level of auxin in epidermal cells of the mesocotyl, consequently constraining the growth of the entire mesocotyl.

  4. Selective Cleavage of the Aryl Ether Bonds in Lignin for Depolymerization by Acidic Lithium Bromide Molten Salt Hydrate under Mild Conditions.

    PubMed

    Yang, Xiaohui; Li, Ning; Lin, Xuliang; Pan, Xuejun; Zhou, Yonghong

    2016-11-09

    The present study demonstrates that the concentrated lithium bromide (LiBr) solution with acid as catalyst was able to selectively cleave the β-O-4 aryl ether bond and lead to lignin depolymerization under mild conditions (e.g., in 60% LiBr with 0.3 M HCl at 110 °C for 2 h). Four industrial lignins from different pulping and biorefining processes, including softwood kraft lignin (SKL), hardwood kraft lignin (HKL), softwood ethanol organosolv lignin (EOL), and acid corncob lignin (ACL), were treated in the LiBr solution. The molecular weight, functional group, and interunit linkages of the lignins were characterized using GPC, FTIR, and NMR. The results indicated that the β-O-4 aryl ether bonds of the lignins were selectively cleaved, and both LiBr and HCl played crucial roles in catalyzing the cleavage of the ether bonds.

  5. Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

    NASA Technical Reports Server (NTRS)

    Graff, Trevor G.; Morris, R. V.; Archilles C. N.; Agresti, D. G.; Ming, D. W.; Hamilton, J. C.; Mertzman, S. A.; Smith, J.

    2012-01-01

    Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO

  6. 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.

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

    USGS Publications Warehouse

    Bindeman, Ilya N.; Lowenstern, Jacob B.

    2016-01-01

    Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°–225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests ~2 orders of magnitude higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick

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

    NASA Astrophysics Data System (ADS)

    Bindeman, Ilya N.; Lowenstern, Jacob B.

    2016-11-01

    Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant "onion-skin" fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2-3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched "hydration fronts" where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between 110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°-225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests 2 orders of magnitude higher rates of diffusion at 60-110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites

  9. 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.

  10. Volatile inventories in clathrate hydrates formed in the primordial nebula.

    PubMed

    Mousis, Olivier; Lunine, Jonathan I; Picaud, Sylvain; Cordier, Daniel

    2010-01-01

    The examination of ambient thermodynamic conditions suggests that clathrate hydrates could exist in the Martian permafrost, on the surface and in the interior of Titan, as well as in other icy satellites. Clathrate hydrates are probably formed in a significant fraction of planetesimals in the solar system. Thus, these crystalline solids may have been accreted in comets, in the forming giant planets and in their surrounding satellite systems. In this work, we use a statistical thermodynamic model to investigate the composition of clathrate hydrates that may have formed in the primordial nebula. In our approach, we consider the formation sequence of the different ices occurring during the cooling of the nebula, a reasonable idealization of the process by which volatiles are trapped in planetesimals. We then determine the fractional occupancies of guests in each clathrate hydrate formed at a given temperature. The major ingredient of our model is the description of the guest-clathrate hydrate interaction by a spherically averaged Kihara potential with a nominal set of parameters, most of which are fitted to experimental equilibrium data. Our model allows us to find that Kr, Ar and N2 can be efficiently encaged in clathrate hydrates formed at temperatures higher than approximately 48.5 K in the primitive nebula, instead of forming pure condensates below 30 K. However, we find at the same time that the determination of the relative abundances of guest species incorporated in these clathrate hydrates strongly depends on the choice of the parameters of the Kihara potential and also on the adopted size of cages. Indeed, by testing different potential parameters, we have noted that even minor dispersions between the different existing sets can lead to non-negligible variations in the determination of the volatiles trapped in clathrate hydrates formed in the primordial nebula. However, these variations are not found to be strong enough to reverse the relative abundances

  11. Changes in microbial communities associated with gas hydrates in subseafloor sediments from the Nankai Trough.

    PubMed

    Katayama, Taiki; Yoshioka, Hideyoshi; Takahashi, Hiroshi A; Amo, Miki; Fujii, Tetsuya; Sakata, Susumu

    2016-08-01

    Little is known about the microbial distribution patterns in subseafloor sediments. This study examines microbial diversity and activities in sediments of the Nankai Trough, where biogenic gas hydrates are deposited. Illumina sequencing of 16S rRNA genes revealed that the prokaryotic community structure is correlated with hydrate occurrence and depth but not with the sedimentary facies. The bacterial phyla 'Atribacteria' lineage JS1 and Chloroflexi dominated in all samples, whereas lower taxonomic units of Chloroflexi accounted for community variation related to hydrate saturation. In archaeal communities, 'Bathyarchaeota' was significantly abundant in the hydrate-containing samples, whereas Marine Benthic Group-B dominated in the upper sediments without hydrates. mcrA gene sequences assigned to deeply branching groups and ANME-1 were detected only in hydrate-containing samples. A predominance of hydrogenotrophic methanogens, Methanomicrobiales and Methanobacteriales, over acetoclastic methanogens was found throughout the depth. Incubation tests on hydrate-containing samples with a stable isotope tracer showed anaerobic methane oxidation activities under both low- and seawater-like salinity conditions. These results indicate that the distribution patterns of microorganisms involved in carbon cycling changed with gas hydrate occurrence, possibly because of the previous hydrate dissociation followed by pore water salinity decrease in situ, as previously proposed by a geochemical study at the study site.

  12. 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.

  13. Some thermodynamical aspects of protein hydration water

    SciTech Connect

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene; Chen, Sow-Hsin

    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.

  14. 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

  15. Lactic acid and thermal treatments trigger the hydrolysis of myo-inositol hexakisphosphate and modify the abundance of lower myo-inositol phosphates in barley (Hordeum vulgare L.).

    PubMed

    Metzler-Zebeli, Barbara U; Deckardt, Kathrin; Schollenberger, Margit; Rodehutscord, Markus; Zebeli, Qendrim

    2014-01-01

    Barley is an important source of dietary minerals, but it also contains myo-inositol hexakisphosphate (InsP6) that lowers their absorption. This study evaluated the effects of increasing concentrations (0.5, 1, and 5%, vol/vol) of lactic acid (LA), without or with an additional thermal treatment at 55°C (LA-H), on InsP6 hydrolysis, formation of lower phosphorylated myo-inositol phosphates, and changes in chemical composition of barley grain. Increasing LA concentrations and thermal treatment linearly reduced (P<0.001) InsP6-phosphate (InsP6-P) by 0.5 to 1 g compared to the native barley. In particular, treating barley with 5% LA-H was the most efficient treatment to reduce the concentrations of InsP6-P, and stimulate the formation of lower phosphorylated myo-inositol phosphates such as myo-inositol tetraphosphate (InsP4) and myo-inositol pentaphosphates (InsP5). Also, LA and thermal treatment changed the abundance of InsP4 and InsP5 isomers with Ins(1,2,5,6)P4 and Ins(1,2,3,4,5)P5 as the dominating isomers with 5% LA, 1% LA-H and 5% LA-H treatment of barley, resembling to profiles found when microbial 6-phytase is applied. Treating barley with LA at room temperature (22°C) increased the concentration of resistant starch and dietary fiber but lowered those of total starch and crude ash. Interestingly, total phosphorus (P) was only reduced (P<0.05) in barley treated with LA-H but not after processing of barley with LA at room temperature. In conclusion, LA and LA-H treatment may be effective processing techniques to reduce InsP6 in cereals used in animal feeding with the highest degradation of InsP6 at 5% LA-H. Further in vivo studies are warranted to determine the actual intestinal P availability and to assess the impact of changes in nutrient composition of LA treated barley on animal performance.

  16. 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.

  17. 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.

  18. Methane hydrate formation in turbidite sediments of northern Cascadia IODP Expedition 311

    SciTech Connect

    Torres, M. E.; Trehu, Ann M.; cespedes, N.; Kastner, Miriam; Wortmann, Ulrich; Kim, J.; Long, Philip E.; Malinverno, Alberto; Pohlman, J. W.; Collett, T. S.

    2008-07-15

    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 N80% 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 (N63 μm) 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.

  19. 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.

  20. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    NASA Astrophysics Data System (ADS)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; D'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

  1. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    PubMed Central

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  2. alpha-Terpineol from hydration of crude sulfate turpentine oil.

    PubMed

    Pakdel, H; Sarron, S; Roy, C

    2001-09-01

    Hydration of alpha-pinene under various conditions was studied and compared with the literature. Optimal reaction conditions have been established for the hydration of alpha-pinene and crude turpentine oil in the absence of catalyst and using a low volume of acetone. A detailed reaction product analysis is reported. The main hydration product, alpha-terpineol, was obtained at a yield of 67 wt % of the initial alpha-pinene by reacting with 15% aqueous sulfuric acid and an excess of acetone in an oil bath heated to 80-85 degrees C over the course of 4 h. A progressive transformation of alpha-terpineol to 4-(2-hydroxypropyl)-1-methylcyclohexanol (1,8-terpine) takes place as the hydration time exceeds 4 h. A crude turpentine oil sample was also hydrated under conditions similar to those of alpha-pinene. The alpha-terpineol yield was 77 wt % of the initial alpha-pinene in the crude turpentine oil. The chemical analysis of the crude turpentine oil before and after hydration was carried out, and the distribution of the products was discussed.

  3. Navigating the Waters of Unconventional Crystalline Hydrates

    PubMed Central

    2015-01-01

    Elucidating the crystal structures, transformations, and thermodynamics of the two zwitterionic hydrates (Hy2 and HyA) of 3-(4-dibenzo[b,f][1,4]oxepin-11-yl-piperazin-1-yl)-2,2-dimethylpropanoic acid (DB7) rationalizes the complex interplay of temperature, water activity, and pH on the solid form stability and transformation pathways to three neutral anhydrate polymorphs (Forms I, II°, and III). HyA contains 1.29 to 1.95 molecules of water per DB7 zwitterion (DB7z). Removal of the essential water stabilizing HyA causes it to collapse to an amorphous phase, frequently concomitantly nucleating the stable anhydrate Forms I and II°. Hy2 is a stoichiometric dihydrate and the only known precursor to Form III, a high energy disordered anhydrate, with the level of disorder depending on the drying conditions. X-ray crystallography, solid state NMR, and H/D exchange experiments on highly crystalline phase pure samples obtained by exquisite control over crystallization, filtration, and drying conditions, along with computational modeling, provided a molecular level understanding of this system. The slow rates of many transformations and sensitivity of equilibria to exact conditions, arising from its varying static and dynamic disorder and water mobility in different phases, meant that characterizing DB7 hydration in terms of simplified hydrate classifications was inappropriate for developing this pharmaceutical. PMID:26075319

  4. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs) complexes with 4-amino­phenyl­arsonic acid

    PubMed Central

    Smith, Graham; Wermuth, Urs D.

    2017-01-01

    The structures of the alkali metal (K, Rb and Cs) complex salts with 4-amino­phenyl­arsonic acid (p-arsanilic acid) manifest an isotypic series with the general formula [M 2(C6H7AsNO3)2(H2O)3], with M = K {poly[di-μ3-4-amino­phenyl­arsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO3)2(H2O)3], (I)}, Rb {poly[di-μ3-4-amino­phenyl­arsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO3)2(H2O)3], (II)}, and Cs {poly[di-μ3-4-amino­phenyl­arsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO3)2(H2O)3], (III)}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water mol­ecule, with the two hydrogen p-arsanilate ligands and the second water mol­ecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I) to eight-coordinate in both (II) and (III), with overall M—O bond-length ranges of 2.694 (5)–3.009 (7) (K), 2.818 (4)–3.246 (4) (Rb) and 2.961 (9)–3.400 (10) Å (Cs). The additional three bonds in (II) and (III) are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100) are generated through a number of bridging bonds involving the water mol­ecules (including hydrogen-bonding inter­actions), as well as through the arsanilate O atoms. These layers are linked across [100] through amine N—H⋯O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures. PMID:28217343

  5. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs) complexes with 4-amino-phenyl-arsonic acid.

    PubMed

    Smith, Graham; Wermuth, Urs D

    2017-02-01

    The structures of the alkali metal (K, Rb and Cs) complex salts with 4-amino-phenyl-arsonic acid (p-arsanilic acid) manifest an isotypic series with the general formula [M2(C6H7AsNO3)2(H2O)3], with M = K {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO3)2(H2O)3], (I)}, Rb {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO3)2(H2O)3], (II)}, and Cs {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO3)2(H2O)3], (III)}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water mol-ecule, with the two hydrogen p-arsanilate ligands and the second water mol-ecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I) to eight-coordinate in both (II) and (III), with overall M-O bond-length ranges of 2.694 (5)-3.009 (7) (K), 2.818 (4)-3.246 (4) (Rb) and 2.961 (9)-3.400 (10) Å (Cs). The additional three bonds in (II) and (III) are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100) are generated through a number of bridging bonds involving the water mol-ecules (including hydrogen-bonding inter-actions), as well as through the arsanilate O atoms. These layers are linked across [100] through amine N-H⋯O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

  6. Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Rossi, Michel J.; Iannarelli, Riccardo

    2015-04-01

    The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in

  7. Creatininium bis­(pyridine-2,6-dicarboxyl­ato)chromate(III) pyridine-2,6-dicarboxylic acid hexa­hydrate

    PubMed Central

    Aghabozorg, Hossein; Derikvand, Zohreh; Olmstead, Marilyn M.; Attar Gharamaleki, Jafar

    2008-01-01

    The title compound, (C4H8N3O)[Cr(C7H3NO4)2]·C7H5NO4·6H2O, was obtained by the reaction of Cr(NO3)3·9H2O with pyridine-2,6-dicarboxylic acid (pydcH2) and creatinine (creat) in aqueous solution (molar ratio 1:2:2). The cation is a protonated creatinine (creatH+) while the anion is a bis-pydc2− CrIII complex. The CrIII is coordinated by four oxygen and two nitro­gen atoms of two (pydc)2– groups and has a disorted octa­hedral coordination environment. The structure also contains a neutral mol­ecule of pydcH2 that is hydrogen bonded to the creatH+ and six mol­ecules of water. Extensive inter­molecular inter­actions, including seventeen classical hydrogen bonds, two weak C—H⋯O bonds, and C—O⋯π stacking inter­actions, with O⋯centroid distances of 3.211 (13) and 3.300 (12) Å, connect the various components in the crystal structure. PMID:21200994

  8. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  9. A co-crystal of nona-hydrated disodium(II) with mixed anions from m-chloro-benzoic acid and furosemide.

    PubMed

    London, Bianca King; Claville, Michelle O Fletcher; Babu, Sainath; Fronczek, Frank R; Uppu, Rao M

    2015-10-01

    In the title compound, [Na2(H2O)9](C7H4ClO2)(C12H10ClN2O5S) {systematic name: catena-poly[[[triaquasodium(I)]-di-μ-aqua-[triaquasodium(I)]-μ-aqua] 3-chlorobenzoate 4-chloro-2-[(furan-2-ylmethyl)amino]-5-sulfamoylbenzoate]}, both the original m-chloro-benzoic acid and furosemide exist with deprotonated carboxyl-ates, and the sodium cations and water mol-ecules exist in chains with stoichiometry [Na2(OH2)9](2+) that propagate in the [-110] direction. Each of the two independent Na(+) ions is coordinated by three monodentate water mol-ecules, two double-water bridges, and one single-water bridge. There is considerable cross-linking between the [Na2(OH2)9](2+) chains and to furosemide sulfonamide and carboxyl-ate by inter-molecular O-H⋯O hydrogen bonds. All hydrogen-bond donors participate in a complex two-dimensional array parallel to the ab plane. The furosemide NH group donates an intra-molecular hydrogen bond to the carboxyl-ate group, and the furosemide NH2 group donates an intra-molecular hydrogen bond to the Cl atom and an inter-molecular one to the m-chloro-benzoate O atom. The plethora of hydrogen-bond donors on the cation/water chain leads to many large rings, up to graph set R 4 (4)(24), involving two chains and two furosemide anions. The chloro-benzoate is involved in only one R 2 (2)(8) ring, with two water mol-ecules cis-coordinated to Na. The furan O atom is not hydrogen bonded.

  10. Preparation, in vitro and in vivo evaluation of polymeric nanoparticles based on hyaluronic acid-poly(butyl cyanoacrylate) and D-alpha-tocopheryl polyethylene glycol 1000 succinate for tumor-targeted delivery of morin hydrate.

    PubMed

    Abbad, Sarra; Wang, Cheng; Waddad, Ayman Yahia; Lv, Huixia; Zhou, Jianping

    2015-01-01

    Herein, we describe the preparation of a targeted cellular delivery system for morin hydrate (MH), based on a low-molecular-weight hyaluronic acid-poly(butyl cyanoacrylate) (HA-PBCA) block copolymer. In order to enhance the therapeutic effect of MH, D-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS) was mixed with HA-PBCA during the preparation process. The MH-loaded HA-PBCA "plain" nanoparticle (MH-PNs) and HA-PBCA/TPGS "mixed" nanoparticles (MH-MNs) were concomitantly characterized in terms of loading efficiency, particle size, zeta potential, critical aggregation concentration, and morphology. The obtained MH-PNs and MH-MNs exhibited a spherical morphology with a negative zeta potential and a particle size less than 200 nm, favorable for drug targeting. Remarkably, the addition of TPGS resulted in about 1.6-fold increase in drug-loading. The in vitro cell viability experiment revealed that MH-MNs enhanced the cytotoxicity of MH in A549 cells compared with MH solution and MH-PNs. Furthermore, blank MNs containing TPGS exhibited selective cytotoxic effects against cancer cells without diminishing the viability of normal cells. In addition, the cellular uptake study indicated that MNs resulted in 2.28-fold higher cellular uptake than that of PNs, in A549 cells. The CD44 receptor competitive inhibition and the internalization pathway studies suggested that the internalization mechanism of the nanoparticles was mediated mainly by the CD44 receptors through a clathrin-dependent endocytic pathway. More importantly, MH-MNs exhibited a higher in vivo antitumor potency and induced more tumor cell apoptosis than did MH-PNs, following intravenous administration to S180 tumor-bearing mice. Overall, the results imply that the developed nanoparticles are promising vehicles for the targeted delivery of lipophilic anticancer drugs.

  11. Preparation, in vitro and in vivo evaluation of polymeric nanoparticles based on hyaluronic acid-poly(butyl cyanoacrylate) and D-alpha-tocopheryl polyethylene glycol 1000 succinate for tumor-targeted delivery of morin hydrate

    PubMed Central

    Abbad, Sarra; Wang, Cheng; Waddad, Ayman Yahia; Lv, Huixia; Zhou, Jianping

    2015-01-01

    Herein, we describe the preparation of a targeted cellular delivery system for morin hydrate (MH), based on a low-molecular-weight hyaluronic acid-poly(butyl cyanoacrylate) (HA-PBCA) block copolymer. In order to enhance the therapeutic effect of MH, D-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS) was mixed with HA-PBCA during the preparation process. The MH-loaded HA-PBCA “plain” nanoparticle (MH-PNs) and HA-PBCA/TPGS “mixed” nanoparticles (MH-MNs) were concomitantly characterized in terms of loading efficiency, particle size, zeta potential, critical aggregation concentration, and morphology. The obtained MH-PNs and MH-MNs exhibited a spherical morphology with a negative zeta potential and a particle size less than 200 nm, favorable for drug targeting. Remarkably, the addition of TPGS resulted in about 1.6-fold increase in drug-loading. The in vitro cell viability experiment revealed that MH-MNs enhanced the cytotoxicity of MH in A549 cells compared with MH solution and MH-PNs. Furthermore, blank MNs containing TPGS exhibited selective cytotoxic effects against cancer cells without diminishing the viability of normal cells. In addition, the cellular uptake study indicated that MNs resulted in 2.28-fold higher cellular uptake than that of PNs, in A549 cells. The CD44 receptor competitive inhibition and the internalization pathway studies suggested that the internalization mechanism of the nanoparticles was mediated mainly by the CD44 receptors through a clathrin-dependent endocytic pathway. More importantly, MH-MNs exhibited a higher in vivo antitumor potency and induced more tumor cell apoptosis than did MH-PNs, following intravenous administration to S180 tumor-bearing mice. Overall, the results imply that the developed nanoparticles are promising vehicles for the targeted delivery of lipophilic anticancer drugs. PMID:25609946

  12. Value of periangiography hydration.

    PubMed

    Kerstein, M D; Puyau, F A

    1984-11-01

    The value of contrast dye to the planning and evaluation of cardiovascular disease cannot be overestimated. However, adverse renal sequellae may cause the surgeon to hesitate in obtaining an arteriogram, especially in patients with compromised renal function. The purpose of this study was to evaluate the incidence of renal dysfunction in patients requiring angiography. Standard contrast angiography for cerebral or peripheral vascular disease was administered to 150 consecutive patients (89 men and 61 women), with an average age of 63.3 years (range 49 to 89 years). All patients received 100 to 150 ml of dye, with a concentration of approximately 50% iodine. Patients were hydrated with 0.5 N saline/5% dextrose, intravenously, for 8 hours before the procedure (1 to 3 ml/kg/hr). In 31 patients (11 women and 20 men) the serum BUN and/or creatinine levels were elevated (mean BUN value of 48 +/- 9 mg/dl; mean creatinine level of 2.8 +/- 0.6 mg/dl). The patients with abnormal renal function received an additional 300 to 500 ml of intravenous fluid, plus 20 to 40 mg intravenous furosemide, 1 hour before roentgenography to establish a diuresis. All patients were hydrated for 6 hours after angiography with the same solution at the same rate (1 to 3 ml/kg/hr). There were no episodes of compromised renal or cardiopulmonary dysfunction because of contrast angiography. In no patient did the BUN or creatinine level rise, nor was there evidence of acute tubular necrosis, as documented by oliguria and abnormal cells in the urine. Angiography is a safe procedure, even with patients who may have compromised renal function, if appropriate prehydration/posthydration and diuretic measures are undertaken.

  13. [NMF and cosmetology of cutaneous hydration].

    PubMed

    Marty, J-P

    2002-01-01

    In the stratum corneum, the water binds to the intracellular hygroscopic and hydrosoluble substances called "natural moisturizing factors" or NMF. These "natural moisturizing factors" contained in the corneocytes are formed during epidermal differentiation and may represent up to 10 p. cent of the corneocyte mass. They are principally amino acids, carboxylic pyrrolidone acid, lactic acid, urea, glucose and mineral ions. Keratinization plays an important part in the formation of NMF that exhibit strong osmotic potential attracting the water molecules. The binding of water to NMF is the static aspect of cutaneous hydration. The second, dynamic, aspect is related to the selective permeability of the stratum corneum and to its lipid barrier properties, the permeability of which depends on the integrity and nature of the inter-corneocyte lipids and their lamellar organization between the cells. In these conditions, hydration cosmetics rely on two concepts that can be isolated or associated: the supply of hydrophilic substances to the stratum corneum, capable of attracting and retaining water (moisturizer) or capable of restoring the barrier in order to restore normal water loss or of protecting it against aggression (occlusive).

  14. A Hydration of an Alkyne Illustrating Steam and Vacuum Distillation.

    ERIC Educational Resources Information Center

    Wasacz, J. P.; Badding, V. G.

    1982-01-01

    Reports on the conversion 2,5-dimethylhexyne-2,5-diol(I) to 2,2,5,5-tetramethyltetrahydrofuran-3-one(II) using aqueous mercuric sulfate without the use of acid. The experiment has been successfully performed in introductory organic chemistry laboratories demonstrating alkyne hydration, steam distillation, vacuum distillation, drying of organic…

  15. 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.

  16. Obsidian hydration dates glacial loading?

    PubMed

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  17. Obsidian Hydration: A New Paleothermometer

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Riciputi, Lee R; Cole, David R; Fayek, Mostafa; Elam, J. Michael

    2006-01-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  18. Obsidian hydration dates glacial loading?

    USGS Publications Warehouse

    Friedman, I.; Pierce, K.L.; Obradovich, J.D.; Long, W.D.

    1973-01-01

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming . The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  19. NATURAL GAS HYDRATES STORAGE PROJECT PHASE II. CONCEPTUAL DESIGN AND ECONOMIC STUDY

    SciTech Connect

    R.E. Rogers

    1999-09-27

    DOE Contract DE-AC26-97FT33203 studied feasibility of utilizing the natural-gas storage property of gas hydrates, so abundantly demonstrated in nature, as an economical industrial process to allow expanded use of the clean-burning fuel in power plants. The laboratory work achieved breakthroughs: (1) Gas hydrates were found to form orders of magnitude faster in an unstirred system with surfactant-water micellar solutions. (2) Hydrate particles were found to self-pack by adsorption on cold metal surfaces from the micellar solutions. (3) Interstitial micellar-water of the packed particles were found to continue forming hydrates. (4) Aluminum surfaces were found to most actively collect the hydrate particles. These laboratory developments were the bases of a conceptual design for a large-scale process where simplification enhances economy. In the design, hydrates form, store, and decompose in the same tank in which gas is pressurized to 550 psi above unstirred micellar solution, chilled by a brine circulating through a bank of aluminum tubing in the tank employing gas-fired refrigeration. Hydrates form on aluminum plates suspended in the chilled micellar solution. A low-grade heat source, such as 110 F water of a power plant, circulates through the tubing bank to release stored gas. The design allows a formation/storage/decomposition cycle in a 24-hour period of 2,254,000 scf of natural gas; the capability of multiple cycles is an advantage of the process. The development costs and the user costs of storing natural gas in a scaled hydrate process were estimated to be competitive with conventional storage means if multiple cycles of hydrate storage were used. If more than 54 cycles/year were used, hydrate development costs per Mscf would be better than development costs of depleted reservoir storage; above 125 cycles/year, hydrate user costs would be lower than user costs of depleted reservoir storage.

  20. Microbial community structure in methane hydrate-bearing sediments of freshwater Lake Baikal.

    PubMed

    Kadnikov, Vitaly V; Mardanov, Andrey V; Beletsky, Alexey V; Shubenkova, Olga V; Pogodaeva, Tatiana V; Zemskaya, Tamara I; Ravin, Nikolai V; Skryabin, Konstantin G

    2012-02-01

    Gas hydrates in marine sediments have been known for many years but recently hydrates were found in the sediments of Lake Baikal, the largest freshwater basin in the world. Marine gas hydrates are associated with complex microbial communities involved in methanogenesis, methane oxidation, sulfate reduction and other biotransformations. However, the contribution of microorganisms to the formation of gas hydrates remains poorly understood. We examined the microbial communities in the hydrate-bearing sediments and water column of Lake Baikal using pyrosequencing of 16S rRNA genes. Aerobic methanotrophic bacteria dominated the water sample collected at the lake floor in the hydrate-bearing site. The shallow sediments were dominated by Archaea. Methanogens of the orders Methanomicrobiales and Methanosarcinales were abundant, whereas representatives of archaeal lineages known to perform anaerobic oxidation of methane, as well as sulfate-reducing bacteria, were not found. Affiliation of archaea to methanogenic rather than methane-oxidizing lineages was supported by analysis of the sequences of the methyl coenzyme M reductase gene. The deeper sediments located at 85-90 cm depth close to the hydrate were dominated by Bacteria, mostly assigned to Chloroflexi, candidate division JS1 and Caldiserica. Overall, our results are consistent with the biological origin of methane hydrates in Lake Baikal.

  1. Hydration of polyethylene glycol-grafted liposomes.

    PubMed

    Tirosh, O; Barenholz, Y; Katzhendler, J; Priev, A

    1998-03-01

    This study aimed to characterize the effect of polyethylene glycol of 2000 molecular weight (PEG2000) attached to a dialkylphosphatidic acid (dihexadecylphosphatidyl (DHP)-PEG2000) on the hydration and thermodynamic stability of lipid assemblies. Differential scanning calorimetry, densitometry, and ultrasound velocity and absorption measurements were used for thermodynamic and hydrational characterization. Using a differential scanning calorimetry technique we showed that each molecule of PEG2000 binds 136 +/- 4 molecules of water. For PEG2000 covalently attached to the lipid molecules organized in micelles, the water binding increases to 210 +/- 6 water molecules. This demonstrates that the two different structural configurations of the PEG2000, a random coil in the case of the free PEG and a brush in the case of DHP-PEG2000 micelles, differ in their hydration level. Ultrasound absorption changes in liposomes reflect mainly the heterophase fluctuations and packing defects in the lipid bilayer. The PEG-induced excess ultrasound absorption of the lipid bilayer at 7.7 MHz for PEG-lipid concentrations over 5 mol % indicates the increase in the relaxation time of the headgroup rotation due to PEG-PEG interactions. The adiabatic compressibility (calculated from ultrasound velocity and density) of the lipid bilayer of the liposome increases monotonically with PEG-lipid concentration up to approximately 7 mol %, reflecting release of water from the lipid headgroup region. Elimination of this water, induced by grafted PEG, leads to a decrease in bilayer defects and enhanced lateral packing of the phospholipid acyl chains. We assume that the dehydration of the lipid headgroup region in conjunction with the increase of the hydration of the outer layer by grafting PEG in brush configuration are responsible for increasing thermodynamic stability of the liposomes at 5-7 mol % of PEG-lipid. At higher PEG-lipid concentrations, compressibility and partial volume of the lipid phase

  2. Hydration of polyethylene glycol-grafted liposomes.

    PubMed Central

    Tirosh, O; Barenholz, Y; Katzhendler, J; Priev, A

    1998-01-01

    This study aimed to characterize the effect of polyethylene glycol of 2000 molecular weight (PEG2000) attached to a dialkylphosphatidic acid (dihexadecylphosphatidyl (DHP)-PEG2000) on the hydration and thermodynamic stability of lipid assemblies. Differential scanning calorimetry, densitometry, and ultrasound velocity and absorption measurements were used for thermodynamic and hydrational characterization. Using a differential scanning calorimetry technique we showed that each molecule of PEG2000 binds 136 +/- 4 molecules of water. For PEG2000 covalently attached to the lipid molecules organized in micelles, the water binding increases to 210 +/- 6 water molecules. This demonstrates that the two different structural configurations of the PEG2000, a random coil in the case of the free PEG and a brush in the case of DHP-PEG2000 micelles, differ in their hydration level. Ultrasound absorption changes in liposomes reflect mainly the heterophase fluctuations and packing defects in the lipid bilayer. The PEG-induced excess ultrasound absorption of the lipid bilayer at 7.7 MHz for PEG-lipid concentrations over 5 mol % indicates the increase in the relaxation time of the headgroup rotation due to PEG-PEG interactions. The adiabatic compressibility (calculated from ultrasound velocity and density) of the lipid bilayer of the liposome increases monotonically with PEG-lipid concentration up to approximately 7 mol %, reflecting release of water from the lipid headgroup region. Elimination of this water, induced by grafted PEG, leads to a decrease in bilayer defects and enhanced lateral packing of the phospholipid acyl chains. We assume that the dehydration of the lipid headgroup region in conjunction with the increase of the hydration of the outer layer by grafting PEG in brush configuration are responsible for increasing thermodynamic stability of the liposomes at 5-7 mol % of PEG-lipid. At higher PEG-lipid concentrations, compressibility and partial volume of the lipid phase

  3. Hydrate formation and growth in pores

    NASA Astrophysics Data System (ADS)

    Jung, Jong-Won; Santamarina, J. Carlos

    2012-04-01

    Gas hydrates consist of guest gas molecules encaged in water cages. Methane hydrate forms in marine and permafrost sediments. In this study, we use optical, mechanical and electrical measurements to monitor hydrate formation and growth in small pores to better understand the hydrate pore habit in hydrate-bearing sediments. Hydrate formation in capillary tubes exposes the complex and dynamic interactions between nucleation, gas diffusion and gas solubility. The observation of hydrate growth in a droplet between transparent plates shows that the hydrate shell does not grow homogeneously but advances in the form of lobes that invade the water phase; in fact, the hydrate shell must be discontinuous and possibly cracked to justify the relatively fast growth rates observed in these experiments. Volume expansion during hydrate formation causes water to flow out of menisci; expelled water either spreads on the surface of water-wet substrates and forms a thin hydrate sheet, or remains next to menisci when substrates are oil-wet. Hydrate formation is accompanied by ion exclusion, yet, there is an overall increase in electrical resistance during hydrate formation. Hydrate growth may become salt-limited in trapped water conditions; in this case, aqueous brine and gas CH4 may be separated by hydrate and the three-phase system remains stable within the pore space of sediments.

  4. Crystallization of a polymorphic hydrate system.

    PubMed

    Tian, F; Qu, H; Louhi-Kultanen, M; Rantanen, J

    2010-02-01

    Nitrofurantoin can form two monohydrates, which have the same chemical composition and molar ratio of water, but differ in the crystal arrangements. The two monohydrates (hydrates I and II) could be produced independently via evaporative crystallization, where supersaturation and solvent composition were both found to have an effect. Hydrate I showed much slower crystallization than hydrate II. During cooling crystallization, the nucleation and growth of hydrate II was again dominant, consuming all supersaturation and leading to no hydrate I formation. Seeding of hydrate I during cooling crystallization was also applied, but the hydrate I seeds were not able to initiate its nucleation rather than dissolving into crystallizing solution. Although solubility tests revealed that hydrate II is more stable than hydrate I due to its lower solubility (110 +/- 4 and 131 +/- 12 microg/mL for hydrates II and I, respectively), this difference is rather small. Therefore, the small free energy difference between the two hydrates, together with the slow crystallization of hydrate I, both lead to a hindrance of hydrate I formation. Furthermore, the crystal structure of hydrate II demonstrated a higher H-bonding extent than hydrate I, suggesting its more favorable crystallization. This is in good agreement with experimental results.

  5. Airway Hydration and COPD

    PubMed Central

    Ghosh, Arunava; Boucher, R.C.; Tarran, Robert

    2015-01-01

    Chronic obstructive pulmonary disease (COPD) is one of the prevalent causes of worldwide mortality and encompasses two major clinical phenotypes, i.e., chronic bronchitis (CB) and emphysema. The most common cause of COPD is chronic tobacco inhalation. Research focused on the chronic bronchitic phenotype of COPD has identified several pathological processes that drive disease initiation and progression. For example, the lung’s mucociliary clearance (MCC) system performs the critical task of clearing inhaled pathogens and toxic materials from the lung. MCC efficiency is dependent on: (i) the ability of apical plasma membrane ion channels such as the cystic fibrosis transmembrane conductance regulator (CFTR) and the epithelial Na+ channel (ENaC) to maintain airway hydration; (ii) ciliary beating; and, (iii) appropriate rates of mucin secretion. Each of these components is impaired in CB and likely contributes to the mucus stasis/accumulation seen in CB patients. This review highlights the cellular components responsible for maintaining MCC and how this process is disrupted following tobacco exposure and with CB. We shall also discuss existing therapeutic strategies for the treatment of chronic bronchitis and how components of the MCC can be used as biomarkers for the evaluation of tobacco or tobacco-like-product exposure. PMID:26068443

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

    PubMed Central

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

    2011-01-01

    Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state 1H, 13C, 29Si, and 27Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications. PMID:21562207

  7. Water Tectonics: Evidence That Hydration Plays a Role in Tectonism

    NASA Astrophysics Data System (ADS)

    Lowry, A. R.; Schutt, D.; Perez-Gussinye, M.; Buehler, J. S.; Berry, M. A.; Ma, X.; Ravat, D.

    2015-12-01

    Several new observations provide evidence that water may play a more important role in tectonism than previously realized. Among these, • Thermodynamical modeling suggests that hydration promotes crustal mineral assemblages with lowered vP/vS and decreased density. This sheds new light on the significance of low crustal vP/vS measured in the western U.S. Cordillera from joint inversion of EarthScope USArray receiver functions and gravity. vP/vS, previously interpreted in terms of quartz abundance, is strikingly low throughout the highest-elevation regions of the western Cordillera. • Rheological modeling of flexural rigidity measurements also can be used to map water variations, primarily in the uppermost mantle. Mantle hydration estimated from flexural rigidity exhibits very similar spatial distribution to crustal hydration inferred from vP/vS, with the notable exception that the Wyoming craton has dry mantle lithosphere but a hydrous crust. • In hydrated lithosphere of the high-elevation western U.S. Cordillera, Moho temperatures estimated from Pn velocities are systematically colder than predictions by simple geothermal models of surface heat flow. These differences can only be reconciled by invoking a previously unrecognized advective term in the deep thermal transfer. • New and improved estimates of magnetic bottom are much deeper than the depth of the magnetite Curie temperature in some apparently hydrous lithosphere (notably, east of the Siletzia accreted terrane). This may indicate exotic magnetic mineralogies thought to occur only under hydrous conditions. Lithospheric hydration may be driven either by dehydration of subducted slab or by entrainment of water into upwellings passing through the mantle transition zone. Conceptualizing hydration as a large-scale process accompanied by increased buoyancy and decreased ductile strength, coupled with widespread changes in mineralogy, mass and energy transfer may help to illuminate many otherwise

  8. Controversies about the occurrence of chloral hydrate in drinking water.

    PubMed

    Dabrowska, Agata; Nawrocki, Jacek

    2009-05-01

    Besides trihalomethanes (THMs) and haloacetic acids (HAAs), chloral hydrate (CH) is the next most prevalent disinfection by-product (DBP) in drinking water, formed as a result of the reaction between chlorine and natural organic matter (NOM). Chloral hydrate (trichloroacetaldehyde) should be limited in drinking water because of its adverse health effect. The controversies concerning the appearance of CH in disinfected water found in literature are discussed in the present paper. According to some authors the CH yield during chlorination of water depends only on TOC. However, there are other data available that do not confirm this relationship. Another fact requiring clarification is the dependence of CH formation on pH. In the present study, CH formation is analysed in different types of water disinfected with different doses of chlorine. Formation of CH is correlated with the dose of Cl(2) and the contact time. The formation of chloral hydrate takes place as long as chlorine is available in the water. Total organic carbon (TOC) is not considered the main factor influencing the production of chloral hydrate in water treated with Cl(2) as the production depends also on the nature of NOM. Higher levels of CH are observed at alkaline conditions (pH>7). A significant correlation (R(2)>0.9) between the concentrations of chloral hydrate and chloroform has been observed. The preozonation increases significantly the chloral hydrate formation potential in the water treated. Biofiltration process does not remove all of CH precursors and its efficiency depends strongly on the contact time. Chloral hydrate was analyzed by gas chromatography with electron capture detector with the detection limit 0.1 microg L(-1).

  9. Tetrahydrofuran hydrate decomposition characteristics in porous media

    NASA Astrophysics Data System (ADS)

    Song, Yongchen; Wang, Pengfei; Wang, Shenglong; Zhao, Jiafei; Yang, Mingjun

    2016-12-01

    Many tetrahydrofuran (THF) hydrate properties are similar to those of gas hydrates. In the present work THF hydrate dissociation in four types of porous media is studied. THF solution was cooled to 275.15 K with formation of the hydrate under ambient pressure, and then it dissociated under ambient conditions. THF hydrate dissociation experiments in each porous medium were conducted three times. Magnetic resonance imaging (MRI) was used to obtain images. Decomposition time, THF hydrate saturation and MRI mean intensity (MI) were measured and analyzed. The experimental results showed that the hydrate decomposition time in BZ-4 and BZ-3 was similar and longer than that in BZ-02. In each dissociation process, the hydrate decomposition time of the second and third cycles was shorter than that of the first cycle in BZ-4, BZ-3, and BZ-02. The relationship between THF hydrate saturation and time is almost linear.

  10. 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.

  11. Hydrated mineral stratigraphy of Ius Chasma, Valles Marineris

    USGS Publications Warehouse

    Roach, L.H.; Mustard, J.F.; Swayze, G.; Milliken, R.E.; Bishop, J.L.; Murchie, S.L.; Lichtenberg, K.

    2010-01-01

    New high-resolution spectral and morphologic imaging of deposits on walls and floor of Ius Chasma extend previous geomorphic mapping, and permit a new interpretation of aqueous processes that occurred during the development of Valles Marineris. We identify hydrated mineralogy based on visible-near infrared (VNIR) absorptions. We map the extents of these units with CRISM spectral data as well as morphologies in CTX and HiRISE imagery. Three cross-sections across Ius Chasma illustrate the interpreted mineral stratigraphy. Multiple episodes formed and transported hydrated minerals within Ius Chasma. Polyhydrated sulfate and kieserite are found within a closed basin at the lowest elevations in the chasma. They may have been precipitates in a closed basin or diagenetically altered after deposition. Fluvial or aeolian processes then deposited layered Fe/Mg smectite and hydrated silicate on the chasma floor, postdating the sulfates. The smectite apparently was weathered out of Noachian-age wallrock and transported to the depositional sites. The overlying hydrated silicate is interpreted to be an acid-leached phyllosilicate transformed from the underlying smectite unit, or a smectite/jarosite mixture. The finely layered smectite and massive hydrated silicate units have an erosional unconformity between them, that marks a change in surface water chemistry. Landslides transported large blocks of wallrock, some altered to contain Fe/Mg smectite, to the chasma floor. After the last episode of normal faulting and subsequent landslides, opal was transported short distances into the chasma from a few m-thick light-toned layer near the top of the wallrock, by sapping channels in Louros Valles. Alternatively, the material was transported into the chasma and then altered to opal. The superposition of different types of hydrated minerals and the different fluvial morphologies of the units containing them indicate sequential, distinct aqueous environments, characterized by alkaline

  12. Laser Desorption Supersonic Jet Spectroscopy of Hydrated Tyrosine

    NASA Astrophysics Data System (ADS)

    Oba, Hikari; Shimozono, Yoko; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Carcabal, Pierre

    2013-06-01

    The structure of tyrosine (tyr) consists of amino-acid chain and phenol, and it has roughly two possible binding sites for water, amino-acid site and phenolic OH site. Investigating how water molecule binds to tyr will give fundamental information for hydrations of peptide and protein. Resonance enhanced multi photon ionization (REMPI) spectrum of tyr-water 1:1 cluster has already been reported by de Vries and co-workers, however, no analysis on the hydrated structures has been reported. In the REMPI spectrum, two clusters of bands are observed; one appears at ˜35600 cm^{-1} energy region which is the almost same with 0-0 transitions of tyr monomer, and another is observed at ˜300 cm^{-1} lower than the former. Based on the electronic transition energy of phenylalanine and the hydrated clusters, the former is expected to be derived from a structure that water binds to amino acid site. On the other hand, it is plausibly predicted that the latter originates from a structure that water binds to phenolic OH group, because the electronic transition of mono hydrated phenol is ˜300 cm^{-1} red-shifted from the monomer. We applied IR dip spectroscopy which can measure conformer selective IR spectra to the tyr-(H_{2}O)_{1} clusters by using laser desorption supersonic jet technique to confirm the assignments. Especially in the phenolic OH bound isomer, it was found that the intra molecular hydrogen bond within amino-acid chain, which is far from the water molecule and cannot interact directly with each other, is strengthened by the hydration. A. Abio-Riziq et al., J. Phys. Chem. A, 115, 6077 (2011). Y. Shimozono, et al., Phys. Chem. Chem. Phys., (2013) DOI: 10.1039/c3cp43573c. T. Ebata et al., Phys. Chem. Chem. Phys., 8, 4783 (2006). T. Watanabe et al., J. Chem. Phys., 105, 408 (1996).

  13. Site Selection for DOE/JIP Gas Hydrate Drilling in the Northern Gulf of Mexico

    SciTech Connect

    Hutchinson, D.R.; Shelander, D.; Dai, J.; McConnell, D.; Shedd, W.; Frye, M.; Ruppel, C.; Boswell, R.; Jones, E.; Collett, T.S.; Rose, K.; Dugan, B.; Wood, W.; Latham, T.

    2008-07-01

    In the late spring of 2008, the Chevron-led Gulf of Mexico Gas Hydrate Joint Industry Project (JIP) expects to conduct an exploratory drilling and logging campaign to better understand gas hydrate-bearing sands in the deepwater Gulf of Mexico. The JIP Site Selection team selected three areas to test alternative geological models and geophysical interpretations supporting the existence of potential high gas hydrate saturations in reservoir-quality sands. The three sites are near existing drill holes which provide geological and geophysical constraints in Alaminos Canyon (AC) lease block 818, Green Canyon (GC) 955, and Walker Ridge (WR) 313. At the AC818 site, gas hydrate is interpreted to occur within the Oligocene Frio volcaniclastic sand at the crest of a fold that is shallow enough to be in the hydrate stability zone. Drilling at GC955 will sample a faulted, buried Pleistocene channel-levee system in an area characterized by seafloor fluid expulsion features, structural closure associated with uplifted salt, and abundant seismic evidence for upward migration of fluids and gas into the sand-rich parts of the sedimentary section. Drilling at WR313 targets ponded sheet sands and associated channel/levee deposits within a minibasin, making this a non-structural play. The potential for gas hydrate occurrence at WR313 is supported by shingled phase reversals consistent with the transition from gas-charged sand to overlying gas-hydrate saturated sand. Drilling locations have been selected at each site to 1) test geological methods and models used to infer the occurrence of gas hydrate in sand reservoirs in different settings in the northern Gulf of Mexico; 2) calibrate geophysical models used to detect gas hydrate sands, map reservoir thicknesses, and estimate the degree of gas hydrate saturation; and 3) delineate potential locations for subsequent JIP drilling and coring operations that will collect samples for comprehensive physical property, geochemical and other

  14. Hydration water in dynamics of a hydrated beta-lactoglobulin

    NASA Astrophysics Data System (ADS)

    Yoshida, K.; Yamaguchi, T.; Bellissent-Funel, M.-C.; Longeville, S.

    2007-02-01

    Incoherent spin-echo signals of a hydrated β-lactoglobulin protein were investigated, at 275 and 293 K. The intermediate scattering functions I(Q,t) were divided in two contributions from surface water and protein, respectively. On one hand, the dynamics of the surface water follows a KWW stretched exponential function (the exponent is ~0.5), on the other hand, that of the protein follows a single exponential. The present results are consistent with our previous results of hydrated C-phycocyanin combining elastic and quasielastic neutron scattering and by molecular dynamics simulation.

  15. Life Origination Hydrate Hypothesis (LOH-Hypothesis)

    PubMed Central

    Ostrovskii, Victor; Kadyshevich, Elena

    2012-01-01

    The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis), according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides), DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor. PMID:25382120

  16. The nature of carbon-bearing phases in hydrated interplanetary dust particles. [Abstract only

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Thomas, K. L.; Mckay, D. S.

    1994-01-01

    We have been quantitatively measuring C abundances in hydrated interplanetary dust particles for the past few years, but in general, we have had to infer the distribution and nature of the C-bearing materials within these particles because of the complex microtextures of hydrated IDPs. Aside from rare carbonate grains, other C-bearing phases are difficult to distinguish from the fine-grained, poorly crystalline phyllosilicates that comprise the bulk of these particles. We know that carbonates alone cannot account for the high C abundances observed in most hydrated IDPs and that additional C-bearing phases must be present. We have recently applied the technique of electron energy-loss spectroscopy (EELS) in the transmission electron microscope (TEM) to identify and form the distribution of C-bearing phases in hydrated IDPs. These preliminary data show that several C-rich hydrated IDPs contain a mixture of two major forms of C, Mg-Fe carbonate and amorphous C. The near-edge structure in the C k-edges from these IDPs shows no evidence for the development of graphite or even poorly graphitized C. We conclude that the 'elemental' C in these IDPs is either very poorly ordered or is exceedingly fine-grained (we refer to this C as 'amorphous C'). The amorphous C is intimately intergrown with the fine-grained phyllosilicates and is evenly distributed within three of the four IDPs analyzed (only G1 contains discrete 'hot spots' of amorphous C). Not all hydrated IDPs contain carbonates.

  17. Constraints on hydrocarbon and organic acid abundances in hydrothermal fluids at the Von Damm vent field, Mid-Cayman Rise (Invited)

    NASA Astrophysics Data System (ADS)

    McDermott, J. M.; Seewald, J.; German, C. R.; Sylva, S. P.

    2013-12-01

    The generation of organic compounds in vent fluids has been of interest since the discovery of seafloor hydrothermal systems, due to implications for the sustenance of present-day microbial populations and their potential role in the origin of life on early Earth. Possible sources of organic compounds in hydrothermal systems include microbial production, thermogenic degradation of organic material, and abiotic synthesis. Abiotic organic synthesis reactions may occur during active circulation of seawater-derived fluids through the oceanic crust or within olivine-hosted fluid inclusions containing carbon-rich magmatic volatiles. H2-rich end-member fluids at the Von Damm vent field on the Mid-Cayman Rise, where fluid temperatures reach 226°C, provide an exciting opportunity to examine the extent of abiotic carbon transformations in a highly reducing system. Our results indicate multiple sources of carbon compounds in vent fluids at Von Damm. An ultramafic-influenced hydrothermal system located on the Mount Dent oceanic core complex at 2350 m depth, Von Damm vent fluids contain H2, CH4, and C2+ hydrocarbons in high abundance relative to basalt-hosted vent fields, and in similar abundance to other ultramafic-hosted systems, such as Rainbow and Lost City. The CO2 content and isotopic composition in end-member fluids are virtually identical to bottom seawater, suggesting that seawater DIC is unchanged during hydrothermal circulation of seawater-derived fluids. Accordingly, end-member CH4 that is present in slightly greater abundance than CO2 cannot be generated from reduction of aqueous CO2 during hydrothermal circulation. We postulate that CH4 and C2+ hydrocarbons that are abundantly present in Von Damm vent fluids reflect leaching of fluids from carbon- and H2-rich fluid inclusions hosted in plutonic rocks. Geochemical modeling of carbon speciation in the Von Damm fluids suggests that the relative abundances of CH4, C2+ hydrocarbons, and CO2 are consistent with

  18. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  19. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence? Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  20. Dissociation heat transfer characteristics of methane hydrates

    SciTech Connect

    Kamath, V.A.; Holder, G.D.

    1987-02-01

    Knowledge of the interfacial heat transfer phenomenon during the dissociation of gas hydrates is essential in modeling the hydrate dissociation process. Such knowledge has applications in natural gas processing, storage, or transportation; in the drilling and recovery of oil and gas in the presence of gas hydrates; in the desalination of sea water; and in the production of natural gas from hydrate reservoirs. The process of hydrate dissociation is a unique phenomenon in which gas and water are simultaneously produced at the dissociated hydrate surface and play an important role in the mechanism of heat transfer to hydrates. An earlier study of propane hydrate dissociation showed that hydrate dissociation is a heat-transfer-limited process and somewhat similar to the nucleate boiling of liquids. In the present study, heat transfer limitations for methane hydrate dissociation were studied for two reasons. First, a comparison of the results of this study with propane hydrate was desired. Second, the effect of hydrate structure and gas molecule type on the rate of heat transfer during hydrate dissociation was sought.

  1. Hydration water dynamics and instigation of protein structuralrelaxation

    SciTech Connect

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-09-01

    Until a critical hydration level is reached, proteins do not function. This critical level of hydration is analogous to a similar lack of protein function observed for temperatures below a dynamical temperature range of 180-220K that also is connected to the dynamics of protein surface water. Restoration of some enzymatic activity is observed in partially hydrated protein powders, sometimes corresponding to less than a single hydration layer on the protein surface, which indicates that the dynamical and structural properties of the surface water is intimately connected to protein stability and function. Many elegant studies using both experiment and simulation have contributed important information about protein hydration structure and timescales. The molecular mechanism of the solvent motion that is required to instigate the protein structural relaxation above a critical hydration level or transition temperature has yet to be determined. In this work we use experimental quasi-elastic neutron scattering (QENS) and molecular dynamics simulation to investigate hydration water dynamics near a greatly simplified protein system. We consider the hydration water dynamics near the completely deuterated N-acetyl-leucine-methylamide (NALMA) solute, a hydrophobic amino acid side chain attached to a polar blocked polypeptide backbone, as a function of concentration between 0.5M-2.0M under ambient conditions. We note that roughly 50-60% of a folded protein's surface is equally distributed between hydrophobic and hydrophilic domains, domains whose lengths are on the order of a few water diameters, that justify our study of hydration dynamics of this simple model protein system. The QENS experiment was performed at the NIST Center for Neutron Research, using the disk chopper time of flight spectrometer (DCS). In order to separate the translational and rotational components in the spectra, two sets of experiments were carried out using different incident neutron wavelengths of 7

  2. Effects of heat stress on proliferation, protein turnover, and abundance of heat shock protein messenger ribonucleic acid in cultured porcine muscle satellite cells.

    PubMed

    Kamanga-Sollo, E; Pampusch, M S; White, M E; Hathaway, M R; Dayton, W R

    2011-11-01

    It is well established that heat stress (HS) negatively affects growth rate in swine. Although reduced feed intake undoubtedly plays a significant role in this reduction, studies in laboratory animals and other nonswine species indicate muscle growth also is affected by HS-related alterations in muscle physiology. Evidence is now emerging that heat shock proteins (Hsp), produced in response to HS and other types of cellular stress, may play an important role in regulating the rate and efficiency of muscle growth. Because muscle satellite cells play a crucial role in postnatal muscle growth, the effects of HS on rates of satellite cell proliferation, protein synthesis, and protein degradation play an important role in determining the rate and extent of muscle growth. Consequently, in the current study we have examined the effects of mild HS (40.5°C for 48 h) on the rates of proliferation, protein synthesis, and protein degradation and on quantities of Hsp90, Hsp70, and Hsp25/27 mRNA and protein in cultured porcine muscle satellite cells (PSC). Mild HS of PSC cultures resulted in 2.5-, 1.4-, and 6.5-fold increases (P < 0.05) in the abundance of Hsp90, Hsp70, and Hsp25/27 mRNA, respectively, relative to control cultures. Abundance of Hsp 90, 70, and 25/27 proteins was also increased in HS PSC cultures compared with those in control cultures. Proliferation rates in HS PSC cultures were 35% less (P < 0.05) than those in control cultures. Protein synthesis rates in HS-fused PSC cultures were 85% greater (P < 0.05) than those in control cultures, and protein degradation rates in HS-fused PSC were 23% less (P < 0.05) than those in control cultures. In light of the crucial role satellite cells play in postnatal muscle growth, the HS-induced changes we have observed in rates of proliferation, protein turnover, and abundance of Hsp mRNA and Hsp protein in PSC cultures indicate that mild HS affects the physiology of PSC in ways that could affect muscle growth in swine.

  3. Evaluation of the geological relationships to gas hydrate formation and stability

    SciTech Connect

    Krason, J.; Finley, P.

    1988-01-01

    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  4. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

    Many efforts have been devoted to quantify excess pore pressures related to gas hydrate dissociation in marine sediments below the BSR using several approaches. Dissociation of gas hydrates in proximity of the BSR, in response to a change in the physical environment (i.e., temperature and/or pressure regime), can liberate excess gas incrising the local pore fluid pressure in the sediment, so decreasing the effective normal stress. So, gas hydrate dissociation may lead to excess pore pressure resulting in sediment deformation or failure, such as submarine landslides, sediment slumping, pockmarks and mud volcanoes, soft-sediment deformation and giant hummocks. Moreover, excess pore pressure may be the result of gas hydrate dissociation due to continuous sedimentation, tectonic uplift, sea level fall, heating or inhibitor injection. In order to detect the presence of the overpressure below the BSR, we propose two approachs. The fist approach models the BSR depth versus pore pressure; in fact, if the free gas below the BSR is in overpressure condition, the base of the gas hydrate stability is deeper with respect to the hydrostatic case. This effect causes a discrepancy between seismic and theoretical BSR depths. The second approach models the velocities versus gas hydrate and free gas concentrations and pore pressure, considering the approximation of the Biot theory in case of low frequency, i.e. seismic frequency. Knowing the P and S seismic velocity from seismic data analysis, it is possibile to jointly estimate the gas hydrate and free gas concentrations and the pore pressure regime. Alternatively, if the S-wave velocity is not availbale (due to lack of OBS/OBC data), an AVO analysis can be performed in order to extract information about Poisson ratio. Our modeling suggests that the areas characterized by shallow waters (i.e., areas in which human infrastructures, such as pipelines, are present) are significantly affected by the presence of overpressure condition

  5. Hydration of highly charged ions.

    PubMed

    Hofer, Thomas S; Weiss, Alexander K H; Randolf, Bernhard R; Rode, Bernd M

    2011-08-01

    Based on a series of ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulations, the broad spectrum of structural and dynamical properties of hydrates of trivalent and tetravalent ions is presented, ranging from extreme inertness to immediate hydrolysis. Main group and transition metal ions representative for different parts of the periodic system are treated, as are 2 threefold negatively charged anions. The results show that simple predictions of the properties of the hydrates appear impossible and that an accurate quantum mechanical simulation in cooperation with sophisticated experimental investigations seems the only way to obtain conclusive results.

  6. The abundance and activation of mTORC1 regulators in skeletal muscle of neonatal pigs are modulated by insulin, amino acids, and age

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Previously we demonstrated that the insulin (INS) and amino acid (AA) -induced activation of the mammalian target of rapamycin complex 1 (mTORC1) is developmentally regulated in neonatal pigs. This study aimed to determine the effects of the post-prandial rise in INS and AA on the activation and abu...

  7. Abundance of amino acid transporters involved in mTORC1 activation in skeletal muscle of neonatal pigs is developmentally regulated

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Previously we demonstrated that the insulinand amino acid-induced activation of the mammalian target of rapamycin complex 1 (mTORC1) is developmentally regulated in neonatal pigs. Recent studies have indicated that members of the System A transporter (SNAT2), the System N transporter (SNAT3), the Sy...

  8. Compact apparatus for photogeneration of hydrated electrons

    NASA Technical Reports Server (NTRS)

    Hart, E.; Schmidt, K.

    1970-01-01

    Flash-photolysis instrument generates hydrated electrons and studies their reactions. It has a three-dimensional, multiple-reaction cell and the capacity to produce up to .1 micromole hydrated electron in a single 40 microsec light pulse.

  9. Natural Gas Hydrates Update 1998-2000

    EIA Publications

    2001-01-01

    Significant events have transpired on the natural gas hydrate research and development front since "Future Supply Potential of Natural Gas Hydrates" appeared in Natural Gas 1998 Issues and Trends and in the Potential Gas Committee's 1998 biennial report.

  10. 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.

  11. Methods to determine hydration states of minerals and cement hydrates

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  12. Molecular Dynamics Modeling of Hydrated Calcium-Silicate-Hydrate (CSH) Cement Molecular Structure

    DTIC Science & Technology

    2014-08-30

    properties of key hydrated cement constituent calcium-silicate-hydrate (CSH) at the molecular, nanometer scale level. Due to complexity, still unknown...public release; distribution is unlimited. Molecular Dynamics Modeling of Hydrated Calcium-Silicate- Hydrate (CSH) Cement Molecular Structure The views... Cement Molecular Structure Report Title Multi-scale modeling of complex material systems requires starting from fundamental building blocks to

  13. Hydration and Thermal Expansion in Anatase Nanoparticles

    SciTech Connect

    Zhu, He; Li, Qiang; Ren, Yang; Fan, Longlong; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2016-06-06

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  14. Hydration and Thermal Expansion in Anatase Nanoparticles.

    PubMed

    Zhu, He; Li, Qiang; Ren, Yang; Fan, Longlong; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2016-08-01

    A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

  15. The mechanism of CO2 hydration: a porous metal oxide nanocapsule catalyst can mimic the biological carbonic anhydrase role.

    PubMed

    Bandeira, Nuno A G; Garai, Somenath; Müller, Achim; Bo, Carles

    2015-11-04

    The mechanism for the hydration of CO2 within a Keplerate nanocapsule is presented. A network of hydrogen bonds across the water layers in the first metal coordination sphere facilitates the proton abstraction and nucleophilic addition of water. The highly acidic properties of the polyoxometalate cluster are crucial for explaining the catalysed hydration.

  16. 77 FR 40032 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee.... SUPPLEMENTARY INFORMATION: Purpose of the Committee: The purpose of the Methane Hydrate Advisory Committee is...

  17. 75 FR 9886 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-04

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  18. Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

    PubMed

    Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

    2011-10-01

    The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

  19. Relative stability of major types of beta-turns as a function of amino acid composition: a study based on Ab initio energetic and natural abundance data.

    PubMed

    Perczel, András; Jákli, Imre; McAllister, Michael A; Csizmadia, Imre G

    2003-06-06

    Folding properties of small globular proteins are determined by their amino acid sequence (primary structure). This holds both for local (secondary structure) and for global conformational features of linear polypeptides and proteins composed from natural amino acid derivatives. It thus provides the rational basis of structure prediction algorithms. The shortest secondary structure element, the beta-turn, most typically adopts either a type I or a type II form, depending on the amino acid composition. Herein we investigate the sequence-dependent folding stability of both major types of beta-turns using simple dipeptide models (-Xxx-Yyy-). Gas-phase ab initio properties of 16 carefully selected and suitably protected dipeptide models (for example Val-Ser, Ala-Gly, Ser-Ser) were studied. For each backbone fold most probable side-chain conformers were considered. Fully optimized 321G RHF molecular structures were employed in medium level [B3LYP/6-311++G(d,p)//RHF/3-21G] energy calculations to estimate relative populations of the different backbone conformers. Our results show that the preference for beta-turn forms as calculated by quantum mechanics and observed in Xray determined proteins correlates significantly.

  20. Observation of hydration of single, modified carbon aerosols

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  1. Is Br2 hydration hydrophobic?

    NASA Astrophysics Data System (ADS)

    Alcaraz-Torres, A.; Gamboa-Suárez, A.; Bernal-Uruchurtu, M. I.

    2017-02-01

    The spectroscopic properties of bromine in aqueous systems suggest it can behave as either hydrophilic or hydrophobic solute. In small water clusters, the halogen bond and the hydrogen-halogen interaction are responsible for its specific way of binding. In water hydrates, it is efficiently hosted by two different cages forming the crystal structure and it has been frequently assumed that there is little or no interaction between the guest and the host. Bromine in liquid solution poses a challenging question due to its non-negligible solubility and the large blue shift measured in its absorption spectra. Using a refined semi-empirical force field, PM3-PIF, we performed a Born-Oppenheimer molecular dynamics study of bromine in liquid water. Here we present a detailed study in which we retrieved the most representative hydration structures in terms of the most frequent positions around bromine and the most common water orientations. Albeit being an approximate description of the total hydration phenomenon, it captures the contribution of the leading molecular interactions in form of the recurrent structures. Our findings confirm that the spectroscopic signature is mainly caused by the closest neighbors. The dynamics of the whole first hydration shell strongly suggests that the external molecules in that structure effectively isolate the bulk from the presence of bromine. The solvation structure fluctuates from a hydrophilic to a hydrophobic-like environment along the studied trajectory.

  2. Attraction between hydrated hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.

    2014-08-01

    According to common knowledge, hydrophilic surfaces repel via hydration forces while hydrophobic surfaces attract, but mounting experimental evidence suggests that also hydrophilic surfaces can attract. Using all-atom molecular dynamics simulations at prescribed water chemical potential we study the crossover from hydration repulsion to hydrophobic attraction for planar polar surfaces of varying stiffness and hydrogen-bonding capability. Rescaling the partial charges of the polar surface groups, we cover the complete spectrum from very hydrophobic surfaces (characterized by contact angles θ ≃ 135°) to hydrophilic surfaces exhibiting complete wetting (θ = 0°). Indeed, for a finite range θadh < θ < 90°, we find a regime where hydrophilic surfaces attract at sub-nanometer separation and stably adhere without intervening water. The adhesive contact angle θadh depends on surface type and lies in the range 65° < θadh < 80°, in good agreement with experiments. Analysis of the total number of hydrogen bonds (HBs) formed by water and surface groups rationalizes this crossover between hydration repulsion and hydrophilic attraction in terms of a subtle balance: Highly polar surfaces repel because of strongly bound hydration water, less polar hydrophilic surfaces attract because water-water HBs are preferred over surface-water HBs. Such solvent reorganization forces presumably underlie also other important phenomena, such as selective ion adsorption to interfaces as well as ion pair formation.

  3. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  4. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  5. Terahertz sensing of corneal hydration.

    PubMed

    Singh, Rahul S; Tewari, Priyamvada; Bourges, Jean Louis; Hubschman, Jean Pierre; Bennett, David B; Taylor, Zachary D; Lee, H; Brown, Elliott R; Grundfest, Warren S; Culjat, Martin O

    2010-01-01

    An indicator of ocular health is the hydrodyanmics of the cornea. Many corneal disorders deteriorate sight as they upset the normal hydrodynamics of the cornea. The mechanisms include the loss of endothelial pump function of corneal dystophies, swelling and immune response of corneal graft rejection, and inflammation and edema, which accompany trauma, burn, and irritation events. Due to high sensitivity to changes of water content in materials, a reflective terahertz (300 GHz and 3 THz) imaging system could be an ideal tool to measure the hydration level of the cornea. This paper presents the application of THz technology to visualize the hydration content across ex vivo porcine corneas. The corneas, with a thickness variation from 470 - 940 µm, were successfully imaged using a reflective pulsed THz imaging system, with a maximum SNR of 50 dB. To our knowledge, no prior studies have reported on the use of THz in measuring hydration in corneal tissues or other ocular tissues. These preliminary findings indicate that THz can be used to accurately sense hydration levels in the cornea using a pulsed, reflective THz imaging system.

  6. Relationship between stearoyl-CoA desaturase 1 gene expression, relative protein abundance, and its fatty acid products in bovine tissues.

    PubMed

    Rezamand, Pedram; Watts, Jason S; Yavah, Katherine M; Mosley, Erin E; Ma, Liying; Corl, Benjamin A; McGuire, Mark A

    2014-08-01

    Stearoyl-CoA desaturase 1 (SCD1) greatly contributes to the unsaturated fatty acids present in milk and meat of cattle. The SCD1 enzyme introduces a double bond into certain saturated fatty acyl-CoAs producing monounsaturated fatty acids (MUFA). The SCD1 enzyme also has been shown to be active in the bovine mammary gland converting t11 18:1 (vaccenic acid) to c9 t11 conjugated linoleic acid (CLA). The objective of this study was to determine any association between the gene expression of SCD1 and occurrence of its products (c9 14:1, c9 16:1, c9 18:1, and c9 t11 18:2) in various bovine tissues. Tissue samples were obtained from lactating Holstein cows (n=28) at slaughter, frozen in liquid nitrogen and stored at -80 °C. Total RNA was extracted and converted to complementary DNA for quantitative real time polymerase chain reaction (PCR) analysis of the SCD1 gene. Extracted lipid was converted to fatty acid methyl esters and analysed by GC. Tissues varied in expression of SCD1 gene with mammary, cardiac, intestinal adipose, and skeletal muscle expressing greater copy number as compared with lung, large intestine, small intestine and liver (371, 369, 328, 286, 257, 145, 73, and 21 copies/ng RNA, respectively). Tissues with high mRNA expression of SCD1 contained greater SCD1 protein whereas detection of SCD1 protein in tissues with low SCD1 mRNA expression was very faint or absent. Across tissues, the desaturase indices for c9 18:1 (r=0.24) and sum of SCD products (r=0.20) were positively correlated with SCD1 gene expression (P<0.01 for both). Within each tissue, the relationship between SCD1 gene expression and the desaturase indices varied. No correlation was detected between SCD1 expression and desaturase indices in the liver, large and small intestines, lung, cardiac or skeletal muscles. Positive correlations, however, were detected between SCD1 expression and the desaturase indices in intestinal adipose tissue (P<0.02 for all) except 14:1, whereas only c9 18:1, c9

  7. Grand canonical ensemble Monte Carlo simulation of the dCpG/proflavine crystal hydrate.

    PubMed

    Resat, H; Mezei, M

    1996-09-01

    The grand canonical ensemble Monte Carlo molecular simulation method is used to investigate hydration patterns in the crystal hydrate structure of the dCpG/proflavine intercalated complex. The objective of this study is to show by example that the recently advocated grand canonical ensemble simulation is a computationally efficient method for determining the positions of the hydrating water molecules in protein and nucleic acid structures. A detailed molecular simulation convergence analysis and an analogous comparison of the theoretical results with experiments clearly show that the grand ensemble simulations can be far more advantageous than the comparable canonical ensemble simulations.

  8. Grand canonical ensemble Monte Carlo simulation of the dCpG/proflavine crystal hydrate.

    PubMed Central

    Resat, H; Mezei, M

    1996-01-01

    The grand canonical ensemble Monte Carlo molecular simulation method is used to investigate hydration patterns in the crystal hydrate structure of the dCpG/proflavine intercalated complex. The objective of this study is to show by example that the recently advocated grand canonical ensemble simulation is a computationally efficient method for determining the positions of the hydrating water molecules in protein and nucleic acid structures. A detailed molecular simulation convergence analysis and an analogous comparison of the theoretical results with experiments clearly show that the grand ensemble simulations can be far more advantageous than the comparable canonical ensemble simulations. Images FIGURE 5 FIGURE 7 PMID:8873992

  9. 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

  10. Clinical and instrumental evaluation of a food supplement in improving skin hydration.

    PubMed

    Primavera, G; Berardesca, E

    2005-08-01

    Topically applied cosmetic products can be helpful in improving skin hydration. The study shows how oral supplementation could be helpful in improving and preventing the skin dehydration. A total of 32 healthy female volunteers entered the study. Of which, 16 were treated with a food supplement based on vegetable ceramides, amino acids, fish cartilage, antioxidants and essential fatty acids for 40 days and 16 with placebo. The results of the clinical and instrumental evaluations carried out in this study, have highlighted how the active treatment is effective in improving skin hydration and in reducing the cutaneous smoothness and roughness and the depth of furrows, in comparison to the placebo. In fact, concerning several important parameters, as stratum corneum hydration and skin roughness, the improvement measured exceeded 25%. We therefore suggest that a combination of treatments (oral and topical) can be more effective in improving skin hydration.

  11. Mesoscale texture of cement hydrates

    PubMed Central

    Ioannidou, Katerina; Krakowiak, Konrad J.; Bauchy, Mathieu; Hoover, Christian G.; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J.-M.; Del Gado, Emanuela

    2016-01-01

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  12. Physical activity, hydration and health.

    PubMed

    Marcos, Ascensión; Manonelles, Pedro; Palacios, Nieves; Wärnberg, Julia; Casajús, José A; Pérez, Margarita; Aznar, Susana; Benito, Pedro J; Martínez-Gomez, David; Ortega, Francisco B; Ortega, Eduardo; Urrialde, Rafael

    2014-06-01

    Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory disea ses and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences.

  13. Seismic imaging of a fractured gas hydrate system in the Krishna-Godavari Basin offshore India

    USGS Publications Warehouse

    Riedel, M.; Collett, T.S.; Kumar, P.; Sathe, A.V.; Cook, A.

    2010-01-01

    Gas hydrate was discovered in the Krishna-Godavari (KG) Basin during the India National Gas Hydrate Program (NGHP) Expedition 1 at Site NGHP-01-10 within a fractured clay-dominated sedimentary system. Logging-while-drilling (LWD), coring, and wire-line logging confirmed gas hydrate dominantly in fractures at four borehole sites spanning a 500m transect. Three-dimensional (3D) seismic data were subsequently used to image the fractured system and explain the occurrence of gas hydrate associated with the fractures. A system of two fault-sets was identified, part of a typical passive margin tectonic setting. The LWD-derived fracture network at Hole NGHP-01-10A is to some extent seen in the seismic data and was mapped using seismic coherency attributes. The fractured system around Site NGHP-01-10 extends over a triangular-shaped area of ~2.5 km2 defined using seismic attributes of the seafloor reflection, as well as " seismic sweetness" at the base of the gas hydrate occurrence zone. The triangular shaped area is also showing a polygonal (nearly hexagonal) fault pattern, distinct from other more rectangular fault patterns observed in the study area. The occurrence of gas hydrate at Site NGHP-01-10 is the result of a specific combination of tectonic fault orientations and the abundance of free gas migration from a deeper gas source. The triangular-shaped area of enriched gas hydrate occurrence is bound by two faults acting as migration conduits. Additionally, the fault-associated sediment deformation provides a possible migration pathway for the free gas from the deeper gas source into the gas hydrate stability zone. It is proposed that there are additional locations in the KG Basin with possible gas hydrate accumulation of similar tectonic conditions, and one such location was identified from the 3D seismic data ~6 km NW of Site NGHP-01-10. ?? 2010.

  14. Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

    PubMed Central

    Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

    2016-01-01

    Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

  15. Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

    NASA Astrophysics Data System (ADS)

    Zhou, Qin; Liu, Zhao-Dong; Liu, Yuan; Jiang, Jun; Xu, Ren-Kou

    2016-11-01

    Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants.

  16. A laboratory effort to quantitatively address clay abundance on Mars

    NASA Astrophysics Data System (ADS)

    Roush, T. L.; Bishop, J. L.; Brown, A. J.; Hunkins, L.; Blake, D. F.; Bristow, T. F.

    2011-12-01

    Data obtained at visible and near-infrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al-OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. In order to constrain the abundances of these phyllosilicates spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/hydroxylated silicates with each other and with two analogs for other martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al- rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 μm. As an initial phase of our effort we used scanning electron microscopy imaging and x-ray diffraction to characterize the grain size distribution, and structural nature, respectively, of the pure end-member materials. Visible and near-infrared reflectance spectra of the 63-90 μm grain size of the end-member samples are shown in Figure 1. We discuss the results of our initial measurements of these samples.

  17. Gas hydrate reservoir characteristics and economics

    SciTech Connect

    Collett, T.S.; Bird, K.J.; Burruss, R.C.; Lee, Myung W.

    1992-06-01

    The primary objective of the DOE-funded USGS Gas Hydrate Program is to assess the production characteristics and economic potential of gas hydrates in northern Alaska. The objectives of this project for FY-1992 will include the following: (1) Utilize industry seismic data to assess the distribution of gas hydrates within the nearshore Alaskan continental shelf between Harrison Bay and Prudhoe Bay; (2) Further characterize and quantify the well-log characteristics of gas hydrates; and (3) Establish gas monitoring stations over the Eileen fault zone in northern Alaska, which will be used to measure gas flux from destabilized hydrates.

  18. Gas hydrate reservoir characteristics and economics

    SciTech Connect

    Collett, T.S.; Bird, K.J.; Burruss, R.C.; Lee, Myung W.

    1992-01-01

    The primary objective of the DOE-funded USGS Gas Hydrate Program is to assess the production characteristics and economic potential of gas hydrates in northern Alaska. The objectives of this project for FY-1992 will include the following: (1) Utilize industry seismic data to assess the distribution of gas hydrates within the nearshore Alaskan continental shelf between Harrison Bay and Prudhoe Bay; (2) Further characterize and quantify the well-log characteristics of gas hydrates; and (3) Establish gas monitoring stations over the Eileen fault zone in northern Alaska, which will be used to measure gas flux from destabilized hydrates.

  19. Model of Methane Hydrate Formation in Mid-ocean Ridges

    NASA Astrophysics Data System (ADS)

    Dmitrievsky, A. N.; Balanyuk, I. E.; Sorokhtin, O. G.; Matveenkov, V. V.; Dongaryan, L. Sh.

    2003-04-01

    MODEL OF METHANE HYDRATE FORMATION IN MID-OCEAN RIDGES A.N. Dmitrievsky, I.E. Balanyuk, O.G.Sorokhtin, V.V. Matveenkov, and L.Sh. Dongaryan P.P.Shirshov Institute of Oceanology Russian Academy of Sciences Moscow, Russia, balanyuk@sio.rssi.ru One among the most perspective direction in studying the ocean floor is the research of hydrothermal fields within the most active zones — rift valleys, where the processes of spreading of the ocean floor, uplift of the deep matter to the surface of the ocean floor, and creation of the new oceanic crust occur. Volcanic activity in these zones is accompanied with the formation of the hydrothermal system executing separation, transfer, and precipitation of a series of chemical elements. It is known that ore deposits with high concentration of iron, manganese, copper, nickel, cobalt are formed as a result of hydrothermal activity. It is much less known that hydrothermal activity in these zones has important but not so evident result — the formation of hydrocarbons in the form of methane hydrates. We propose the hypothesis of formation of methane hydrate deposits over the shallow slopes of the mid-oceanic ridges as an outcome of the action of two factors: the thermal convection of water in fractured-porous rocks of the crust and the reaction of serpentinization of the crust. The intensive exhalation of hydrocarbons takes place in the process of serpentinization. The conditions of water convection in the porous media are favorable for the formation and accumulation of methane hydrates in the near-surface layers of the oceanic crust. The carbonic-acid gas dissolved in the seawater is involved into the process of methane hydrate formation. It was established that the most favorable conditions for this mechanism are over the slopes of the Mid-Atlantic Ridge. All types of water areas where gas hydrates occur can be conditionally subdivided into following geodynamic zones: the abyssal basins of the inner and marginal seas, the

  20. Relative Abundance of Nitrotoga spp. in a Biofilter of a Cold-Freshwater Aquaculture Plant Appears To Be Stimulated by Slightly Acidic pH.

    PubMed

    Hüpeden, Jennifer; Wegen, Simone; Off, Sandra; Lücker, Sebastian; Bedarf, Yvonne; Daims, Holger; Kühn, Carsten; Spieck, Eva

    2016-01-08

    The functioning of recirculation aquaculture systems (RAS) is essential to maintain water quality for fish health, and one crucial process here is nitrification. The investigated RAS was connected to a rainbow trout production system and operated at an average temperature of 13°C and pH 6.8. Community analyses of the nitrifying biofilm revealed a coexistence of Nitrospira and Nitrotoga, and it is hypothesized that a slightly acidic pH in combination with lower temperatures favors the growth of the latter. Modification of the standard cultivation approach toward lower pH values of 5.7 to 6.0 resulted in the successful enrichment (99% purity) of Nitrotoga sp. strain HW29, which had a 16S rRNA sequence similarity of 99.0% to Nitrotoga arctica. Reference cultures of Nitrospira defluvii and the novel Nitrotoga sp. HW29 were used to confirm differentiation of these nitrite oxidizers in distinct ecological niches. Nitrotoga sp. HW29 revealed pH and temperature optima of 6.8 and 22°C, respectively, whereas Nitrospira defluvii displayed the highest nitrite oxidation rate at pH 7.3 and 32°C. We report here the occurrence of Nitrotoga as one of the main nitrite-oxidizing bacteria in freshwater aquaculture systems and indicate that a slightly acidic pH, in addition to temperatures below 20°C, can be applied as a selective isolation criterion for this microorganism.

  1. Relative Abundance of Nitrotoga spp. in a Biofilter of a Cold-Freshwater Aquaculture Plant Appears To Be Stimulated by Slightly Acidic pH

    PubMed Central

    Hüpeden, Jennifer; Wegen, Simone; Off, Sandra; Lücker, Sebastian; Bedarf, Yvonne; Daims, Holger; Kühn, Carsten

    2016-01-01

    The functioning of recirculation aquaculture systems (RAS) is essential to maintain water quality for fish health, and one crucial process here is nitrification. The investigated RAS was connected to a rainbow trout production system and operated at an average temperature of 13°C and pH 6.8. Community analyses of the nitrifying biofilm revealed a coexistence of Nitrospira and Nitrotoga, and it is hypothesized that a slightly acidic pH in combination with lower temperatures favors the growth of the latter. Modification of the standard cultivation approach toward lower pH values of 5.7 to 6.0 resulted in the successful enrichment (99% purity) of Nitrotoga sp. strain HW29, which had a 16S rRNA sequence similarity of 99.0% to Nitrotoga arctica. Reference cultures of Nitrospira defluvii and the novel Nitrotoga sp. HW29 were used to confirm differentiation of these nitrite oxidizers in distinct ecological niches. Nitrotoga sp. HW29 revealed pH and temperature optima of 6.8 and 22°C, respectively, whereas Nitrospira defluvii displayed the highest nitrite oxidation rate at pH 7.3 and 32°C. We report here the occurrence of Nitrotoga as one of the main nitrite-oxidizing bacteria in freshwater aquaculture systems and indicate that a slightly acidic pH, in addition to temperatures below 20°C, can be applied as a selective isolation criterion for this microorganism. PMID:26746710

  2. Aldehyde oxidase 1 is highly abundant in hepatic steatosis and is downregulated by adiponectin and fenofibric acid in hepatocytes in vitro

    SciTech Connect

    Neumeier, Markus; Weigert, Johanna; Schaeffler, Andreas; Weiss, Thomas S.; Schmidl, Christian; Buettner, Roland; Bollheimer, Cornelius; Aslanidis, Charalampos; Schoelmerich, Juergen; Buechler, Christa . E-mail: christa.buechler@klinik.uni-regensburg.de

    2006-11-24

    Adiponectin protects the liver from steatosis caused by obesity or alcohol and therefore the influence of adiponectin on human hepatocytes was analyzed. GeneChip experiments indicated that recombinant adiponectin downregulates aldehyde oxidase 1 (AOX1) expression and this was confirmed by real-time RT-PCR and immunoblot. AOX1 is a xenobiotic metabolizing protein and produces reactive oxygen species (ROS), that promote cell damage and fibrogenesis. Adiponectin and fenofibric acid activate peroxisome proliferator-activated receptor-{alpha} (PPAR-{alpha}) and both suppress AOX1 protein and this is blocked by the PPAR-{alpha} antagonist RU486. Obesity is associated with low adiponectin, reduced hepatic PPAR-{alpha} activity and fatty liver, and AOX1 was found induced in the liver of rats on a high-fat diet when compared to controls. Free fatty acids and leptin, that are elevated in obesity, failed to upregulate AOX1 in vitro. The current data indicate that adiponectin reduces AOX1 by activating PPAR-{alpha} whereas fatty liver disease is associated with elevated hepatic AOX1. High AOX1 may be associated with higher ROS well described to induce fibrogenesis in liver tissue but may also influence drug metabolism and activity.

  3. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, T.S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The "standard" and "quick look" Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in all of the gas hydrate accumulations assessed in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  4. Handbook of gas hydrate properties and occurrence

    SciTech Connect

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  5. Characterization of relative abundance of lactic acid bacteria species in French organic sourdough by cultural, qPCR and MiSeq high-throughput sequencing methods.

    PubMed

    Michel, Elisa; Monfort, Clarisse; Deffrasnes, Marion; Guezenec, Stéphane; Lhomme, Emilie; Barret, Matthieu; Sicard, Delphine; Dousset, Xavier; Onno, Bernard

    2016-12-19

    In order to contribute to the description of sourdough LAB composition, MiSeq sequencing and qPCR methods were performed in association with cultural methods. A panel of 16 French organic bakers and farmer-bakers were selected for this work. The lactic acid bacteria (LAB) diversity of their organic sourdoughs was investigated quantitatively and qualitatively combining (i) Lactobacillus sanfranciscensis-specific qPCR, (ii) global sequencing with MiSeq Illumina technology and (iii) molecular isolates identification. In addition, LAB and yeast enumeration, pH, Total Titratable Acidity, organic acids and bread specific volume were analyzed. Microbial and physico-chemical data were statistically treated by Principal Component Analysis (PCA) and Hierarchical Ascendant Classification (HAC). Total yeast counts were 6 log10 to 7.6 log10CFU/g while LAB counts varied from 7.2 log10 to 9.6 log10CFU/g. Values obtained by L. sanfranciscensis-specific qPCR were estimated between 7.2 and 10.3 log10CFU/g, except for one sample at 4.4 log10CFU/g. HAC and PCA clustered the sixteen sourdoughs into three classes described by their variables but without links to bakers' practices. L. sanfranciscensis was the dominant species in 13 of the 16 sourdoughs analyzed by Next Generation Sequencing (NGS), by the culture dependent method this species was dominant only in only 10 samples. Based on isolates identification, LAB diversity was higher for 7 sourdoughs with the recovery of L. curvatus, L. brevis, L. heilongjiangensis, L. xiangfangensis, L. koreensis, L. pontis, Weissella sp. and Pediococcus pentosaceus, as the most representative species. L. koreensis, L. heilongjiangensis and L. xiangfangensis were identified in traditional Asian food and here for the first time as dominant in organic sourdough. This study highlighted that L. sanfranciscensis was not the major species in 6/16 sourdough samples and that a relatively high LAB diversity can be observed in French organic sourdough.

  6. 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

  7. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    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. Copyright 2009 by the American Geophysical Union.

  8. Thermal conductivity of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

    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.

  9. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunelé, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  10. 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.

  11. Controlled-source electromagnetic and seismic delineation of subseafloor fluid flow structures in a gas hydrate province, offshore Norway

    NASA Astrophysics Data System (ADS)

    Attias, Eric; Weitemeyer, Karen; Minshull, Tim A.; Best, Angus I.; Sinha, Martin; Jegen-Kulcsar, Marion; Hölz, Sebastian; Berndt, Christian

    2016-08-01

    Deep sea pockmarks underlain by chimney-like or pipe structures that contain methane hydrate are abundant along the Norwegian continental margin. In such hydrate provinces the interaction between hydrate formation and fluid flow has significance for benthic ecosystems and possibly climate change. The Nyegga region, situated on the western Norwegian continental slope, is characterized by an extensive pockmark field known to accommodate substantial methane gas hydrate deposits. The aim of this study is to detect and delineate both the gas hydrate and free gas reservoirs at one of Nyegga's pockmarks. In 2012, a marine controlled-source electromagnetic (CSEM) survey was performed at a pockmark in this region, where high-resolution 3-D seismic data were previously collected in 2006. 2-D CSEM inversions were computed using the data acquired by ocean bottom electrical field receivers. Our results, derived from unconstrained and seismically constrained CSEM inversions, suggest the presence of two distinctive resistivity anomalies beneath the pockmark: a shallow vertical anomaly at the underlying pipe structure, likely due to gas hydrate accumulation, and a laterally extensive anomaly attributed to a free gas zone below the base of the gas hydrate stability zone. This work contributes to a robust characterization of gas hydrate deposits within subseafloor fluid flow pipe structures.

  12. Gas hydrate cool storage system

    DOEpatents

    Ternes, Mark P.; Kedl, Robert J.

    1985-01-01

    This invention is a process for formation of a gas hydrate to be used as a cool storage medium using a refrigerant in water. Mixing of the immiscible refrigerant and water is effected by addition of a surfactant and agitation. The difficult problem of subcooling during the process is overcome by using the surfactant and agitation and performance of the process significantly improves and approaches ideal.

  13. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, Timothy S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The `standard' and `quick look' Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  14. 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.

  15. 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.

  16. Gas hydrate resources of northern Alaska

    USGS Publications Warehouse

    Collett, T.S.

    1997-01-01

    Large amounts of natural gas, composed mainly of methane, can occur in arctic sedimentary basins in the form of gas hydrates under appropriate temperature and pressure conditions. Gas hydrates are solids, composed of rigid cages of water molecules that trap molecules of gas. These substances are regarded as a potential unconventional source of natural gas because of their enormous gas-storage capacity. Most published gas hydrate resource estimates are highly simplified and based on limited geological data. The gas hydrate resource assessment for northern Alaska presented in this paper is based on a "play analysis" scheme, in which geological factors controlling the accumulation and preservation of gas hydrates are individually evaluated and risked for each hydrate play. This resource assessment identified two gas hydrate plays; the in-place gas resources within the gas hydrates of northern Alaska are estimated to range from 6.7 to 66.8 trillion cubic metres of gas (236 to 2,357 trillion cubic feet of gas), at the 0.50 and 0.05 probability levels respectively. The mean in-place hydrate resource estimate for northern Alaska is calculated to be 16.7 trillion cubic metres of gas (590 trillion cubic feet of gas). If this assessment is valid, the amount of natural gas stored as gas hydrates in northern Alaska could be almost seven times larger then the estimated total remaining recoverable conventional natural gas resources in the entire United States.

  17. Comprehensive Study of Hydrated IDPs: X-Ray Diffraction, IR Spectroscopy and Electron Microscopic Analysis

    NASA Technical Reports Server (NTRS)

    Nakamura, K.; Keller, L. P.; Nakamura, T.; Noguchi, T.; Nozaki, W.; Tomeoka, K.

    2003-01-01

    Chondritic hydrated interplanetary dust particles (IDPs) comprise up to 50% of all IDPs collected in the stratosphere(1). Although much is known about the mineralogy, chemistry and carbon abundance of hydrated IDPs (2-4) controversies still exist regarding their formation, history, and relationship to other primitive solar system materials. Hydrated IDPs are generally believed to be derived from asteroidal sources that have undergone some degree of aqueous alteration. However, the high C contents of hydrated IDPs (by 2 to 6X CI levels (3,4) indicate that they are probably not derived from the same parent bodies sampled by the known chondritic meteorites. We report the comprehensive study of individual hydrated IDPs. The strong depletion in Ca (I) has been used as a diagnostic feature of hydrated IDPs. The particles are embedded in elemental sulfur or low viscosity epoxy and ultramicrotomed thin sections are observed using a transmission electron microscope (TEM) equipped with an energy-dispersive X-ray detector (EDX) followed by other measurements including: 1) FTIR microspectroscopy to understand the significant constraints on the organic functionality and the nature of the C-bearing phases and 2) powder X-ray difiaction using a synchrotron X-ray source to understand the bulk mineralogy of the particles.

  18. Gas Hydrates on Mars: In-situ Resources for Human Habitation?

    NASA Astrophysics Data System (ADS)

    Max, M. D.; Pellenbarg, R. E.

    2002-05-01

    The apparent presence of abundant water on Mars, combined with the recent discovery of deep lithoautotrophic bacteria on Earth raises the possibility that a similar development of early life was established on Mars early in its history. CH4 would be a likely by-product of that deep biosphere metabolism. Where methane may have been produced over a long period of time, considerable volumes of it can be expected to have migrated toward the planet?s surface. Although confirmation of the presence of gas hydrate in the Martian subsurface has yet to be made, its occurrence is consistent with the temperature and pressure regimes expected at depth. The possible existence of substantial deposits of gas hydrates in the Martian subsurface, comparable to those now known on Earth, may be of critical importance to exploration and colonization of Mars because hydrate concentrates resources. Both CO2 and CH4 hydrates compress about 164 m3 of gas (at Earth STP) along with about 0.87m3 of pure water into each m3 of gas hydrate. The successful retrieval of concentrated CO2, CH4 and water from relatively shallow depths within the Martian cryosphere may provide the key of human occupation of Mars. In addition to the basic elements of fuel and water necessary to support the eventual expansion of human life across the surface of the planet virtually all shelter and hard goods can be fabricated from plastics produced from chemical components of these hydrate deposits.

  19. Gas hydrates: Technology status report

    SciTech Connect

    Not Available

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  20. Gemini near-infrared observations of Europa's Hydrated Surface Materials

    NASA Astrophysics Data System (ADS)

    Tsang, C.; Spencer, J. R.; Grundy, W. M.; Dalton, J. B.

    2012-12-01

    Europa is a highly dynamic icy moon of Jupiter. It is thought the moon harbors a subsurface ocean, with the potential to sustain life, with Europa being a key target of ESA's forthcoming Jupiter Icy Moons Orbiter (JUICE) mission. However, much is not known concerning the chemistry of the subsurface ocean. The surface is dominated by water ice, with a hydrated non-ice material component providing the distinctive albedo contrasts seen at visible and near-infrared wavelengths. These non-ice materials are concentrated at disrupted surface regions, providing a diagnostic probe for the chemistry and characteristics of the liquid ocean beneath. Leading but potentially competing theories on the composition of these hydrated non-ice materials suggest either sulfuric acid-water mixtures (Carlson et al., 1999) or hydrated magnesium/sodium salts (McCord et al., 1999). Recent reanalysis of Galileo-NIMS observations suggest a mixture of both - hydrated salts are present at all longitudes but the sulfuric acid hydrates are localized on the trailing side. We present preliminary analysis of new ground-based Gemini disk-resolved spectroscopy of Europa using the Near-Infrared Integrated Field Spectrometer (NIFS), taken in late 2011, at H (1.49 - 1.80 μm) and K bands (1.99 - 2.40 μm) with spectral resolving powers of ~ 5300. At these NIR wavelengths, with spectral resolution much better than Galileo-NIMS, the spectral absorption and continuum characteristics of these ice and non-ice materials can be separated out. In addition, the spatial resolution potentially allows identification of localized materials whose signature would be diluted in disk-integrated spectra. These observations of the trailing hemisphere use Altair adaptive optics to achieve spatial resolutions of 0.1" (~310 km per pixel) or better, potentially leading to better identification of the non-ice materials and their spatial distributions. References Carlson, R.W., R.E. Johnson, and M.S. Anderson 1999. Sulfuric acid

  1. Geochemical signature of methane-related archaea associated with gas hydrate occurrences on the Sakhalin slope

    NASA Astrophysics Data System (ADS)

    DongHun, Lee; youngkeun, Jin; JongKu, Gal; Hirotsugu, Minami; Akihiro, Hachikubo; KyungHoon, Shin

    2015-04-01

    Only 3% of the advective methane in gas hydrates bearing sediments is released into the atmosphere as the result of the anaerobic oxidation of methane (AOM), which is a specific microbial process (methanotroph) occurring in marine sediments. We investigate the molecular and isotopic signature of gas and archaeal lipid biomarkers at gas hydrate bearing core sediments during the project of Sakhalin Slope Gas Hydrate 2014 (SSGH 2014). Our objective of this expedition is to identify relative abundance of methane-related archaea and pathway for understanding of the geochemical methane cycles between two core sediments (gas hydrate occurrence site and background site). At both sites, the molecular and isotopic data (δ13CCH4 and δ13CCO2) of gases indicate that methane is originated from microbial production via carbon dioxide reduction. The isotopic fractionation factor (ɛC = δ13CCO2 - δ13CCH4) near Sulfate Methane Transition Zone (SMTZ) in gas hydrate bearing sediment is significantly lower (ca. 20), considering more faster rates of AOM by the methanotrophic activity. Additionally, there is no correlation of bulk sediments (Total Orgaic Carbon (TOC), Total Sulfur (TS)) in gas hydrate occurrence site demonstrating that reduced sulfur is incorporated into the TS during the microbial AOM processes. The depleted-δ34STS values as low as -32.95‰ suggest that sulfate reduction coupled to AOM was more active and affect the sulfur isotope values of TS. The relative higher abundance of archaeal lipid biomarkers (archaeol, sn-2-hydroxyarchaeol, GDGT-1 and -2) and their depleted-δ13C values (sn-2-hydroxyarchaeol : -100‰) can be considered as the evidences of AOM by methanotroph related with euryarchaeota, consuming the methane migrated from the deeper reservoirs such as gas hydrate. Consequently, the geochemical signature of molecular and isotope values in analyzed gases and archaeal lipid biomarkers in the Sakhalin Slope can be used as a possible indicators which can

  2. Abundances in Przybylski's star

    NASA Astrophysics Data System (ADS)

    Cowley, C. R.; Ryabchikova, T.; Kupka, F.; Bord, D. J.; Mathys, G.; Bidelman, W. P.

    2000-09-01

    We have derived abundances for 54 elements in the extreme roAp star HD101065. ESO spectra with a resolution of about 80000, and S/N of 200 or more were employed. The adopted model has Teff=6600K, and log(g)=4.2. Because of the increased line opacity and consequent low gas pressure, convection plays no significant role in the temperature structure. Lighter elemental abundances through the iron group scatter about standard abundance distribution (SAD) (solar) values. Iron and nickel are about one order of magnitude deficient while cobalt is enhanced by 1.5dex. Heavier elements, including the lanthanides, generally follow the solar pattern but enhanced by 3 to 4dex. Odd-Z elements are generally less abundant than their even-Z neighbours. With a few exceptions (e.g. Yb), the abundance pattern among the heavy elements is remarkably coherent, and resembles a displaced solar distribution.

  3. Binning of shallowly sampled metagenomic sequence fragments reveals that low abundance bacteria play important roles in sulfur cycling and degradation of complex organic polymers in an acid mine drainage community

    NASA Astrophysics Data System (ADS)

    Dick, G. J.; Andersson, A.; Banfield, J. F.

    2007-12-01

    Our understanding of environmental microbiology has been greatly enhanced by community genome sequencing of DNA recovered directly the environment. Community genomics provides insights into the diversity, community structure, metabolic function, and evolution of natural populations of uncultivated microbes, thereby revealing dynamics of how microorganisms interact with each other and their environment. Recent studies have demonstrated the potential for reconstructing near-complete genomes from natural environments while highlighting the challenges of analyzing community genomic sequence, especially from diverse environments. A major challenge of shotgun community genome sequencing is identification of DNA fragments from minor community members for which only low coverage of genomic sequence is present. We analyzed community genome sequence retrieved from biofilms in an acid mine drainage (AMD) system in the Richmond Mine at Iron Mountain, CA, with an emphasis on identification and assembly of DNA fragments from low-abundance community members. The Richmond mine hosts an extensive, relatively low diversity subterranean chemolithoautotrophic community that is sustained entirely by oxidative dissolution of pyrite. The activity of these microorganisms greatly accelerates the generation of AMD. Previous and ongoing work in our laboratory has focused on reconstrucing genomes of dominant community members, including several bacteria and archaea. We binned contigs from several samples (including one new sample and two that had been previously analyzed) by tetranucleotide frequency with clustering by Self-Organizing Maps (SOM). The binning, evaluated by comparison with information from the manually curated assembly of the dominant organisms, was found to be very effective: fragments were correctly assigned with 95% accuracy. Improperly assigned fragments often contained sequences that are either evolutionarily constrained (e.g. 16S rRNA genes) or mobile elements that are

  4. Ruthenium hydroxide supported on magnetic nanoparticles: a benign aqueous protocol for hydration of nitriles

    EPA Science Inventory

    Amides are an important class of compounds in the chemical and pharmaceutical industry1,2. Conventionally, amides have been synthesized by the hydration of nitriles, catalyzed by strong acids3 and bases4. Many by-products such as carboxylic acids are produced due to hydrolysis of...

  5. Short-chain fatty acid-supplemented total parenteral nutrition alters intestinal structure, glucose transporter 2 (GLUT2) mRNA and protein, and proglucagon mRNA abundance in normal rats.

    PubMed

    Tappenden, K A; Drozdowski, L A; Thomson, A B; McBurney, M I

    1998-07-01

    Intestinal adaptation is a complex physiologic process that is not completely understood. Intravenous short-chain fatty acids (SCFAs) enhance intestinal adaptation after 80% enterectomy in rats. The purpose of this study was to examine rapid responses to SCFA-supplemented total parenteral nutrition (TPN) in the normal small intestine. After jugular catheterization, 31 Sprague-Dawley rats (weighing 258 +/- 3 g) were randomly assigned to receive standard TPN or an isoenergetic, isonitrogenous TPN solution supplemented with SCFAs (TPN+SCFA). Intestinal samples were obtained after 24 or 72 h of nutrient infusion. TPN+SCFA for 24 h increased (P < 0.05) the ileal RNA concentration (microg RNA/mg ileum) whereas TPN+SCFA for 72 h increased (P < 0.05) the ileal DNA concentration (microg DNA/mg ileum) and decreased (P < 0.05) the ileal protein concentration (microg protein/mg ileum). Ileal proglucagon mRNA abundance was elevated (P < 0.05) after 24 h of TPN+SCFA infusion and returned to levels seen with control TPN by 72 h. Glucose transporter 2 (GLUT2) mRNA was significantly higher (P < 0.05) in the TPN+SCFA groups at both time points when compared with control TPN groups. Ileal GLUT2 protein abundance in the 72-h TPN+SCFA group was significantly higher (P < 0.05) than that of all other groups. Sodium-glucose cotransporter (SGLT-1) mRNA and protein abundance and uptake of D-fructose and D-glucose did not differ between groups. Jejunal uptake of L-glucose and lauric acid was significantly higher (P < 0.05) after 72 h of TPN+SCFA than after 24 h, whereas the 24- and 72-h TPN groups did not differ. In summary, SCFAs led to rapid changes in ileal proglucagon and glucose transporter expression in rats receiving TPN and provide insights into therapeutic management of individuals with short bowel syndrome or intestinal malabsorption syndromes.

  6. Characterization of non-stoichiometric hydration and the dehydration behavior of sitafloxacin hydrate.

    PubMed

    Suzuki, Tetsuya; Araki, Tetsuya; Kitaoka, Hiroaki; Terada, Katsuhide

    2012-01-01

    Sitafloxacin (STFX) hydrate is a non-stoichiometric hydrate. The hydration state of STFX hydrate varies non-stoichiometrically depending on the relative humidity and temperature, though X-ray powder diffraction (XRPD) of STFX hydrate was not affected by storing at low and high relative humidities. The detailed properties of crystalline water of STFX hydrate were estimated in terms of hygroscopicity, thermal analysis combined with X-ray powder diffractometry, crystallography and density functional theory (DFT) calculation. STFX hydrate changed the water contents continuously and reversibly from an equivalent amount of dihydrate through that of sesquihydrate depending on the relative humidity at 25°C. Thermal analysis and X-ray powder diffraction (XRPD) simultaneous measurement also revealed that STFX hydrate dehydrated into a hydrated state equivalent to monohydrate by heating up to 100°C, whereas XRPD patterns were slightly affected. This indicated that the crystal structure of STFX hydrate was retained at the dehydration level of monohydrate. Single-crystal X-ray structural analysis showed that two STFX molecules and four water molecule sites were contained in an asymmetric unit. STFX molecules formed a channel structure where water molecules were included. At the partially dehydrated state, at least two of four water molecules were considered to be disordered in occupancy and/or coordinates. Insight into the crystal structure of STFX hydrate stored at low and high relative humidities and geometry of the hydrogen bond were helpful to estimate the origin of non-stoichiometric hydration of STFX hydrate.

  7. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

    Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  8. Quantitative analyses of carbon in anhydrous and hydrated interplanetary dust particles

    NASA Technical Reports Server (NTRS)

    Thomas, Kathie L.; Keller, Lindsay P.; Blanford, George E.; Mckay, David S.

    1994-01-01

    Carbon is an important and significant component of most anhydrous and hydrated IDP's. We have analyzed approx. 40 anhydrous and hydrated chondritic IDP's for major and minor elements, including C and O. Quantitative analyses of light elements in small particles are difficult and require careful procedures in order to obtain reliable results. In our work, we have completed extensive analytical checks to verify the accuracy and precision of C abundances in IDP's. In our present work, additional methods are used to verify C abundances in IDP's including analysis of IDP thin sections embedded in S, and direct observation of carbonaceous material in thin sections. Our work shows conclusively that C is strongly enriched in IDP's relative to CI abundances.

  9. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

  10. Development of Alaskan gas hydrate resources

    SciTech Connect

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  11. Structural characteristics of hydration sites in lysozyme.

    PubMed

    Soda, Kunitsugu; Shimbo, Yudai; Seki, Yasutaka; Taiji, Makoto

    2011-06-01

    A new method is presented for determining the hydration site of proteins, where the effect of structural fluctuations in both protein and hydration water is explicitly considered by using molecular dynamics simulation (MDS). The whole hydration sites (HS) of lysozyme are composed of 195 single HSs and 38 clustered ones (CHS), and divided into 231 external HSs (EHS) and 2 internal ones (IHS). The largest CHSs, 'Hg' and 'Lβ', are the IHSs having 2.54 and 1.35 mean internal hydration waters respectively. The largest EHS, 'Clft', is located in the cleft region. The real hydration structure of a CHS is an ensemble of multiple structures. The transition between two structures occurs through recombinations of some H-bonds. The number of the experimental X-ray crystal waters is nearly the same as that of the estimated MDS hydration waters for 70% of the HSs, but significantly different for the rest of HSs.

  12. Fundamentals and applications of gas hydrates.

    PubMed

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties.

  13. Synbiotic Lactobacillus acidophilus NCFM and cellobiose does not affect human gut bacterial diversity but increases abundance of lactobacilli, bifidobacteria and branched-chain fatty acids: a randomized, double-blinded cross-over trial.

    PubMed

    van Zanten, Gabriella C; Krych, Lukasz; Röytiö, Henna; Forssten, Sofia; Lahtinen, Sampo J; Abu Al-Soud, Waleed; Sørensen, Søren; Svensson, Birte; Jespersen, Lene; Jakobsen, Mogens

    2014-10-01

    Probiotics, prebiotics, and combinations thereof, that is synbiotics, have been reported to modulate gut microbiota of humans. In this study, effects of a novel synbiotic on the composition and metabolic activity of human gut microbiota were investigated. Healthy volunteers (n = 18) were enrolled in a double-blinded, randomized, and placebo-controlled cross-over study and received synbiotic [Lactobacillus acidophilus NCFM (10(9) CFU) and cellobiose (5 g)] or placebo daily for 3 weeks. Fecal samples were collected and lactobacilli numbers were quantified by qPCR. Furthermore, 454 tag-encoded amplicon pyrosequencing was used to monitor the effect of synbiotic on the composition of the microbiota. The synbiotic increased levels of Lactobacillus spp. and relative abundances of the genera Bifidobacterium, Collinsella, and Eubacterium while the genus Dialister was decreased (P < 0.05). No other effects were found on microbiota composition. Remarkably, however, the synbiotic increased concentrations of branched-chain fatty acids, measured by gas chromatography, while short-chain fatty acids were not affected.

  14. Hydration of atmospherically relevant molecular clusters: computational chemistry and classical thermodynamics.

    PubMed

    Henschel, Henning; Navarro, Juan C Acosta; Yli-Juuti, Taina; Kupiainen-Määttä, Oona; Olenius, Tinja; Ortega, Ismael K; Clegg, Simon L; Kurtén, Theo; Riipinen, Ilona; Vehkamäki, Hanna

    2014-04-10

    Formation of new particles through clustering of molecules from condensable vapors is a significant source for atmospheric aerosols. The smallest clusters formed in the very first steps of the condensation process are, however, not directly observable by experimental means. We present here a comprehensive series of electronic structure calculations on the hydrates of clusters formed by up to four molecules of sulfuric acid, and up to two molecules of ammonia or dimethylamine. Though clusters containing ammonia, and certainly dimethylamine, generally exhibit lower average hydration than the pure acid clusters, populations of individual hydrates vary widely. Furthermore, we explore the predictions obtained using a thermodynamic model for the description of these hydrates. The similar magnitude and trends of hydrate formation predicted by both methods illustrate the potential of combining them to obtain more comprehensive models. The stabilization of some clusters relative to others due to their hydration is highly likely to have significant effects on the overall processes that lead to formation of new particles in the atmosphere.

  15. Potential geologic hazards of Arctic gas hydrates

    SciTech Connect

    Collett, T.S. )

    1990-05-01

    Sediments of the Arctic region may contain enormous quantities of natural gas in the form of gas hydrates, which are crystalline substances composed of water and mostly methane gas. These ice-like substances are generally found in two distinct environments: (1) offshore in sediments of outer continental margins and (2) nearshore and onshore in areas associated with the occurrence of permafrost. Recently, US, Canadian, and Soviet researchers have described numerous drilling and production problems attributed to the presence of gas hydrates, including uncontrolled gas releases during drilling, collapsed casings, and gas leakage to the surface. When the drill bit penetrates a gas hydrate, the drilling mud, unless cooled significantly by the operator, will become highly gasified as the hydrate decomposes. The hydrate adjacent to the well bore will continue to decompose and gasify the drilling mud as long as drilling and/or production introduces heat into the hydrate-bearing interval. The production of hot fluids from depth through the permafrost and gas hydrate-bearing intervals adversely raises formation temperatures, thus decomposing the gas hydrates. If the disassociated, free gas is trapped behind the casing, reservoir pressures may substantially increase and cause the casing to collapse. In several wells in northern Alaska, the disassociated free gas has leaked to the surface outside the conductor casing. An additional drilling hazard associated with gas hydrates results from the sealing attributes of hydrates, which may trap large volumes of over pressured free gas at shallow depths. Even though documented problems attributed to the presence of gas hydrates have been relatively few, it is likely that as exploration and development activity moves farther offshore into deeper water (>300 m) and to higher latitudes in the Arctic, the frequency of gas hydrate-related problems will increase.

  16. Gas hydrates of outer continental margins

    SciTech Connect

    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 of 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.

  17. 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.

  18. Use of Hydration Inhibitors to Improve Bond Durability of Aluminum Adhesive Joints

    NASA Technical Reports Server (NTRS)

    Davis, G. D.; Ahearn, J. S.; Matienzo, L. J.; Venables, J. D.

    1985-01-01

    An investigation is conducted of the mechanisms by which nitrilotris methylene phosphonic acid (NTMP) and related compounds are adsorbed onto oxidized aluminum surfaces to inhibit hydration and increase the durability of adhesive bonds formed with inhibitor-treated panels. P - O - Al bonds are identified as the basis of adsorption, and it is found that water initially adsorbed onto the etched aluminum surfaces is displaced by the NTMP. The hydration of the NTMP-treated surfaces occurs in three stages, namely the reverisble physisorption of water, the slow dissolution of NTMP followed by rapid hydration of the freshly exposed Al2O3 to AlOOH and further hydration of the surface to Al(OH)3. Five properties of an ideal inhibitor are identified.

  19. 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.

  20. 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

  1. Physical Properties of Gas Hydrates: A Review

    SciTech Connect

    Gabitto, Jorge; Tsouris, Costas

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 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.

  2. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  3. A novel retinoic acid, catechin hydrate and mustard oil-based emulsion for enhanced cytokine and antibody responses against multiple strains of HIV-1 following mucosal and systemic vaccinations

    PubMed Central

    Yu, Mingke; Vajdy, Michael

    2011-01-01

    Non-replicating protein- or DNA-based antigens generally require immune-enhancing adjuvants and delivery systems. It has been particularly difficult to raise antibodies against gp120 of HIV-1, which constitutes an important approach in HIV vaccine design. While almost all effort in adjuvant research has focused on mimicking the pathogens and the danger signals they engender in the host, relatively little effort has been spent on nutritive approaches. In this study, a new nutritive immune-enhancing delivery system (NIDS) composed of vitamin A, a polyphenol-flavonoid catechin hydrate, and mustard oil was tested for its adjuvant effect in immune responses against the gp120 protein of HIV-1CN54. Following a combination of two mucosal and two systemic vaccinations of mice, we found significant enhancement of both local and systemic antibodies as well as cytokine responses. These data have important implications for vaccine and adjuvant design against HIV-1 and other pathogens. PMID:21272602

  4. 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.

  5. Catastrophic growth of gas hydrates in the presence of kinetic hydrate inhibitors.

    PubMed

    Cha, Minjun; Shin, Kyuchul; Seo, Yutaek; Shin, Ju-Young; Kang, Seong-Pil

    2013-12-27

    The effect of the concentration of kinetic hydrate inhibitors, polyvinylpyrrolidone (PVP), and polyvinylcaprolactam (PVCap) on the onset and growth of synthetic natural gas hydrates is investigated by measuring the hydrate onset time and gas consumption rate. Although the hydrate onset time is extended by increasing the concentration from 0.5 to 3.0 wt % for both PVP and PVCap, the growth rate of hydrates shows that the different tendency depends on the type of kinetic hydrate inhibitor and its concentration. For PVCap solution, the hydrate growth was slow for more than 1000 min after the onset at the concentration of 0.5 and 1.5 wt %. However, the growth rate becames almost 8 times faster at the concentration of 3.0 wt %, representing the catastrophic growth of hydrate just after the hydrate onset. (13)C NMR spectra of hydrates formed at 3.0 wt % of PVP and PVCap indicate the existence of both structures I and II. Cage occupancy of methane in large cages of structure II decreases significantly when compared to that for pure water. These results suggest that increasing the concentration of KHI up to 3.0 wt % may induce the earlier appearance of catastrophic hydrate growth and the existence of metastable structure I; thus, there needs to be an upper limit for using KHI to manage the formation of gas hydrates.

  6. 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…

  7. OXYGEN ABUNDANCES IN CEPHEIDS

    SciTech Connect

    Luck, R. E.; Andrievsky, S. M.; Korotin, S. N.; Kovtyukh, V. V. E-mail: serkor@skyline.od.ua E-mail: scan@deneb1.odessa.ua

    2013-07-01

    Oxygen abundances in later-type stars, and intermediate-mass stars in particular, are usually determined from the [O I] line at 630.0 nm, and to a lesser extent, from the O I triplet at 615.7 nm. The near-IR triplets at 777.4 nm and 844.6 nm are strong in these stars and generally do not suffer from severe blending with other species. However, these latter two triplets suffer from strong non-local thermodynamic equilibrium (NLTE) effects and thus see limited use in abundance analyses. In this paper, we derive oxygen abundances in a large sample of Cepheids using the near-IR triplets from an NLTE analysis, and compare those abundances to values derived from a local thermodynamic equilibrium (LTE) analysis of the [O I] 630.0 nm line and the O I 615.7 nm triplet as well as LTE abundances for the 777.4 nm triplet. All of these lines suffer from line strength problems making them sensitive to either measurement complications (weak lines) or to line saturation difficulties (strong lines). Upon this realization, the LTE results for the [O I] lines and the O I 615.7 nm triplet are in adequate agreement with the abundance from the NLTE analysis of the near-IR triplets.

  8. [alpha]-Oxocarboxylic Acids

    ERIC Educational Resources Information Center

    Kerber, Robert C.; Fernando, Marian S.

    2010-01-01

    Several [alpha]-oxocarboxylic acids play key roles in metabolism in plants and animals. However, there are inconsistencies between the structures as commonly portrayed and the reported acid ionization constants, which result because the acids are predominantly hydrated in aqueous solution; that is, the predominant form is RC(OH)[subscript 2]COOH…

  9. Methane hydrate research at NETL: Research to make methane production from hydrates a reality

    SciTech Connect

    Taylor, C.E.; Link, D.D.; English, N.

    2007-03-01

    Research is underway at NETL to understand the physical properties of methane hydrates. Five key areas of research that need further investigation have been identified. These five areas, i.e. thermal properties of hydrates in sediments, kinetics of natural hydrate dissociation, hysteresis effects, permeability of sediments to gas flow and capillary pressures within sediments, and hydrate distribution at porous scale, are important to the production models that will be used for producing methane from hydrate deposits. NETL is using both laboratory experiments and computational modeling to address these five key areas. The laboratory and computational research reinforce each other by providing feedback. The laboratory results are used in the computational models and the results from the computational modeling is used to help direct future laboratory research. The data generated at NETL will be used to help fulfill The National Methane Hydrate R&D Program of a “long-term supply of natural gas by developing the knowledge and technology base to allow commercial production of methane from domestic hydrate deposits by the year 2015” as outlined on the NETL Website [NETL Website, 2005. http://www.netl.doe.gov/scngo/Natural%20Gas/hydrates/index.html]. Laboratory research is accomplished in one of the numerous high-pressure hydrate cells available ranging in size from 0.15 mL to 15 L in volume. A dedicated high-pressure view cell within the Raman spectrometer allows for monitoring the formation and dissociation of hydrates. Thermal conductivity of hydrates (synthetic and natural) at a certain temperature and pressure is performed in a NETL-designed cell. Computational modeling studies are investigating the kinetics of hydrate formation and dissociation, modeling methane hydrate reservoirs, molecular dynamics simulations of hydrate formation, dissociation, and thermal properties, and Monte Carlo simulations of hydrate formation and dissociation.

  10. Evaluation of the geological relationships to gas hydrate formation and stability. Progress report, June 16--September 30, 1988

    SciTech Connect

    Krason, J.; Finley, P.

    1988-12-31

    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  11. 78 FR 26337 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-06

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  12. 78 FR 37536 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-21

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  13. 76 FR 59667 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

  14. Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Hudson, R. L.; Moore, M. H.; Carlson, R. W.

    2011-01-01

    We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the revolutionary and new

  16. Bacterial dominance in subseafloor sediments characterized by methane hydrates

    USGS Publications Warehouse

    Briggs, Brandon R.; Inagaki, Fumio; Morono, Yuki; Futagami, Taiki; Huguet, Carme; Rosell-Mele, Antoni; Lorenson, T.D.; Colwell, Frederick S.

    2015-01-01

    The degradation of organic carbon in subseafloor sediments on continental margins contributes to the largest reservoir of methane on Earth. Sediments in the Andaman Sea are composed of ~ 1% marine-derived organic carbon and biogenic methane is present. Our objective was to determine microbial abundance and diversity in sediments that transition the gas hydrate occurrence zone (GHOZ) in the Andaman Sea. Microscopic cell enumeration revealed that most sediment layers harbored relatively low microbial abundance (103–105 cells cm−3). Archaea were never detected despite the use of both DNA- and lipid-based methods. Statistical analysis of terminal restriction fragment length polymorphisms revealed distinct microbial communities from above, within, and below the GHOZ, and GHOZ samples were correlated with a decrease in organic carbon. Primer-tagged pyrosequences of bacterial 16S rRNA genes showed that members of the phylum Firmicutes are predominant in all zones. Compared with other seafloor settings that contain biogenic methane, this deep subseafloor habitat has a unique microbial community and the low cell abundance detected can help to refine global subseafloor microbial abundance.

  17. Bacterial dominance in subseafloor sediments characterized by methane hydrates.

    PubMed

    Briggs, Brandon R; Inagaki, Fumio; Morono, Yuki; Futagami, Taiki; Huguet, Carme; Rosell-Mele, Antoni; Lorenson, Thomas D; Colwell, Frederick S

    2012-07-01

    The degradation of organic carbon in subseafloor sediments on continental margins contributes to the largest reservoir of methane on Earth. Sediments in the Andaman Sea are composed of ~ 1% marine-derived organic carbon and biogenic methane is present. Our objective was to determine microbial abundance and diversity in sediments that transition the gas hydrate occurrence zone (GHOZ) in the Andaman Sea. Microscopic cell enumeration revealed that most sediment layers harbored relatively low microbial abundance (10(3)-10(5) cells cm(-3)). Archaea were never detected despite the use of both DNA- and lipid-based methods. Statistical analysis of terminal restriction fragment length polymorphisms revealed distinct microbial communities from above, within, and below the GHOZ, and GHOZ samples were correlated with a decrease in organic carbon. Primer-tagged pyrosequences of bacterial 16S rRNA genes showed that members of the phylum Firmicutes are predominant in all zones. Compared with other seafloor settings that contain biogenic methane, this deep subseafloor habitat has a unique microbial community and the low cell abundance detected can help to refine global subseafloor microbial abundance.

  18. Solubility of hematite revisited: effects of hydration.

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2007-11-01

    Measured pH and dissolved ferric iron concentration ([Fe(III)diss]) in contact with well-characterized hematite indicated an equilibrium with hematite immediately after synthesis, but [Fe(III)diss] increased with hydration time to be consistent with the predicted solubility of goethite or hydrous ferric oxide (HFO), hydrated analogues of hematite. X-ray diffraction did not detect structural modification of hematite after 190 days of hydration, but Mössbauer spectroscopy detected hydration that penetrated several crystalline layers. When the hematite suspension was diluted with water, solids were invariably identified as hematite, but [Fe(III)diss] and pH indicated an equilibrium with goethite or HFO. This is the first experimental confirmation that the interfacial hydration of anhydrous hematite results in higher solubility than predicted by bulk thermodynamic properties of hematite. Correspondence of the results with previously published measurements and implications for environmental chemistry of ferric oxides are also discussed.

  19. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  20. The abundant class III chitinase homolog in young developing banana fruits behaves as a transient vegetative storage protein and most probably serves as an important supply of amino acids for the synthesis of ripening-associated proteins.

    PubMed

    Peumans, Willy J; Proost, Paul; Swennen, Rony L; Van Damme, Els J M

    2002-10-01

    Analyses of the protein content and composition revealed dramatic changes in gene expression during in situ banana (Musa spp.) fruit formation/ripening. The total banana protein content rapidly increases during the first 60 to 70 d, but remains constant for the rest of fruit formation/ripening. During the phase of rapid protein accumulation, an inactive homolog of class III chitinases accounts for up to 40% (w/v) of the total protein. Concomitant with the arrest of net protein accumulation, the chitinase-related protein (CRP) progressively decreases and several novel proteins appear in the electropherograms. Hence, CRP behaves as a fruit-specific vegetative storage protein that accumulates during early fruit formation and serves as a source of amino acids for the synthesis of ripening-associated proteins. Analyses of individual proteins revealed that a thaumatin-like protein, a beta-1,3-glucanase, a class I chitinase, and a mannose-binding lectin are the most abundant ripening-associated proteins. Because during the ripening of prematurely harvested bananas, similar changes take place as in the in situ ripening bananas, CRP present in immature fruits is a sufficient source of amino acids for a quasi-normal synthesis of ripening-associated proteins. However, it is evident that the conversion of CRP in ripening-associated proteins takes place at an accelerated rate, especially when climacteric ripening is induced by ethylene. The present report also includes a discussion of the accumulation of the major banana allergens and the identification of suitable promoters for the production of vaccines in transgenic bananas.

  1. The Abundant Class III Chitinase Homolog in Young Developing Banana Fruits Behaves as a Transient Vegetative Storage Protein and Most Probably Serves as an Important Supply of Amino Acids for the Synthesis of Ripening-Associated Proteins1

    PubMed Central

    Peumans, Willy J.; Proost, Paul; Swennen, Rony L.; Van Damme, Els J.M.

    2002-01-01

    Analyses of the protein content and composition revealed dramatic changes in gene expression during in situ banana (Musa spp.) fruit formation/ripening. The total banana protein content rapidly increases during the first 60 to 70 d, but remains constant for the rest of fruit formation/ripening. During the phase of rapid protein accumulation, an inactive homolog of class III chitinases accounts for up to 40% (w/v) of the total protein. Concomitant with the arrest of net protein accumulation, the chitinase-related protein (CRP) progressively decreases and several novel proteins appear in the electropherograms. Hence, CRP behaves as a fruit-specific vegetative storage protein that accumulates during early fruit formation and serves as a source of amino acids for the synthesis of ripening-associated proteins. Analyses of individual proteins revealed that a thaumatin-like protein, a β-1,3-glucanase, a class I chitinase, and a mannose-binding lectin are the most abundant ripening-associated proteins. Because during the ripening of prematurely harvested bananas, similar changes take place as in the in situ ripening bananas, CRP present in immature fruits is a sufficient source of amino acids for a quasi-normal synthesis of ripening-associated proteins. However, it is evident that the conversion of CRP in ripening-associated proteins takes place at an accelerated rate, especially when climacteric ripening is induced by ethylene. The present report also includes a discussion of the accumulation of the major banana allergens and the identification of suitable promoters for the production of vaccines in transgenic bananas. PMID:12376669

  2. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated and is

  3. Overview on Hydrate Coring, Handling and Analysis

    SciTech Connect

    Jon Burger; Deepak Gupta; Patrick Jacobs; John Shillinglaw

    2003-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Worldwide, gas hydrate is estimated to hold about 1016 kg of organic carbon in the form of methane (Kvenvolden et al., 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In June 2002, Westport Technology Center was requested by the Department of Energy (DOE) to prepare a ''Best Practices Manual on Gas Hydrate Coring, Handling and Analysis'' under Award No. DE-FC26-02NT41327. The scope of the task was specifically targeted for coring sediments with hydrates in Alaska, the Gulf of Mexico (GOM) and from the present Ocean Drilling Program (ODP) drillship. The specific subjects under this scope were defined in 3 stages as follows: Stage 1: Collect information on coring sediments with hydrates, core handling, core preservation, sample transportation, analysis of the core, and long term preservation. Stage 2: Provide copies of the first draft to a list of experts and stakeholders designated by DOE. Stage 3: Produce a second draft of the manual with benefit of input from external review for delivery. The manual provides an overview of existing information available in the published literature and reports on coring, analysis, preservation and transport of gas hydrates for laboratory analysis as of June 2003. The manual was delivered as draft version 3 to the DOE Project Manager for distribution in July 2003. This Final Report is provided for records purposes.

  4. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-06-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-07-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  6. Evaluation of CO2 Substitution for CH4 as a Mechanism for Concurrent Gas Production and CO2 Sequestration in Hydrate-Bearing Geologic Media

    NASA Astrophysics Data System (ADS)

    Moridis, G. J.; Reagan, M. T.; Silpngarmlert, S.

    2010-12-01

    Natural hydrates in geologic media contain CH4 in overwhelming abundance. In addition to the conventional methods of CH4-hydrate dissociation (depressurization, thermal stimulation, the use of inhibitors, and combinations thereof), CO2 substitution for CH4 has been proposed as a potential method that could simultaneously achieve two goals: the release of CH4 from the CH4-hydrates for gas production, and the replacement of CH4 by CO2 in the clathrates, thus forming either binary CH4+CO2-hydrates or pure CO2-hydrates and enabling CO2 sequestration. The reaction of CO2 substitution for CH4 in the clathrates is thermodynamically favorable, resulting in binary or CO2-hydrates that are more thermodynamically stable than CH4-hydrates. In this numerical study we first evaluate the performance of a new equation-of-state (EOS) module developed as a code unit for the TOUGH+ general simulator. The EOS describes the thermodynamic and flow behavior of binary CH4+CO2-hydrates in geologic media, and covers the entire composition spectrum in both the gas and the hydrate phase. The EOS includes fast parametric relationships that describe the 3-dimensional P-T-X phase diagram of the CH4+CO2+H2O system, which (a) were developed from 3D regression of thermodynamic data obtained from the CSMGem code (a statistical thermodynamics simulator that is based on the minimization of Gibbs energy of hydrate systems) and (b) were validated using laboratory measurements. The TOUGH+ simulator with the CH4+CO2-hydrate EOS is then validated using results from laboratory studies that involve replacement of CH4 by CO2 in hydrate-bearing cores. Finally, we investigate the technical feasibility of such replacement at the reservoir scale, and the conditions under which it may be successful, in realistic settings involving systems of vertical and horizontal wells.

  7. Methane Hydrates: Major Energy Source for the Future or Wishful Thinking?

    SciTech Connect

    Thomas, Charles Phillip

    2001-09-01

    Methane hydrates are methane bearing, ice-like materials that occur in abundance in permafrost areas such as on the North Slope of Alaska and Canada and as well as in offshore continental margin environments throughout the world including the Gulf of Mexico and the East and West Coasts of the United States. Methane hydrate accumulations in the United States are currently estimated to be about 200,000 Tcf, which is enormous when compared to the conventional recoverable resource estimate of 2300 Tcf. On a worldwide basis, the estimate is 700,000 Tcf or about two times the total carbon in coal, oil and conventional gas in the world. The enormous size of this resource, if producible to any degree, has significant implications for U.S. and worldwide clean energy supplies and global environmental issues. Historically the petroleum industry's interests in methane hydrates have primarily been related to safety issues such as wellbore stability while drilling, seafloor stability, platform subsidence, and pipeline plugging. Many questions remain to be answered to determine if any of this potential energy resource is technically and economically viable to produce. Major technical hurdles include: 1) methods to find, characterize, and evaluate the resource; 2) technology to safely and economically produce natural gas from methane hydrate deposits; and 3) safety and seafloor stability issues related to drilling through gas hydrate accumulations to produce conventional oil and gas. The petroleum engineering profession currently deals with gas hydrates in drilling and production operations and will be key to solving the technical and economic problems that must be overcome for methane hydrates to be part of the future energy mix in the world.

  8. Efficient recovery of CO2 from flue gas by clathrate hydrate formation in porous silica gels.

    PubMed

    Seo, Yu-Taek; Moudrakovski, Igor L; Ripmeester, John A; Lee, Jong-Won; Lee, Huen

    2005-04-01

    Thermodynamic measurements and NMR spectroscopic analysis were used to show that it is possible to recover CO2 from flue gas by forming a mixed hydrate that removes CO2 preferentially from CO2/N2 gas mixtures using water dispersed in the pores of silica gel. Kinetic studies with 1H NMR microimaging showed that the dispersed water in the silica gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor and excess water. Hydrate phase equilibria for the ternary CO2-N2-water system in silica gel pores were measured, which show that the three-phase hydrate-water-rich liquid-vapor equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO2 in the vapor phase decreased. 13C cross-polarization NMR spectral analysis and direct measurement of the CO2 content in the hydrate phase suggested that the mixed hydrate is structure I at gas compositions of more than 10 mol % CO2, and that the CO2 molecules occupy mainly the more abundant 5(12)6(2) cages. This makes it possible to achieve concentrations of more than 96 mol % CO2 gas in the product after three cycles of hydrate formation and dissociation. 1H NMR microimaging showed that hydrate yields of better than 85%, based on the amount of water, could be obtained in 1 h when a steady state was reached, although approximately 90% of this yield was achieved after approximately 20 min of reaction time.

  9. From powder to solution: hydration dependence of human hemoglobin dynamics correlated to body temperature.

    PubMed

    Stadler, A M; Digel, I; Embs, J P; Unruh, T; Tehei, M; Zaccai, G; Büldt, G; Artmann, G M

    2009-06-17

    A transition in hemoglobin (Hb), involving partial unfolding and aggregation, has been shown previously by various biophysical methods. The correlation between the transition temperature and body temperature for Hb from different species, suggested that it might be significant for biological function. To focus on such biologically relevant human Hb dynamics, we studied the protein internal picosecond motions as a response to hydration, by elastic and quasielastic neutron scattering. Rates of fast diffusive motions were found to be significantly enhanced with increasing hydration from fully hydrated powder to concentrated Hb solution. In concentrated protein solution, the data showed that amino acid side chains can explore larger volumes above body temperature than expected from normal temperature dependence. The body temperature transition in protein dynamics was absent in fully hydrated powder, indicating that picosecond protein dynamics responsible for the transition is activated only at a sufficient level of hydration. A collateral result from the study is that fully hydrated protein powder samples do not accurately describe all aspects of protein picosecond dynamics that might be necessary for biological function.

  10. Correlation Between Chain Architecture and Hydration Water Structure in Polysaccharides

    NASA Astrophysics Data System (ADS)

    Grossutti, Michael; Dutcher, John

    The physical properties of confined water can differ dramatically from those of bulk water. Hydration water associated with polysaccharides provides a particularly important example of confined water, with differences in polysaccharide structure providing different spatially confined environments for water adsorption. We have used attenuated total reflection infrared (ATR-IR) spectroscopy to investigate the structure of hydration water in films of three different polysaccharides under controlled relative humidity (RH) conditions. We compare the results obtained for films of highly branched, monodisperse phytoglycogen nanoparticles to those obtained for two unbranched polysaccharides, hyaluronic acid (HA) and chitosan. We find similarities between water structuring in the two linear polysaccharides, and significant differences for phytoglycogen. In particular, the phytoglycogen nanoparticles exhibited high network water connectivity, and a large increase in the fraction of multimer water clusters with increasing RH, whereas the water structure for HA and chitosan was found to be insensitive to changes in RH. These measurements provide unique insight into the relationship between the chain architecture and hydration of polysaccharides.

  11. Hydration, charge, size, and shape characteristics of peptides from their CZE analyses.

    PubMed

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

    2008-02-01

    A CZE model is presented for peptide characterization on the basis of well-established physicochemical equations. The effective mobility is used as basic data in the model to estimate relevant peptide properties such as, for instance, hydration, net and total electrical charge numbers, hydrodynamic size and shape, particle average orientation, and pH-microenvironment from the charge regulation phenomenon. Therefore 102 experimental effective mobilities of different peptides are studied and discussed in relation to previous work. An equation for the estimation of peptide hydration as a function of ionizing, polar, and non-polar amino acid residues is included in the model. It is also shown that the shape-orientation factor of peptides may be either lower or higher than one, and its value depends on a complex interplay among total charge number, molar mass, hydration, and amino acid sequence.

  12. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  13. Gas Hydrate Storage of Natural Gas

    SciTech Connect

    Rudy Rogers; John Etheridge

    2006-03-31

    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  14. Hydration and hydrolysis of thorium(IV) in aqueous solution and the structures of two crystalline thorium(IV) hydrates.

    PubMed

    Torapava, Natallia; Persson, Ingmar; Eriksson, Lars; Lundberg, Daniel

    2009-12-21

    Solid octaaqua(kappa(2)O-perchlorato)thorium(IV) perchlorate hydrate, [Th(H(2)O)(8)(ClO(4))](ClO(4))(3).H(2)O, 1, and aquaoxonium hexaaquatris(kappaO-trifluoromethanesulfonato)thorium(IV) trisaquahexakis(kappaO-trifluoromethanesulfonato)thorinate(IV), H(5)O(2)[Th(H(2)O)(6)(OSO(2)CF(3))(3)][Th(H(2)O)(3)(OSO(2)CF(3))(6)], 2, were crystallized from concentrated perchloric and trifluoromethanesulfonic acid solutions, respectively. 1 adopts a severely distorted tricapped trigonal prismatic configuration with an additional oxygen from the perchlorate ion at a longer distance. 2 consists of individual hexaaquatris(kappaO-trifluoromethanesulfonato)thorium(IV) and trisaquahexakis(kappaO-trifluoromethanesulfonato)thorinate(IV) ions and an aquaoxonium ion bridging these two ions through hydrogen bonding. The hydrated thorium(IV) ion is nine-coordinated in aqueous solution as determined by extended X-ray absorption fine structure (EXAFS) and large angle X-ray scattering (LAXS). The LAXS studies also showed a second hydration sphere of about 18 water molecules, and traces of a 3rd hydration sphere. Structural studies in aqueous solution of the hydrolysis products of thorium(IV) have identified three different types of hydrolysis species: a mu(2)O-hydroxo dimer, [Th(2)(OH)(2)(H(2)O)(12)](6+), a mu(2)O-hydroxo tetramer, [Th(4)(OH)(8)(H(2)O)(16)](8+), and a mu(3)O-oxo hexamer, [Th(6)O(8)(H(2)O)(n)](8+). Detailed structures of these three hydrolysis species are given. A compilation of reported solid state structures of actinoid(IV) compounds with oxygen donor ligands show a strong correlation between the An-O bond distance and the coordination number. The earlier reported U-O bond distance in the hydrated uranium(IV) ion in aqueous solution, confirmed in this study, is related to nine-coordination. The hydrated tri- and tetravalent actinoid ions in aqueous solution all seem to be nine-coordinated. The trivalent ions show a significant difference in bond distance to prismatic and

  15. DNA hydration studied by neutron fiber diffraction

    SciTech Connect

    Fuller, W.; Forsyth, V.T.; Mahendrasingam, A.; Langan, P.; Pigram, W.J.

    1994-12-31

    The development of neutron high angle fiber diffraction to investigate the location of water around the deoxyribonucleic acid (DNA) double-helix is described. The power of the technique is illustrated by its application to the D and A conformations of DNA using the single crystal diffractometer, D19, at the Institute Laue-Langevin, Grenoble and the time of flight diffractometer, SXD, at the Rutherford Appleton ISIS Spallation Neutron Source. These studies show the existence of bound water closely associated with the DNA. The patterns of hydration in these two DNA conformations are quite distinct and are compared to those observed in X-ray single crystal studies of two-stranded oligodeoxynucleotides. Information on the location of water around the DNA double-helix from the neutron fiber diffraction studies is combined with that on the location of alkali metal cations from complementary X-ray high angle fiber diffraction studies at the Daresbury Laboratory SRS using synchrotron radiation. These analyses emphasize the importance of viewing DNA, water and ions as a single system with specific interactions between the three components and provide a basis for understanding the effect of changes in the concentration of water and ions in inducing conformations] transitions in the DNA double-helix.

  16. Interactions of Organic Additives with Ionic Crystal Hydrates

    NASA Astrophysics Data System (ADS)

    Füredi-Milhofer, H.; Sikirić, M.; Tunik, L.; Filipović-Vinceković, N.; Garti, N.

    The interactions of two groups of hydrated model crystals, calcium hydrogenphosphate dihydrate (DCPD) vs. octacalcium phosphate (OCP) and calcium oxalate monohydrate (COM) vs. calcium oxalate dihydrate (COD) with different organic additives are considered. DCPD precipitates as platelet-like crystals with the dominant faces shielded by hydrated layers and charged lateral faces. In the second system COM has charged surfaces, while all faces of COD are covered with layers containing water molecules. The organic molecules tested include negatively charged, flexible and rigid small and macromolecules (glutamic and aspartic acid, citrate, hexaammonium polyphosphate, phytate and polyaspartate) and anionic surfactants (sodium dodecyl sulphate, SDS, sodium diisooctyl sulfosuccinate, AOT, sodium cholate NaC and disodium oleoamido PEG-2 sulfosuccinate, PEG). Two types of effects have been demonstrated: (1) Effect on crystal growth morphology: Flexible organic molecules with high charge density and anionic surfactants affected the growth morphology of DCPD and COM by selectively interacting with the charged lateral faces while rigid molecules (phytate, polyaspartate) specifically recognized the dominant (010) face of DCPD due to structural and stereochemical compatibility. (2) Effect on phase composition: Anionic surfactants at concentrations above the cmc promoted growth of OCP and COD respectively by selectively adsorbing at, and inhibiting growth oif nuclei of DCPD and/or COM, which were dominant in the respective control systems. The effect was especially pronounced in the calcium oxalate precipitation system, where in some cases complete reversal of the phase composition occurred. The important role of the hydrated layer, as part of the structure of the investigated crystal hydrates, in the above crystal additive interactions is discussed.

  17. Diffusion of CO2 During Hydrate Formation and Dissolution

    SciTech Connect

    Franklin M. Orr, Jr.

    2002-08-20

    Experiments were performed to measure the rate of diffusion of CO2 through hydrate films. Hydrate films were created in a capillary tube, and the growth of the hydrate film was measured. Difficulties were encountered in creating hydrate repeatedly, and some non-uniform growth of the films was observed. Sufficient observations were obtained to demonstrate that hydrate growth occurs preferentially on the hydrate/water side of the interface, rather than at the hydrate/CO2 interface. Diffusion coefficients were estimated from observations of the rate of growth of the hydrate film along with estimates of the solubility of CO2 in water and of the concentration gradient across the hydrate layer. The experimental observations indicate that hydrate formation occurs much more rapidly at the hydrate water interface than at the hydrate/CO2 interface. Any growth of hydrate at the CO2/hydrate interface was too slow to be observed at the time scale of the experiments. That observation is consistent with the idea that CO2 can move more easily through the hydrate, presumably by hopping between hydrate cages, than water can move through the hydrate, presumably by lattice hopping. Estimated diffusion coefficients were in the range 1-3E-06 cm2/sec. Those values are about an order of magnitude lower than the diffusion coefficient for CO2 in liquid water, but four orders of magnitude larger than the value for diffusion of CO2 in a solid. The rate of diffusion through the hydrate controls both the creation of new hydrate at the hydrate/water interface and the rate at which CO2 dissolves in the liquid water and diffuses away from the hydrate layer. Formation of a hydrate layer reduces the rate at which CO2 dissolves in liquid water.

  18. 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.

  19. Detection and Production of Methane Hydrate

    SciTech Connect

    George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

    2011-12-31

    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 remote 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

  20. [The outcome of hydration in functional dysphonia].

    PubMed

    García Real, T; García Real, A; Díaz Román, T; Cañizo Fernández Roldán, A

    2002-01-01

    Functional dysphonia has high prevalence among professional voice users. Different aspects should be considered in vocal therapy. One of them is hydration. The aim of the present study is to assess the effect of hydration on a few aspect of vocal dysfunction. 75 subjects were distributed into three different groups. 23 participated as a control group, 27 received hydration treatment and 25 received hydration treatment plus voice training. Dryness, mucosity, phonatory effort, hoarseness, fundamental frequency (Fo), maximum phonatory time (MPT), time of speech and laryngeal status were the variables evaluated at time 0 and 14 days later, immediately after the completion of the treatment of each group. Statistical differences regarding dryness (p = 0.003) and hoarseness (p = 0.033) were found between the control group and the groups receiving treatment. There were no statistical differences in severity and frequency of variables measured at time 0 at 14 days later in the control group. However, all variables except laryngeal status, improved significantly in the groups receiving hydration alone. Only clinical variables improved in the combined group. These findings indicated a therapeutic benefit of hydration, with or without voice training, for functional dysphonia. Further studies using acoustic and stroboscopic analysis are required in order to define the effect of hydration on the compliance of glottic sphincter.

  1. Gas Hydrates Research Programs: An International Review

    SciTech Connect

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  2. Multiphasic finite element modeling of concrete hydration

    SciTech Connect

    Buffo-Lacarriere, L.; Sellier, A. . E-mail: alain.sellier@insa-toulouse.fr; Escadeillas, G.; Turatsinze, A.

    2007-02-15

    This paper presents a model predicting the development of hydration and its consequences on temperature and water content. As it considers the effects of climatic conditions, the proposed model is a promising tool to evaluate the temperature, hydric and hydration fields of structures in situ. The hydration model predicts the hydration evolution of several main species (not only clinker but also mineral additions like fly ash or silica fume for instance). For each component, the modeling considers hydration development and chemical interaction between reactions. It also takes into account temperature and water content effects on reaction kinetics through thermal and hydric activation. Hydration development in turn modifies the thermal and hydric states of material. The result is a numerical model coupling hydration, and the thermal and hydric states of cement-based material. The model was tested on a 27 m{sup 3} concrete block in situ equipped with temperature sensors situated in the core and close to the face exposed to solar radiation.

  3. Prospecting for marine gas hydrate resources

    USGS Publications Warehouse

    Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.

    2016-01-01

    As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.

  4. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2003-12-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the US have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by maurer Technology, noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R and D in the area of onshore hydrate deposition. They plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. They also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. They are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. They hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, the goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by Maurer Technology, Noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition. We plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. We also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. We are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. We hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, our goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  6. Dynamics of hydration water in protein

    NASA Astrophysics Data System (ADS)

    Bellissent-Funel, M.-C.; Teixeira, J.; Bradley, K. F.; Chen, S. H.

    1992-06-01

    Incoherent quasi-elastic neutron scattering studies of in vivo deuterated C-phycocyanin, at different levels of hydration, have been made. We show that the mobility at high temperature, (sim 300 K) of the water molecules near the protein surface can be described by relatively simple models. At full hydration the high temperature data can be interpreted using a model where each water molecule is diffusing in a confined space of 3 Å in radius. At low hydration, and 298 K, the diffusional behaviour is typical of jump diffusion with a residence time 10 times larger than the one in bulk water at the same temperature.

  7. Tapping methane hydrates for unconventional natural gas

    USGS Publications Warehouse

    Ruppel, Carolyn

    2007-01-01

    Methane hydrate is an icelike form of concentrated methane and water found in the sediments of permafrost regions and marine continental margins at depths far shallower than conventional oil and gas. Despite their relative accessibility and widespread occurrence, methane hydrates have never been tapped to meet increasing global energy demands. With rising natural gas prices, production from these unconventional gas deposits is becoming economically viable, particularly in permafrost areas already being exploited for conventional oil and gas. This article provides an overview of gas hydrate occurrence, resource assessment, exploration, production technologies, renewability, and future challenges.

  8. Carbon dioxide hydrate and floods on Mars.

    PubMed

    Milton, D J

    1974-02-15

    Ground ice on Mars probably consists largely of carbon dioxide hydrate, CO(2) . 6H(2)O. This hydrate dissociates upon release of pressure at temperatures between 0 degrees and 10 degrees C. The heat capacity of the ground would be sufficient to produce up to 4 percent (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near surface temperature was in this range would have produced chaotic terrain and flood channels.

  9. Carbon dioxide hydrate and floods on Mars

    NASA Technical Reports Server (NTRS)

    Milton, D. J.

    1974-01-01

    Ground ice on Mars probably consists largely of carbon dioxide hydrate. This hydrate dissociates upon release of pressure at temperatures between 0 and 10 C. The heat capacity of the ground would be sufficient to produce up to 4% (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near-surface temperature was in this range would have produced chaotic terrain and flood channels.

  10. Clathrate hydrates in cometary nuclei and porosity

    NASA Technical Reports Server (NTRS)

    Smoluchowski, R.

    1988-01-01

    Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

  11. Glass powder blended cement hydration modelling

    NASA Astrophysics Data System (ADS)

    Saeed, Huda

    The use of waste materials in construction is among the most attractive options to consume these materials without affecting the environment. Glass is among these types of potential waste materials. In this research, waste glass in powder form, i.e. glass powder (GP) is examined for potential use in enhancing the characteristics of concrete on the basis that it is a pozzolanic material. The experimental and the theoretical components of the work are carried out primarily to prove that glass powder belongs to the "family" of the pozzolanic materials. The chemical and physical properties of the hydrated activated glass powder and the hydrated glass powder cement on the microstructure level have been studied experimentally and theoretically. The work presented in this thesis consists of two main phases. The first phase contains experimental investigations of the reaction of glass powder with calcium hydroxide (CH) and water. In addition, it includes experiments that are aimed at determining the consumption of water and CH with time. The reactivity, degree of hydration, and nature of the pore solution of the glass powder-blended cement pastes and the effect of adding different ratios of glass powder on cement hydration is also investigated. The experiments proved that glass powder has a pozzolanic effect on cement hydration; hence it enhances the chemical and physical properties of cement paste. Based on the experimental test results, it is recommended to use a glass powder-to-cement ratio (GP/C) of 10% as an optimum ratio to achieve the best hydration and best properties of the paste. Two different chemical formulas for the produced GP C-S-H gel due to the pure GP and GP-CH pozzolanic reaction hydration are proposed. For the pure GP hydration, the produced GP C-S-H gel has a calcium-to-silica ratio (C/S) of 0.164, water-to-silica ratio (H/S) of 1.3 and sodium/silica ratio (N/S) of 0.18. However, for the GP-CH hydration, the produced GP C-S-H gel has a C/S ratio of 1

  12. Ammonia abundances in comets

    NASA Astrophysics Data System (ADS)

    Wyckoff, S.; Tegler, S.; Engel, L.

    The emission band strengths of the NH2 bands of Comets Halley, Hartley-Good, Thiele, and Borrelly were measured to determine the NH2 column densities for the comets. Production rates obtained using the Haser and vectorial models are in agreement within the observational errors, suggesting that a simple two-step decay model may be used to approximate the NH2 distribution in a comet's coma. Ammonia-to-water abundance ratios from 0.01 to 0.4 percent were found for the four comets. The ratio in Comet Halley is found to be Q(NH3)/Q(H2O) = 0.002 + or - 0.001. No significant difference in the ammonia abundance was found before or after perihelion in Comet Halley.

  13. Antioxidant defences in hydrated and desiccated states of the tardigrade Paramacrobiotus richtersi.

    PubMed

    Rizzo, Angela M; Negroni, Manuela; Altiero, Tiziana; Montorfano, Gigliola; Corsetto, Paola; Berselli, Patrizia; Berra, Bruno; Guidetti, Roberto; Rebecchi, Lorena

    2010-06-01

    Reactive oxygen species (ROS) are formed in all aerobic organisms, potentially leading to oxidative damage of all biological molecules. A number of defence mechanisms have developed to protect the organism from attack by ROS. Desiccation tolerance is correlated with an increase in the antioxidant potential in several organisms, but the regulation of the antioxidant defence system is complex and its role in desiccation-tolerant organisms is not yet firmly established. To determine if anhydrobiotic tardigrades have an antioxidant defence system, capable of counteracting ROS, we compared the activity of several antioxidant enzymes, the fatty acid composition and Heat shock protein expression in two physiological states (desiccated vs. hydrated) of the tardigrade Paramacrobiotus richtersi. In hydrated tardigrades, superoxide dismutase and catalase show comparable activities, while in desiccated specimens the activity of superoxide dismutase increases. Both glutathione peroxidase and glutathione were induced by desiccation. The percentage of fatty acid composition of polyunsaturated fatty acids and the amount of thiobarbituric acid reactive substances are higher in desiccated animals than in hydrated ones. Lastly, desiccated tardigrades did not differ significantly from the hydrated ones in the relative levels of Hsp70 and Hsp90. These results indicate that the possession of antioxidant metabolism could represent a crucial strategy to avoid damages during desiccation in anhydrobiotic tardigrades.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    Tréhu, 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.; Weinberger, J. L.

    2004-06-01

    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.

  16. Microbial Communities from Methane Hydrate-Bearing Deep Marine Sediments

    SciTech Connect

    Reed, David William; Fujita, Yoshiko; Delwiche, Mark Edmond; Blackwelder, David Bradley; Colwell, Frederick Scott; Uchida, T.

    2002-08-01

    Microbial communities in cores obtained from methane hydrate-bearing deep marine sediments (down to more than 300 m below the seafloor) in the forearc basin of the Nankai Trough near Japan were characterized with cultivation-dependent and -independent techniques. Acridine orange direct count data indicated that cell numbers generally decreased with sediment depth. Lipid biomarker analyses indicated the presence of viable biomass at concentrations greater than previously reported for terrestrial subsurface environments at similar depths. Archaeal lipids were more abundant than bacterial lipids. Methane was produced from both acetate and hydrogen in enrichments inoculated with sediment from all depths evaluated, at both 10 and 35°C. Characterization of 16S rRNA genes amplified from the sediments indicated that archaeal clones could be discretely grouped within the Euryarchaeota and Crenarchaeota domains. The bacterial clones exhibited greater overall diversity than the archaeal clones, with sequences related to the Bacteroidetes, Planctomycetes, Actinobacteria, Proteobacteria, and green nonsulfur groups. The majority of the bacterial clones were either members of a novel lineage or most closely related to uncultured clones. The results of these analyses suggest that the microbial community in this environment is distinct from those in previously characterized methane hydrate-bearing sediments.

  17. Possible Albedo Proton Signature of Hydrated Lunar Surface Layer

    NASA Astrophysics Data System (ADS)

    Schwadron, N.; Wilson, J. K.; Looper, M. D.; Jordan, A.; Spence, H. E.; Blake, J. B.; Case, A. W.; Iwata, Y.; Kasper, J. C.; Farrell, W. M.; Lawrence, D. J.; Livadiotis, G.; Mazur, J. E.; Petro, N. E.; Pieters, C. M.; Robinson, M. S.; Smith, S. S.; Townsend, L. W.; Zeitlin, C. J.

    2015-12-01

    We find evidence for a surface layer of hydrated material in the lunar regolith using "albedo protons" measured by the Cosmic Ray Telescope for the Effects of Radiation (CRaTER) on the Lunar Reconnaissance Orbiter (LRO). Fluxes of these albedo protons, which are emitted from the regolith due to steady bombardment by high-energy radiation (Galactic Cosmic Rays), are observed to peak near the poles, and cannot be accounted for by either heavy element enrichment (e.g., enhanced Fe abundance), or by deeply buried (> 50 cm) hydrogenous material. The latitudinal distribution of albedo protons does not correlate with that of epithermal or high-energy neutrons. The high latitude enhancement may be due to the conversion of upward directed secondary neutrons from the lunar regolith into tertiary protons due to neutron-proton collisions in a thin (~ 1-10 cm) layer of hydrated regolith near the surface that is more prevalent near the poles. The CRaTER instrument thus provides critical measurements of volatile distributions within lunar regolith and potentially, with similar sensors and observations, at other bodies within the Solar System.

  18. Free gas in the regional hydrate stability zone: Implications for hydrate distribution and fracturing behavior

    NASA Astrophysics Data System (ADS)

    Daigle, H.; Dugan, B.

    2010-12-01

    We show that hydrate distribution and fracture genesis in the hydrate stability zone are largely governed by the phase of methane supply. In systems where methane is supplied primarily as free gas, hydrate saturation increases upwards in the hydrate stability zone, and fractures nucleate in the middle of the stability zone where hydrate saturation is highest. In systems where methane is supplied primarily as a dissolved phase in the pore water, hydrate saturation decreases upwards in the stability zone, and fractures nucleate at the base of the stability zone. These interpretations are based on our one-dimensional model that incorporates multiphase flow and free gas within the regional hydrate stability zone (RHSZ). The RHSZ is defined as the interval in which methane hydrate may occur at seawater salinity (3.35% by mass). As hydrate forms and excludes salt from the crystal structure, the porewater salinity increases. Free gas enters the RHSZ when the porewater salinity increases to the value required for three-phase (dissolved methane + gas hydrate + free gas) equilibrium. Our model also incorporates changes to capillary pressure as hydrate forms and occludes the pore system. We model the system until the excess pore pressure exceeds the vertical effective stress in the domain due to capillary effects and pore occlusion, at which point we assume fractures nucleate. We test our model at Hydrate Ridge, where methane supply is dominantly in the gas phase, and show that hydrate saturation increases upwards and fractures nucleate high within the stability zone, eventually allowing gas to vent to the seafloor. We also model Blake Ridge, where methane supply is dominantly in the dissolved phase, and show that hydrate saturation is greatest at the base of the stability zone; fractures nucleate here and in some cases could propagate through the regional hydrate stability zone, allowing methane-charged water to vent to the seafloor. These two systems represent endmembers of

  19. Understanding effect of structure and stability on transformation of CH4 hydrate to CO2 hydrate

    NASA Astrophysics Data System (ADS)

    Liu, Jinxiang; Yan, Yujie; Liu, Haiying; Xu, Jiafang; Zhang, Jun; Chen, Gang

    2016-03-01

    Understanding the transformation process of CH4 hydrate to CO2 hydrate is crucial to develop the CH4sbnd CO2 replacement technique for CH4 production and CO2 sequestration. Ab initio calculations show that the transformation will slightly distort the host lattice and decrease the binding strength of guest molecules, but it is a thermodynamically spontaneous process dominated by the entropic contribution. Moreover, ab initio molecular dynamics simulations suggest that the dynamics of the host lattice is independent on the guest molecules, while CO2 in hydrate exhibits slower translational and rotational motion than CH4 in hydrate.

  20. Hydration states of AFm cement phases

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Wadsö, Lars

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  1. Hydrate Control for Gas Storage Operations

    SciTech Connect

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  2. Polyethylene oxide hydration in grafted layers

    NASA Astrophysics Data System (ADS)

    Dormidontova, Elena; Wang, Zilu

    Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

  3. ConocoPhillips Gas Hydrate Production Test

    SciTech Connect

    Schoderbek, David; Farrell, Helen; Howard, James; Raterman, Kevin; Silpngarmlert, Suntichai; Martin, Kenneth; Smith, Bruce; Klein, Perry

    2013-06-30

    Work began on the ConocoPhillips Gas Hydrates Production Test (DOE award number DE-NT0006553) on October 1, 2008. This final report summarizes the entire project from January 1, 2011 to June 30, 2013.

  4. Overview: Gas hydrate geology and geography

    SciTech Connect

    Malone, R.D.

    1993-01-01

    Several geological factors which are directly responsible for the presence or absence of gas hydrates have been reviewed and are: tectonic position of the region; sedimentary environments; structural deformation; shale diapirism; hydrocarbon generation and migration; thermal regime in the hydrate formation zone (HFZ); pressure conditions; and hydrocarbon gas supply to the HFZ. Work on gas hydrate formation in the geological environment has made significant advances, but there is still much to be learned. Work is continuing in the deeper offshore areas through the Ocean Drilling Program, Government Agencies, and Industry. The pressure/temperature conditions necessary for formation has been identified for various compositions of natural gas through laboratory investigations and conditions for formation are being advanced through drilling in areas where gas hydrates exist.

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Thomas Williams; Bjorn Paulsson; Alexander Goertz

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a drilling hazard by the oil and gas industry for years. Drilling engineers working in Russia, Canada and the USA have documented numerous problems, including drilling kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates as a potential energy source agree that the resource potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained from physical samples taken from actual hydrate-bearing rocks. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The project team drilled and continuously cored the Hot Ice No. 1 well on Anadarko-leased acreage beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and used for determining physical characteristics of hydrates and surrounding rock. After the well was logged, a 3D vertical seismic profile (VSP) was recorded to calibrate the shallow geologic section with seismic data and to investigate techniques to better resolve lateral subsurface variations of potential hydrate-bearing strata. Paulsson Geophysical Services, Inc. deployed their 80 level 3C clamped borehole seismic receiver array in the wellbore to record samples every 25 ft. Seismic vibrators were successively positioned at 1185 different surface positions in a circular pattern around the wellbore. This technique generated a 3D image of the subsurface. Correlations were

  6. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Steve Runyon; Mike Globe; Kent Newsham; Robert Kleinberg; Doug Griffin

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  7. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored a well (the Hot Ice No. 1) on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in the

  8. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  9. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2004-11-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored a well (the Hot Ice No. 1) on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in the

  10. Spectroscopic methods in gas hydrate research.

    PubMed

    Rauh, Florian; Mizaikoff, Boris

    2012-01-01

    Gas hydrates are crystalline structures comprising a guest molecule surrounded by a water cage, and are particularly relevant due to their natural occurrence in the deep sea and in permafrost areas. Low molecular weight molecules such as methane and carbon dioxide can be sequestered into that cage at suitable temperatures and pressures, facilitating the transition to the solid phase. While the composition and structure of gas hydrates appear to be well understood, their formation and dissociation mechanisms, along with the dynamics and kinetics associated with those processes, remain ambiguous. In order to take advantage of gas hydrates as an energy resource (e.g., methane hydrate), as a sequestration matrix in (for example) CO(2) storage, or for chemical energy conservation/storage, a more detailed molecular level understanding of their formation and dissociation processes, as well as the chemical, physical, and biological parameters that affect these processes, is required. Spectroscopic techniques appear to be most suitable for analyzing the structures of gas hydrates (sometimes in situ), thus providing access to such information across the electromagnetic spectrum. A variety of spectroscopic methods are currently used in gas hydrate research to determine the composition, structure, cage occupancy, guest molecule position, and binding/formation/dissociation mechanisms of the hydrate. To date, the most commonly applied techniques are Raman spectroscopy and solid-state nuclear magnetic resonance (NMR) spectroscopy. Diffraction methods such as neutron and X-ray diffraction are used to determine gas hydrate structures, and to study lattice expansions. Furthermore, UV-vis spectroscopic techniques and scanning electron microscopy (SEM) have assisted in structural studies of gas hydrates. Most recently, waveguide-coupled mid-infrared spectroscopy in the 3-20 μm spectral range has demonstrated its value for in situ studies on the formation and dissociation of gas

  11. 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.

  12. 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.; ,

    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.

  13. Exploitation of subsea gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    Natural gas hydrates are considered to be a potential energy resource in the future. They occur in permafrost areas as well as in subsea sediments and are stable at high pressure and low temperature conditions. According to estimations the amount of carbon bonded in natural gas hydrates worldwide is two times larger than in all known conventional fossil fuels. Besides technical challenges that have to be overcome climate and safety issues have to be considered before a commercial exploitation of such unconventional reservoirs. The potential of producing natural gas from subsea gas hydrate deposits by various means (e.g. depressurization and/or injection of carbon dioxide) is numerically studied in the frame of the German research project »SUGAR«. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into a numerical model. The physics of the process leads to strong non-linear couplings between hydraulic fluid flow, hydrate dissociation and formation, hydraulic properties of the sediment, partial pressures and seawater solution of components and the thermal budget of the system described by the heat equation. This paper is intended to provide an overview of the recent development regarding the production of natural gas from subsea gas hydrate reservoirs. It aims at giving a broad insight into natural gas hydrates and covering relevant aspects of the exploitation process. It is focused on the thermodynamic principles and technological approaches for the exploitation. The effects occurring during natural gas production within hydrate filled sediment layers are identified and discussed by means of numerical simulation results. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is described and compared for different strategies. The simulations are complemented by calculations for different safety relevant problems.

  14. Preservation of methane hydrate at 1 atm

    USGS Publications Warehouse

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

    2001-01-01

    A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

  15. Influence of hydration and cation binding on parvalbumin dynamics

    NASA Astrophysics Data System (ADS)

    Zanotti, J.-M.; Parello, J.; Bellissent-Funel, M.-C.

    Due to structural characteristics, parvalbumin exerts a major role in intracellular Mg2+ and Ca2+ concentration regulation during the muscular contraction-relieving cycle. This structure-function relationship being established, we are investigating the structure-dynamics-function relationship to take into account the protein dynamics. Because of the strong incoherent neutron scattering cross section of hydrogen and of the abundance of this element in proteins, incoherent inelastic neutron scattering is a unique probe to study vibrations and localised motions in biological macromolecules. We take advantage of the complementarities in energy or time resolution of various neutron spectrometers (time of flight, backscattering, spin-echo) to probe the parvalbumin dynamics from a fraction of a picosecond to a few nanoseconds. Influences of hydration and of the nature of the cation on parvalbumin dynamics are discussed.

  16. Implications of abundant hygroscopic minerals in the Martian regolith

    NASA Technical Reports Server (NTRS)

    Clark, B. C.

    1978-01-01

    Converging lines of evidence suggest that a significant portion of the Martian surface fines may consist of salts and smectite clays. Salts can form stoichiometric hydrates as well as eutectic solutions with depressed freezing points; clays contain bound water of constitution and adsorb significant quantities of water from the vapor phase. The formation of ice may be suppressed by these minerals in some regions on Mars, and their presence in abundance would imply important consequences for atmospheric and geologic processes and the prospects for exobiology.

  17. Measurement of clathrate hydrates via Raman spectroscopy

    USGS Publications Warehouse

    Sum, A.K.; Burruss, R.C.; Sloan, E.D.

    1997-01-01

    Raman spectra of clathrate hydrate guest molecules are presented for three known structures (I (sI), II (sII), and H (sH)) in the following systems: CH4 (sI), CO2 (sI), C3H8 (sII), CH4 + CO2 (sI), CD4 + C3H8 (sII), CH4 + N2 (sI), CH4 + THF-d8 (sII), and CH4 + C7D14 (sH). Relative occupancy of CH4 in the large and small cavities of sI were determined by deconvoluting the ??1 symmetric bands, resulting in hydration numbers of 6.04 ?? 0.03. The frequency of the ??1 bands for CH4 in structures I, II, and H differ statistically, so that Raman spectroscopy is a potential tool to identify hydrate crystal structure. Hydrate guest compositions were also measured for two vapor compositions of the CH4 + CO2 system, and they compared favorably with predictions. The large cavities were measured to be almost fully occupied by CH4 and CO2, whereas only a small fraction of the small cavities are occupied by CH4. No CO2 was found in the small cavities. Hydration numbers from 7.27 to 7.45 were calculated for the mixed hydrate.

  18. Fe-containing phases in hydrated cements

    SciTech Connect

    Dilnesa, B.Z.; Wieland, E.; Lothenbach, B.; Dähn, R.; Scrivener, K.L.

    2014-04-01

    In this study synchrotron X-ray absorption spectroscopy (XAS) has been applied, an element specific technique which allows Fe-containing phases to be identified in the complex mineral mixture of hydrated cements. Several Fe species contributed to the overall Fe K-edge spectra recorded on the cement samples. In the early stage of cement hydration ferrite was the dominant Fe-containing mineral. Ferrihydrite was detected during the first hours of the hydration process. After 1 day the formation of Al- and Fe-siliceous hydrogarnet was observed, while the amount of ferrihydrite decreased. The latter finding agrees with thermodynamic modeling, which predicts the formation of Fe-siliceous hydrogarnet in Portland cement systems. The presence of Al- and Fe-containing siliceous hydrogarnet was further substantiated in the residue of hydrated cement by performing a selective dissolution procedure. - Highlights: • Fe bound to ferrihydrite at early age hydration • Fe found to be stable in siliceous hydrogarnet at longer term age hydration • Fe-containing AFt and AFm phases are less stable than siliceous hydrogarnet. • The study demonstrates EXAFS used to identify amorphous or poorly crystalline phases.

  19. Electrical properties of polycrystalline methane hydrate

    USGS Publications Warehouse

    Du Frane, W. L.; Stern, L.A.; Weitemeyer, K.A.; Constable, S.; Pinkston, J.C.; Roberts, J.J.

    2011-01-01

    Electromagnetic (EM) remote-sensing techniques are demonstrated to be sensitive to gas hydrate concentration and distribution and complement other resource assessment techniques, particularly seismic methods. To fully utilize EM results requires knowledge of the electrical properties of individual phases and mixing relations, yet little is known about the electrical properties of gas hydrates. We developed a pressure cell to synthesize gas hydrate while simultaneously measuring in situ frequency-dependent electrical conductivity (σ). Synthesis of methane (CH4) hydrate was verified by thermal monitoring and by post run cryogenic scanning electron microscope imaging. Impedance spectra (20 Hz to 2 MHz) were collected before and after synthesis of polycrystalline CH4 hydrate from polycrystalline ice and used to calculate σ. We determined the σ of CH4 hydrate to be 5 × 10−5 S/m at 0°C with activation energy (Ea) of 30.6 kJ/mol (−15 to 15°C). After dissociation back into ice, σ measurements of samples increased by a factor of ~4 and Ea increased by ~50%, similar to the starting ice samples.

  20. Hydrate Shell Growth Measured Using NMR.

    PubMed

    Haber, Agnes; Akhfash, Masoumeh; Loh, Charles K; Aman, Zachary M; Fridjonsson, Einar O; May, Eric F; Johns, Michael L

    2015-08-18

    Benchtop nuclear magnetic resonance (NMR) pulsed field gradient (PFG) and relaxation measurements were used to monitor the clathrate hydrate shell growth occurring in water droplets dispersed in a continuous cyclopentane phase. These techniques allowed the growth of hydrate inside the opaque exterior shell to be monitored and, hence, information about the evolution of the shell's morphology to be deduced. NMR relaxation measurements were primarily used to monitor the hydrate shell growth kinetics, while PFG NMR diffusion experiments were used to determine the nominal droplet size distribution (DSD) of the unconverted water inside the shell core. A comparison of mean droplet sizes obtained directly via PFG NMR and independently deduced from relaxation measurements showed that the assumption of the shell model-a perfect spherical core of unconverted water-for these hydrate droplet systems is correct, but only after approximately 24 h of shell growth. Initially, hydrate growth is faster and heat-transfer-limited, leading to porous shells with surface areas larger than that of spheres with equivalent volumes. Subsequently, the hydrate growth rate becomes mass-transfer-limited, and the shells become thicker, spherical, and less porous.

  1. Ground movements associated with gas hydrate production

    SciTech Connect

    Siriwardane, H.J.

    1992-10-01

    The mechanics of ground movements during hydrate production can be more closely simulated by considering similarities with ground movements associated with subsidence in permafrost regions than with gob compaction in a longwall mine. The purpose of this research work is to investigate the potential strata movements associated with hydrate production by considering similarities with ground movements in permafrost regions. The work primarily involves numerical modeling of subsidence caused by hydrate dissociation. The investigation is based on the theories of continuum mechanics , thermomechanical behavior of frozen geo-materials, and principles of rock mechanics and geomechanics. It is expected that some phases of the investigation will involve the use of finite element method, which is a powerful computer-based method which has been widely used in many areas of science and engineering. Parametric studies will be performed to predict expected strata movements and surface subsidence for different reservoir conditions and properties of geological materials. The results from this investigation will be useful in predicting the magnitude of the subsidence problem associated with gas hydrate production. The analogy of subsidence in permafrost regions may provide lower bounds for subsidence expected in hydrate reservoirs. Furthermore, it is anticipated that the results will provide insight into planning of hydrate recovery operations.

  2. Proton percolation on hydrated lysozyme powders.

    PubMed

    Careri, G; Giansanti, A; Rupley, J A

    1986-09-01

    The framework of percolation theory is used to analyze the hydration dependence of the capacitance measured for protein samples of pH 3-10, at frequencies from 10 kHz to 4 MHz. For all samples there is a critical value of the hydration at which the capacitance sharply increases with increase in hydration level. The threshold h(c) = 0.15 g of water per g of protein is independent of pH below pH 9 and shows no solvent deuterium isotope effect. The fractional coverage of the surface at h(c) is in close agreement with the prediction of theory for surface percolation. We view the protonic conduction process described here for low hydration and previously for high hydration as percolative proton transfer along threads of hydrogen-bonded water molecules. A principal element of the percolation picture, which explains the invariance of h(c) to change in pH and solvent, is the sudden appearance of long-range connectivity and infinite clusters at the threshold h(c). The relationship of the protonic conduction threshold to other features of protein hydration is described. The importance of percolative processes for enzyme catalysis and membrane transport is discussed.

  3. The hydration properties of carboxybetaine zwitterion brushes.

    PubMed

    Du, Hongbo; Qian, Xianghong

    2016-04-15

    Combined quantum mechanical calculations and classical molecular dynamics simulations were conducted to investigate the hydration properties of carboxybetaine zwitterion brushes with varying separation distances between the quaternary ammonium cation and carboxylic anion. The brushes consist of zwitterion trimers and are investigated to mimic interacting zwitterion chains grafted on a substrate as well as polymers with interacting zwitterion side chains. Our results show that the values of both positive and negative charges, their separation distances as well as chain interactions appear to play a critical role in the hydration properties of the zwitterions. The overall hydration property of these zwitterions is dictated by the competition between the strong hydration of the charged groups and the dehydration of the hydrocarbon chains. The strongest hydration occurs when the -CH2- unit in the hydrocarbon chain reaches 6-8 for these trimers. Further increase in the hydrocarbon chain length to 10-14 leads to significant and sudden dehydration of the trimers. The water structure and the water residence time surrounding the zwitterions also demonstrate substantial alteration at this length scale. This hydrophilic-to-hydrophobic transition is induced by the hydrophobic interactions of the trimer chains. Our hydration results could explain the observed trend of the superiority of the methylated carbohydrates and poly(ethylene glycol) as antifouling materials compared to corresponding hydroxyl-terminated compounds.

  4. Clathrate hydrates in the solar system

    NASA Technical Reports Server (NTRS)

    Miller, S. L.

    1985-01-01

    Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.

  5. Surfactant effects on SF6 hydrate formation.

    PubMed

    Lee, Bo Ram; Lee, Ju Dong; Lee, Hyun Ju; Ryu, Young Bok; Lee, Man Sig; Kim, Young Seok; Englezos, Peter; Kim, Myung Hyun; Kim, Yang Do

    2009-03-01

    Sulfur hexafluoride (SF(6)) has been widely used in a variety of industrial processes, but it is one of the most potent greenhouse gases. For this reason, it is necessary to separate or collect it from waste gas streams. One separation method is through hydrate crystal formation. In this study, SF(6) hydrate was formed in aqueous surfactant solutions of 0.00, 0.01, 0.05, 0.15 and 0.20 wt% to investigate the effects of surfactants on the hydrate formation rates. Three surfactants, Tween 20 (Tween), sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), were tested in a semi-batch stirred vessel at the constant temperature and pressures of 276.2 K and 0.78 MPa, respectively. All surfactants showed kinetic promoter behavior for SF(6) hydrate formation. It was also found that SF(6) hydrate formation proceeded in two stages with the second stage being the most rapid. In situ Raman spectroscopy analysis revealed that the increased gas consumption rate with the addition of surfactant was possibly due to the increased gas filling rate in the hydrate cavity.

  6. Weakly Hydrated Surfaces and the Binding Interactions of Small Biological Solutes

    SciTech Connect

    Brady, J. W.; Tavagnacco, L.; Ehrlich, L.; Chen, M.; Schnupf, U.; Himmel, M. E.; Saboungi, M. L.; Cesaro, A.

    2012-04-01

    Extended planar hydrophobic surfaces, such as are found in the side chains of the amino acids histidine, phenylalanine, tyrosine, and tryptophan, exhibit an affinity for the weakly hydrated faces of glucopyranose. In addition, molecular species such as these, including indole, caffeine, and imidazole, exhibit a weak tendency to pair together by hydrophobic stacking in aqueous solution. These interactions can be partially understood in terms of recent models for the hydration of extended hydrophobic faces and should provide insight into the architecture of sugar-binding sites in proteins.

  7. Weakly hydrated surfaces and the binding interactions of small biological solutes.

    PubMed

    Brady, John W; Tavagnacco, Letizia; Ehrlich, Laurent; Chen, Mo; Schnupf, Udo; Himmel, Michael E; Saboungi, Marie-Louise; Cesàro, Attilio

    2012-04-01

    Extended planar hydrophobic surfaces, such as are found in the side chains of the amino acids histidine, phenylalanine, tyrosine, and tryptophan, exhibit an affinity for the weakly hydrated faces of glucopyranose. In addition, molecular species such as these, including indole, caffeine, and imidazole, exhibit a weak tendency to pair together by hydrophobic stacking in aqueous solution. These interactions can be partially understood in terms of recent models for the hydration of extended hydrophobic faces and should provide insight into the architecture of sugar-binding sites in proteins.

  8. Hydration during intense exercise training.

    PubMed

    Maughan, R J; Meyer, N L

    2013-01-01

    Hydration status has profound effects on both physical and mental performance, and sports performance is thus critically affected. Both overhydration and underhydration - if sufficiently severe - will impair performance and pose a risk to health. Athletes may begin exercise in a hypohydrated state as a result of incomplete recovery from water loss induced in order to achieve a specific body mass target or due to incomplete recovery from a previous competition or training session. Dehydration will also develop in endurance exercise where fluid intake does not match water loss. The focus has generally been on training rather than on competition, but sweat loss and fluid replacement in training may have important implications. Hypohydration may impair training quality and may also increase stress levels. It is unclear whether this will have negative effects (reduced training quality, impaired immunity) or whether it will promote a greater adaptive response. Hypohydration and the consequent hyperthermia, however, can enhance the effectiveness of a heat acclimation program, resulting in improved endurance performance in warm and temperate environments. Drinking in training may be important in enhancing tolerance of the gut when athletes plan to drink in competition. The distribution of water between body water compartments may also be important in the initiation and promotion of cellular adaptations to the training stimulus.

  9. Solid state characterization of the anti-HIV drug TMC114: interconversion of amorphous TMC114, TMC114 ethanolate and hydrate.

    PubMed

    Van Gyseghem, Elke; Stokbroekx, Sigrid; de Armas, Hector Novoa; Dickens, Jules; Vanstockem, Marc; Baert, Lieven; Rosier, Jan; Schueller, Laurent; Van den Mooter, Guy

    2009-12-08

    The interconversion of the ethanolate, hydrate and amorphous form of TMC114 ((3-[(4-amino-benzenesulfonyl)-isobutyl-amino]-1-benzyl-2-hydroxypropyl)-carbamic acid hexahydrofuro-[2,3-b]furan-3-yl ester) in open conditions was characterized. TMC114 hydrate and ethanolate form isostructural channel solvates. The crystal structure of TMC114 was obtained from single crystal X-ray diffraction, confirming that it is a channel solvate. Ethanol and water can exchange with one another. TMC114 ethanolate converts into TMC114 hydrate at moderate or high relative humidity (RH) at 25 degrees C, and it converts back into the ethanolate in ethanol atmosphere. The hydration level of the hydrate is determined by the environmental humidity. TMC114 hydrate collapses to the amorphous product when water is removed by drying at low RH or increasing temperature. TMC114 ethanolate becomes amorphous at elevated temperature in a dry environment below the desolvation temperature. Amorphous TMC114 obtained by dehydrating the hydrate during storage at room temperature/<5% RH, by increasing the temperature, or via desolvating the ethanolate by heating, converts into the hydrate at moderate or high RH at ambient conditions, and into TMC114 ethanolate in an ethanol atmosphere. Under ambient conditions, TMC114 ethanolate may convert into the hydrate, whereas the opposite will not occur under these conditions. The amorphous form, prepared by melting-quenching shows a limited water uptake. Whereas TMC114 ethanolate is stable in the commercialized drug product, special conditions can trigger its conversion.

  10. Hydration Mechanisms, Crystal Preferred Orientation, and Anisotropy in the Upper Mantle and Transition Zone

    NASA Astrophysics Data System (ADS)

    Smyth, J. R.; Ye, Y.; Jacobsen, S. D.

    2011-12-01

    Nominally anhydrous silicate minerals of the upper mantle and transition zone incorporate H2O into their structures at mantle temperatures and pressures as ordered hydroxyl defects. These defects can commonly be identified by single-crystal X-ray diffraction and polarized infrared spectroscopy. Regional or large-scale mantle hydration can account for two to ten times the mass of water in Earth's oceans affecting anisotropic elastic properties of the mantle's constituent minerals such that hydration causes distinct patterns of seismic anisotropy. Recent crystallographic studies indicate that the principal hydration mechanism of the nominally anhydrous minerals is by protonation of octahedral (Mg,Fe) cation vacancies. Here we show that in the most abundant minerals of the upper 660km, olivine (alpha), wadsleyite (beta), and ringwoodite (gamma) polymorphs of Mg2SiO4, hydrated point defects order to form planes of weakness that can control lattice preferred orientation and velocity anisotropy in various regions of the upper mantle and transition zone. In olivine, ordering of protonated (Mg,Fe) vacancies in the M1 octahedral site predicts that hydration will enhance c-axis alignment parallel to the direction of shear in the (010) plane, as in type-B LPO with SH > SV by up to 10% under horizontal shear. In wadsleyite, vacancies and protons order into the M3 octahedral sites which form double edge-sharing chains of octahedra parallel to a. This vacancy ordering predicts a slip vector of [100] on {011} planes and, unlike olivine, would produce SH < SV by up to 2-6% under horizontal or vertical shear. In ringwoodite, velocity anisotropy is weak, but shear velocity differences of one or two percent are possible. Velocity and electrical conductivity anisotropy may thus be useful indicators of hydration in planetary interiors.

  11. Flare Plasma Iron Abundance

    NASA Technical Reports Server (NTRS)

    Dennis, Brian R.; Dan, Chau; Jain, Rajmal; Schwartz, Richard A.; Tolbert, Anne K.

    2008-01-01

    The equivalent width of the iron-line complex at 6.7 keV seen in flare X-ray spectra suggests that the iron abundance of the hottest plasma at temperatures >approx.10 MK may sometimes be significantly lower than the nominal coronal abundance of four times the photospheric value that is commonly assumed. This conclusion is based on X-ray spectral observations of several flares seen in common with the Ramaty High Energy Solar Spectroscopic Imager (RHESSI) and the Solar X-ray Spectrometer (SOXS) on the second Indian geostationary satellite, GSAT-2. The implications of this will be discussed as it relates to the origin of the hot flare plasma - either plasma already in the corona that is directly heated during the flare energy release process or chromospheric plasma that is heated by flare-accelerated particles and driven up into the corona. Other possible explanations of lower-than-expected equivalent widths of the iron-line complex will also be discussed.

  12. Hydrate pingoes at Nyegga: some characteristic features

    NASA Astrophysics Data System (ADS)

    Hovland, M.

    2009-04-01

    Hydrate pingoes were observed on the seafloor during two different remotely operated vehicle (ROV)-dives, conducted by Statoil at complex-pockmark G11, at Nyegga, off Mid-Norway. Confirmation that these structures actually represent hydrate ice-cored sediment mounds (pingoes), was done by other investigators (Ivanov et al., 2006). Because it is expected that hydrate pingoes represent relatively dynamic seafloor topographic structures and that their shape and size most probably will change over relatively short time, it is important to know how to recognise them visually. Hovland and Svensen (2006) highlighted five different characteristic aspects that define hydrate pingoes on the sea floor: 1) They are dome- or disc-shaped features, which may attain any size from ~0.5 m in height and upwards. Inside pockmark G11, they were up to 1 m high. 2) They are circular or oval in plan view and may attain lateral sizes on the seafloor ranging upwards from ~0.5 m. Inside G11 they had lengths of several metres and widths of up to 4 m. 3) They have dense communities of organisms growing on their surfaces. At G11, they were overgrown with small pogonophoran tube-worms. 4) They have patches of white or grey bacterial mats growing on their surface, indicating advection (seepage) of reduced pore-waters. 5) They have small pits and patches of fluidized sediments on their surface, indicating pit corrosion of the sub-surface gas hydrate. Because gas hydrates often form in high-porosity, near-surface sediments, where water is readily available, it is thought that they will build up at locations where gases are actively migrating upwards from depth. However, gas hydrates are not stable in the presence of ambient seawater, as seawater is deficient in guest molecule gases (normally methane). Therefore, they tend to build up below surface above conduits for gas flow from depth. But, the near-surface hydrate ice-lenses will continually be corroded by seawater circulating into the sediments

  13. Pf1 bacteriophage hydration by magic angle spinning solid-state NMR

    SciTech Connect

    Sergeyev, Ivan V.; Bahri, Salima; McDermott, Ann E.; Day, Loren A.

    2014-12-14

    High resolution two- and three-dimensional heteronuclear correlation spectroscopy ({sup 1}H–{sup 13}C, {sup 1}H–{sup 15}N, and {sup 1}H–{sup 13}C–{sup 13}C HETCOR) has provided a detailed characterization of the internal and external hydration water of the Pf1 virion. This long and slender virion (2000 nm × 7 nm) contains highly stretched DNA within a capsid of small protein subunits, each only 46 amino acid residues. HETCOR cross-peaks have been unambiguously assigned to 25 amino acids, including most external residues 1–21 as well as residues 39–40 and 43–46 deep inside the virion. In addition, the deoxyribose rings of the DNA near the virion axis are in contact with water. The sets of cross-peaks to the DNA and to all 25 amino acid residues were from the same hydration water {sup 1}H resonance; some of the assigned residues do not have exchangeable side-chain protons. A mapping of the contacts onto structural models indicates the presence of water “tunnels” through a highly hydrophobic region of the capsid. The present results significantly extend and modify results from a lower resolution study, and yield a comprehensive hydration surface map of Pf1. In addition, the internal water could be distinguished from external hydration water by means of paramagnetic relaxation enhancement. The internal water population may serve as a conveniently localized magnetization reservoir for structural studies.

  14. Pf1 bacteriophage hydration by magic angle spinning solid-state NMR

    NASA Astrophysics Data System (ADS)

    Sergeyev, Ivan V.; Bahri, Salima; Day, Loren A.; McDermott, Ann E.

    2014-12-01

    High resolution two- and three-dimensional heteronuclear correlation spectroscopy (1H-13C, 1H-15N, and 1H-13C-13C HETCOR) has provided a detailed characterization of the internal and external hydration water of the Pf1 virion. This long and slender virion (2000 nm × 7 nm) contains highly stretched DNA within a capsid of small protein subunits, each only 46 amino acid residues. HETCOR cross-peaks have been unambiguously assigned to 25 amino acids, including most external residues 1-21 as well as residues 39-40 and 43-46 deep inside the virion. In addition, the deoxyribose rings of the DNA near the virion axis are in contact with water. The sets of cross-peaks to the DNA and to all 25 amino acid residues were from the same hydration water 1H resonance; some of the assigned residues do not have exchangeable side-chain protons. A mapping of the contacts onto structural models indicates the presence of water "tunnels" through a highly hydrophobic region of the capsid. The present results significantly extend and modify results from a lower resolution study, and yield a comprehensive hydration surface map of Pf1. In addition, the internal water could be distinguished from external hydration water by means of paramagnetic relaxation enhancement. The internal water population may serve as a conveniently localized magnetization reservoir for structural studies.

  15. Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Snead, C. J.; Keller, L. P.; McKeegan, K. D.; Messenger, S.

    2016-01-01

    Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass

  16. Hydration of NaDNA by neutron quasi-elastic scattering.

    PubMed Central

    Schreiner, L J; Pintar, M M; Dianoux, A J; Volino, F; Rupprecht, A

    1988-01-01

    Preliminary results of neutron quasi-elastic scattering experiments are reported for hydrated paracrystals of sodium deoxyribonucleic acid (NaDNA). The samples were investigated at two water contents: 3.5 +/- 1.0 and 9.5 +/- 1.5 mol H2O per mole nucleotide. The results of the scattering experiments were almost independent of whether the NaDNA fibers were oriented parallel or perpendicular to the momentum transfer. The data indicate that at the lower hydration the water molecules do not diffuse appreciably on the time scale of the neutron measurements (approximately 3 X 10(-10) s). At the higher hydration the water molecules diffuse isotropically in a sphere of 9 A in diameter with a diffusion coefficient of (5 +/- 2) X 10(-6) cm2 s-1. PMID:3342269

  17. About transformation of the deep-water methane bubbles into hydrate powder and hydrate foam

    NASA Astrophysics Data System (ADS)

    Egorov, A. V.; Nigmatulin, R. I.; Rozhkov, A. N.; Sagalevich, A. M.; Chernyaev, E. S.

    2012-04-01

    During the Russian Academy of Sciences "MIRI na Baikale, 2008-2010" expedition, deep-water experiments with the bubbles of methane seeping from the bottom at depths 405, 860 and 1400 meters were carried out. These depths correspond to gas hydrate stability zone. Bubbles were caught by the trap which was looked like an inverted glass. It was found that the behavior of bubbles in a trap depends on the depth. At depth of 405 meters formation of hydrates was not observed. Having got to a trap at the depth of 860 meters, bubbles became covered by solid hydrate envelope, kept the initial form, and after a time period collapsed in a number of hydrate fragments which showed all properties of a granular matter. No visible changes in the hydrate granular matter were observed in the course of lifting it to a depth of 380 meters. Shallower, the decomposition of the hydrate granular matter into methane gas was observed. In the experiments at depth of 1400 meters the caught bubbles, becoming covered by hydrate envelope formed solid hydrate foam in the trap. At lifting this foam structure was deformed slightly but simultaneously a free gas left the foam and filled the trap. The volume of free gas in the trap at lifting varied according to the Boyle-Mariotte law.

  18. Controls on Gas Hydrate Formation and Dissociation

    SciTech Connect

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  19. Properties of equilibrium carbon dioxide hydrate in porous medium

    NASA Astrophysics Data System (ADS)

    Voronov, V. P.; Gorodetskii, E. E.; Podnek, V. E.; Grigoriev, B. A.

    2016-09-01

    Specific heat capacity, dissociation heat and hydration number of carbon dioxide hydrate in porous medium are determined by adiabatic calorimetry method. The measurements were carried out in the temperature range 250-290 K and in pressure range 1-5 MPa. The measured specific heat of the hydrate is approximately 2.7 J/(g K), which is significantly larger than the specific heat of methane hydrate. In particular, at heating, larger value of the specific heat of carbon dioxide hydrate is a result of gas emission from the hydrate. The hydration number at the hydrate-gas coexistence changes from 6.2 to 6.9. The dissociation heat of carbon dioxide hydrate varies from the 55 kJ/mol near the upper quadruple point to the 57 kJ/mol near the lower quadruple point.

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

    PubMed

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

    2012-05-01

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

  1. Facile synthesis of highly active hydrated yttrium oxide towards arsenate adsorption.

    PubMed

    Yu, Yang; Yu, Ling; Sun, Min; Paul Chen, J

    2016-07-15

    A novel hydrated yttrium oxide adsorbent with high capacity towards the arsenate (As(V)) adsorption was fabricated by a one-step hydrothermal process. Structure analysis identified the hydrated yttrium oxide to be Y2O(OH)4·1.5H2O, which displayed as irregular rods in the range of tens to hundreds of nanometers. The adsorbent exhibited favorable As(V) adsorption efficiency in a wide pH range from 4.0 to 7.0, with the maximum adsorption capacity of 480.2mg-As/g obtained at pH 5.0. Both the kinetics and isotherm studies demonstrated that the adsorption of the As(V) was a monolayer chemical adsorption process, in which the ion exchange between the hydroxyl groups on the hydrated yttrium oxide and arsenate anions played a key role in the uptake of the As(V). During the adsorption, the As(V) anions were replaced the hydroxyl groups and bound to the hydrated yttrium oxide via the linkage of AsOY. The presence of fluoride and phosphate greatly hindered the As(V) uptake on the hydrated yttrium oxide, whereas the bicarbonate, sulfate and humic acid showed insignificant impacts on the removal.

  2. Origin and evolution of fracture-hosted methane hydrate deposits

    NASA Astrophysics Data System (ADS)

    Daigle, Hugh; Dugan, Brandon

    2010-11-01

    Fracture-hosted methane hydrate deposits exist at many sites worldwide. These sites often have hydrate present as vein and fracture fill, as well as disseminated through the pore space. We estimate that thousands to millions of years are required to form fracture systems by hydraulic fracturing driven by occlusion of the pore system by hydrate. This time scale is a function of rates of fluid flow and permeability loss. Low-permeability layers in a sedimentary column can reduce this time if the permeability contrast with respect to the surrounding sediments is of order 10 or greater. Additionally, we find that tensile fracturing produced by hydrate heave around hydrate lenses is a viable fracture mechanism over all but the lowermost part of the hydrate stability zone. With our coupled fluid flow-hydrate formation model we assess fracture formation at four well-studied hydrate provinces: Blake Ridge offshore South Carolina, Hydrate Ridge offshore Oregon, Keathley Canyon Block 151 offshore Louisiana, and the Krishna-Godavari Basin offshore India. We conclude that hydraulic fracturing due to pore pressure buildup is reasonable only at Hydrate Ridge and the Krishna-Godavari Basin owing to sediment age constraints, and that hydrate-filled fractures observed at Blake Ridge and Keathley Canyon Block 151 are formed either by hydrate heave or in preexisting fractures. Our findings offer new insight into the processes and time scales associated with fracture-hosted hydrate deposits, which help further our understanding of hydrate systems.

  3. High