Specimen preparation for cryogenic coherent X-ray diffraction imaging of biological cells and cellular organelles by using the X-ray free-electron laser at SACLA

PubMed Central

Kobayashi, Amane; Sekiguchi, Yuki; Oroguchi, Tomotaka; Okajima, Koji; Fukuda, Asahi; Oide, Mao; Yamamoto, Masaki; Nakasako, Masayoshi

2016-01-01

Coherent X-ray diffraction imaging (CXDI) allows internal structures of biological cells and cellular organelles to be analyzed. CXDI experiments have been conducted at 66 K for frozen-hydrated biological specimens at the SPring-8 Angstrom Compact Free-Electron Laser facility (SACLA). In these cryogenic CXDI experiments using X-ray free-electron laser (XFEL) pulses, specimen particles dispersed on thin membranes of specimen disks are transferred into the vacuum chamber of a diffraction apparatus. Because focused single XFEL pulses destroy specimen particles at the atomic level, diffraction patterns are collected through raster scanning the specimen disks to provide fresh specimen particles in the irradiation area. The efficiency of diffraction data collection in cryogenic experiments depends on the quality of the prepared specimens. Here, detailed procedures for preparing frozen-hydrated biological specimens, particularly thin membranes and devices developed in our laboratory, are reported. In addition, the quality of the frozen-hydrated specimens are evaluated by analyzing the characteristics of the collected diffraction patterns. Based on the experimental results, the internal structures of the frozen-hydrated specimens and the future development for efficient diffraction data collection are discussed. PMID:27359147

Specimen preparation for cryogenic coherent X-ray diffraction imaging of biological cells and cellular organelles by using the X-ray free-electron laser at SACLA.

PubMed

Kobayashi, Amane; Sekiguchi, Yuki; Oroguchi, Tomotaka; Okajima, Koji; Fukuda, Asahi; Oide, Mao; Yamamoto, Masaki; Nakasako, Masayoshi

2016-07-01

Coherent X-ray diffraction imaging (CXDI) allows internal structures of biological cells and cellular organelles to be analyzed. CXDI experiments have been conducted at 66 K for frozen-hydrated biological specimens at the SPring-8 Angstrom Compact Free-Electron Laser facility (SACLA). In these cryogenic CXDI experiments using X-ray free-electron laser (XFEL) pulses, specimen particles dispersed on thin membranes of specimen disks are transferred into the vacuum chamber of a diffraction apparatus. Because focused single XFEL pulses destroy specimen particles at the atomic level, diffraction patterns are collected through raster scanning the specimen disks to provide fresh specimen particles in the irradiation area. The efficiency of diffraction data collection in cryogenic experiments depends on the quality of the prepared specimens. Here, detailed procedures for preparing frozen-hydrated biological specimens, particularly thin membranes and devices developed in our laboratory, are reported. In addition, the quality of the frozen-hydrated specimens are evaluated by analyzing the characteristics of the collected diffraction patterns. Based on the experimental results, the internal structures of the frozen-hydrated specimens and the future development for efficient diffraction data collection are discussed.

Cryogenic x-ray diffraction microscopy utilizing high-pressure cryopreservation

NASA Astrophysics Data System (ADS)

Lima, Enju; Chushkin, Yuriy; van der Linden, Peter; Kim, Chae Un; Zontone, Federico; Carpentier, Philippe; Gruner, Sol M.; Pernot, Petra

2014-10-01

We present cryo x-ray diffraction microscopy of high-pressure-cryofixed bacteria and report high-convergence imaging with multiple image reconstructions. Hydrated D. radiodurans cells were cryofixed at 200 MPa pressure into ˜10-μm-thick water layers and their unstained, hydrated cellular environments were imaged by phasing diffraction patterns, reaching sub-30-nm resolutions with hard x-rays. Comparisons were made with conventional ambient-pressure-cryofixed samples, with respect to both coherent small-angle x-ray scattering and the image reconstruction. The results show a correlation between the level of background ice signal and phasing convergence, suggesting that phasing difficulties with frozen-hydrated specimens may be caused by high-background ice scattering.

A cylindrical specimen holder for electron cryo-tomography

PubMed Central

Palmer, Colin M.; Löwe, Jan

2014-01-01

The use of slab-like flat specimens for electron cryo-tomography restricts the range of viewing angles that can be used. This leads to the “missing wedge” problem, which causes artefacts and anisotropic resolution in reconstructed tomograms. Cylindrical specimens provide a way to eliminate the problem, since they allow imaging from a full range of viewing angles around the tilt axis. Such specimens have been used before for tomography of radiation-insensitive samples at room temperature, but never for frozen-hydrated specimens. Here, we demonstrate the use of thin-walled carbon tubes as specimen holders, allowing the preparation of cylindrical frozen-hydrated samples of ribosomes, liposomes and whole bacterial cells. Images acquired from these cylinders have equal quality at all viewing angles, and the accessible tilt range is restricted only by the physical limits of the microscope. Tomographic reconstructions of these specimens demonstrate that the effects of the missing wedge are substantially reduced, and could be completely eliminated if a full tilt range was used. The overall quality of these tomograms is still lower than that obtained by existing methods, but improvements are likely in future. PMID:24275523

Hard X-ray Ptychography: Making It Cool, Colorful and Fast

NASA Astrophysics Data System (ADS)

Deng, Junjing

Ptychography is a recently developed coherent imaging technique for extended objects, with a resolution not limited by the lens. Because X-rays have short wavelengths and high penetration ability, X-ray ptychography provides a powerful and unique tool for studying thick samples at high spatial resolution. We have advanced X-ray ptychography by making it cool, colorful, and fast. We make it cool by carrying out ptychography experiments at cryogenic conditions to image frozen-hydrated specimens. This largely removes the limitations of radiation damage on the achievable resolution, and allows one to obtain excellent preservation of structure and chemistry in biological specimens. We make it colorful by combining it with X-ray fluorescence measurements of chemical element distributions. In studies of biological specimens, this means that ptychography can reveal cellular ultrastructure at high contrast and at a resolution well beyond that of X-ray focusing optics, while X-ray fluorescence is used to simultaneously image the distribution of trace elements in cells (such as metals that play key roles in cell functions and which can be used in various disease therapeutic agents). Because X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular materials, this combined approach provides the unique tool to obtain simultaneous views of ultrastructure and elemental compositions of specimens. We make it fast by using continuous-scan (or "fly-scan") methods. Conventional ptychography is implemented in a move-settle-measure approach, which is slow due to the positioning overheads. To overcome this bottleneck, we have developed fly-scan ptychography that is able to speed up the data collection, and real time on-site data analysis can be achieved by using a parallelized reconstruction code. With these advances, we conducted combined cryo X-ray ptychography and fluorescence imaging at 5.2 keV in a more practical way using fly scan, well-preserved cryogenic samples and rapid reconstructions, and obtained images of a whole frozen-hydrated eukaryotic cell at 18 nm resolution which we believe to be the highest spatial resolution obtained in X-ray imaging of frozen-hydrated biological samples to date. After a successful demonstration of fly-scan 3D ptychography on a gold test sample, we also obtained fly-scan 3D ptychography and fluorescence data on frozen-hydrated cells with an imaging speedup of factor more than 7. Finally, we applied fly-scan X-ray ptychography on un-thinned integrated circuits (ICs) using 10 keV X-rays, and were able to see the circuit details within the thick IC chips with a high resolution of 11.6 nm. All of these achievements point the way toward high-speed X-ray imaging without lens-imposed resolution limit.

X-ray diffraction microscopy on frozen hydrated specimens

NASA Astrophysics Data System (ADS)

Nelson, Johanna

X-rays are excellent for imaging thick samples at high resolution because of their large penetration depth compared to electrons and their short wavelength relative to visible light. To image biological material, the absorption contrast of soft X-rays, especially between the carbon and oxygen K-shell absorption edges, can be utilized to give high contrast, high resolution images without the need for stains or labels. Because of radiation damage and the desire for high resolution tomography, live cell imaging is not feasible. However, cells can be frozen in vitrified ice, which reduces the effect of radiation damage while maintaining their natural hydrated state. X-ray diffraction microscopy (XDM) is an imaging technique which eliminates the limitations imposed by current focusing optics simply by removing them entirely. Far-field coherent diffraction intensity patterns are collected on a pixelated detector allowing every scattered photon to be collected within the limits of the detector's efficiency and physical size. An iterative computer algorithm is then used to invert the diffraction intensity into a real space image with both absorption and phase information. This technique transfers the emphasis away from fabrication and alignment of optics, and towards data processing. We have used this method to image a pair of freeze-dried, immuno-labeled yeast cells to the highest resolution (13 nm) yet obtained for a whole eukaryotic cell. We discuss successes and challenges in working with frozen hydrated specimens and efforts aimed at high resolution imaging of vitrified eukaryotic cells in 3D.

X-ray ptychographic and fluorescence microscopy of frozen-hydrated cells using continuous scanning

DOE PAGES

Deng, Junjing; Vine, David J.; Chen, Si; ...

2017-03-27

X-ray microscopy can be used to image whole, unsectioned cells in their native hydrated state. It complements the higher resolution of electron microscopy for submicrometer thick specimens, and the molecule-specific imaging capabilites of fluorescence light microscopy. We describe here the first use of fast, continuous x-ray scanning of frozen hydrated cells for simultaneous sub-20 nm resolution ptychographic transmission imaging with high contrast, and sub-100 nm resolution deconvolved x-ray fluorescence imaging of diffusible and bound ions at native concentrations, without the need to add specific labels. Here, by working with cells that have been rapidly frozen without the use of chemicalmore » fixatives, and imaging them under cryogenic conditions, we are able to obtain images with well preserved structural and chemical composition, and sufficient stability against radiation damage to allow for multiple images to be obtained with no observable change.« less

Soft X-Ray Diffraction Microscopy of a Frozen Hydrated Yeast Cell

DOE PAGES

Huang, Xiaojing; Nelson, Johanna; Kirz, Janos; ...

2009-11-01

We report the first image of an intact, frozen hydrated eukaryotic cell using x-ray diffraction microscopy, or coherent x-ray diffraction imaging. By plunge freezing the specimen in liquid ethane and maintaining it below -170 °C, artifacts due to dehydration, ice crystallization, and radiation damage are greatly reduced. In this example, coherent diffraction data using 520 eV x rays were recorded and reconstructed to reveal a budding yeast cell at a resolution better than 25 nm. This demonstration represents an important step towards high resolution imaging of cells in their natural, hydrated state, without limitations imposed by x-ray optics.

Peculiarities of CO2 sequestration in the Permafrost area

NASA Astrophysics Data System (ADS)

Guryeva, Olga; Chuvilin, Evgeny; Moudrakovski, Igor; Lu, Hailong; Ripmeester, John; Istomin, Vladimir

2010-05-01

Natural gas and gas-condensate accumulations in North of Western Siberia contain an admixture of CO2 (about 0.5-1.0 mol.%). Recently, the development and transportation of natural gas in the Yamal peninsula has become of interest to Russian scientists. They suggest liquifaction of natural gas followed by delivery to consumers using icebreaking tankers. The technique of gas liquefaction requires CO2 to be absent from natural gas, and therefore the liquefaction technology includes the amine treatment of gas. This then leads to a problem with utilization of recovered CO2. It is important to note, that gas reservoirs in the northern part of Russia are situated within the Permafrost zone. The thickness of frozen sediment reaches 500 meters. That is why one of the promising places for CO2 storage can be gas-permeable collectors in under-permafrost horizons. The favorable factors for preserving CO2 in these places are as follows: low permeability of overlying frozen sediments, low temperatures, the existence of a CO2 hydrate stability zone, and the possibility of sequestration at shallow depths (less then 800-1000 meters). When CO2 (in liquid or gas phase) is pumped into the under-permafrost collectors it is possible that some CO2 migrates towards the hydrate stability zone and hydrate-saturated horizons can be formed. This can result on the one hand in the increase of effective capacity of the collector, and on the other hand, in the increase of isolating properties of cap rock. Therefore, CO2 injection sometimes can be performed without a good cap rock. In connection with the abovementioned, to elaborate an effective technology for CO2 injection it is necessary to perform a comprehensive experimental investigation with computer simulation of different utilization schemes, including the process of CO2 hydrate formation in porous media. There are two possible schemes of hydrate formation in pore medium of sediments: from liquid CO2 or the gas. The pore water in the sediment may be either in frozen or liquid states. To study these processes, an experimental investigation of hydrate formation kinetics from liquid and gaseous CO2 has been performed using the method of NMR imaging*. Experiments were made with samples of quartz sand (particles' diameter 0,21-0,297mm) with different water saturation in the range of temperatures between -3 and +8oC and pressures between 3 and 6 MPa. The experiments performed revealed the main regularities of hydrate accumulation from liquid CO2 in sediment. The influence of temperature on the rate of pore hydrate growth was analyzed. For example, the rate of hydrate growth at +7.2oC was 6 times smaller then at -3 оС. Fast hydrate formation from liquid CO2 was observed in sand samples with water saturation below 20-30%. With an increase in water saturation to 50%, the rate of hydrate formation decreased significantly, and when water saturation was 60% or more, nucleation was not observed during the time of the experiment (1-3 days). Experimental results revealed that pressure variation in the range between 4 and 6 MPa does not have any influence on the kinetics of hydrate formation from liquid CO2. Comparison of kinetics of hydrate formation from liquid and gas CO2 showed that hydrate accumulation is faster from gas CO2 then from liquid CO2. Thus, 50% of pore water that reacted with liquid CO2 transformed into hydrate in 0.8 hours after nucleation, and when reacted with CO2-gas, it transformed in 0.3 hours. The completed experiments allowed us to consider the peculiarities of hydrate formation and filtration of liquid and gaseous CO2 towards the hydrate stability zone, which is important to take into account during the elaboration of industrial techniques of CO2 injection in under-permafrost collectors. * Experiments have been made in the laboratory of NRC of Canada.

Effect of Chitin Isolated from Crustaceans and Cephalopods on Denaturation of Fish Myofibrillar Protein and the State of Water during Frozen Storage

NASA Astrophysics Data System (ADS)

Yamashita, Yasumitsu; Zhang, Nong; Nozaki, Yukinori

The effect of chitin hydrolysate made from shell of crustaceans and cartilage of cephalopods on the denaturation and the state of water of lizard fish myofibrillar protein (Mf) during frozen storage at -250°C for 120 days were investigated. 5.0% chitin hydrolysate (dried matter) added Mf samples were frozen at -25°C and storage for 120 days, and the change of inactivation of Mf Ca-ATPase and the change of unfrozen water in Mf were examined during the frozen storage. The decrease of Mf Ca-ATPase during frozen storage were slow by addition of chitin hydrolysate. The amount of unfrozen water in Mf were increased by addition of chitin hydrolysate, and decreaced gradually during frozen storage. On the other hand, the amount of unfrozen water of the control were decreaced suddenly during frozen storage. Above results suggest that chitin hydrolysate has cryoprotective effect on Mf. It is guessed that the mechanism of cryoprotective effect of chitin hydrolysate may be caused by an interaction between hydration sphere of Mf and equatorial OH groups in the molecular structure of chitin hydrolysate.

A cylindrical specimen holder for electron cryo-tomography.

PubMed

Palmer, Colin M; Löwe, Jan

2014-02-01

The use of slab-like flat specimens for electron cryo-tomography restricts the range of viewing angles that can be used. This leads to the "missing wedge" problem, which causes artefacts and anisotropic resolution in reconstructed tomograms. Cylindrical specimens provide a way to eliminate the problem, since they allow imaging from a full range of viewing angles around the tilt axis. Such specimens have been used before for tomography of radiation-insensitive samples at room temperature, but never for frozen-hydrated specimens. Here, we demonstrate the use of thin-walled carbon tubes as specimen holders, allowing the preparation of cylindrical frozen-hydrated samples of ribosomes, liposomes and whole bacterial cells. Images acquired from these cylinders have equal quality at all viewing angles, and the accessible tilt range is restricted only by the physical limits of the microscope. Tomographic reconstructions of these specimens demonstrate that the effects of the missing wedge are substantially reduced, and could be completely eliminated if a full tilt range was used. The overall quality of these tomograms is still lower than that obtained by existing methods, but improvements are likely in future. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Natural gas hydrate in sediments imaged by cryogenic SEM: Insights from lab experiments on synthetic hydrates as interpretive guides.

NASA Astrophysics Data System (ADS)

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

2006-12-01

In the investigation of natural gas hydrates, distinguishing in situ grain textures and microstructures from artifacts produced during retrieval, storage, and examination can be quite challenging. Using cryogenic scanning electron microscopy, we investigated the physical states of gas hydrates produced in our lab as well as of those in drill core of hydrate-bearing sediment from marine and Arctic permafrost environments. Here, we compare grain and pore structures observed in samples from the Cascadia margin (courtesy IODP Expedition 311), McKenzie River Delta (Mallik Well 5L-38), and Gulf of Mexico (RSV Marion Dufresne 2002), with those present in hydrocarbon hydrates grown in our laboratory and subjected to controlled P-T conditions. The following trends are apparent for the natural gas hydrates imaged to-date: (1) Samples typically contain massive domains of polycrystalline gas hydrate that in turn contain isolated gas-filled pores that are sometimes lined with euhedral hydrate crystals. Pores are typically 5 50 microns in diameter and occupy roughly 10-30 percent of the domain. Grain sizes, where visible, are commonly 20 to 50 microns. (2) Hydrate grain boundaries, particularly near the exposed sample surface, are often replaced by a nanoporous material. Based on its location and behavior, this material is presumed to be gas-charged porous ice produced by hydrate decomposition along grain surfaces. In some samples, grains are instead bounded by a framework of dense, tabular material embedded within the sample, best revealed upon sublimation of the hydrate. Their composition is yet unknown but may be salt or carbonate-bearing minerals. (3) Where hydrate grows into clayey sediments, the clays typically arrange with platelets subparallel around the pods or veins of hydrate. (4) Domains of nano-to-micro- porous water ice are also seen in all recovered natural samples, presumed to be hydrate decomposition product produced during drill-core retrieval and handling. Based on lab experiments, we believe the initial liquid product is frozen as a result of the local temperature reduction accompanying the endothermic dissociation reaction. The porous texture is then preserved by liquid nitrogen quenching. (5) Samples from both marine and permafrost environments also display closely juxtaposed regions of dense and porous hydrate and ice. Although the close association of these regions remains puzzling, lab tests verify that dense hydrate can exhibit such porous appearance along it's surface after even minor decomposition at cold conditions (below 273 K). In turn, companion experiments show that nanoporous hydrate anneals to a densely crystalline habit at conditions within the hydrate stability region above 273 K, suggesting that nanoporous gas hydrate is not stable at most in situ natural conditions.

An improved cryo-FIB method for fabrication of frozen hydrated lamella.

PubMed

Zhang, Jianguo; Ji, Gang; Huang, Xiaojun; Xu, Wei; Sun, Fei

2016-05-01

Cryo-electron tomography (cryo-ET) provides great insights into the ultrastructure of cells and tissues in their native state and provides a promising way to study the in situ 3D structures of macromolecular complexes. However, this technique has been limited on the very thin specimen, which is not applicable for most cells and tissues. Besides cryo-sectioning approach, cryo focused ion beam (cryo-FIB) appeared recently to achieve 'artifact-free' thin frozen hydrated lamella via fabrication. Considering that the current cryo-FIB methods need modified holders or cartridges, here, with a "D-shaped" molybdenum grid and a specific shutter system, we developed a simple cryo-FIB approach for thin frozen hydrated lamella fabrication, which fits both standard transmission cryo-electron microscopes with side-entry cryo-holders and state-of-the-art ones with AutoGrids. Our approach will expand the usage of cryo-FIB approach in many labs. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

A Versatile High-Vacuum Cryo-transfer System for Cryo-microscopy and Analytics

PubMed Central

Tacke, Sebastian; Krzyzanek, Vladislav; Nüsse, Harald; Wepf, Roger Albert; Klingauf, Jürgen; Reichelt, Rudolf

2016-01-01

Cryogenic microscopy methods have gained increasing popularity, as they offer an unaltered view on the architecture of biological specimens. As a prerequisite, samples must be handled under cryogenic conditions below their recrystallization temperature, and contamination during sample transfer and handling must be prevented. We present a high-vacuum cryo-transfer system that streamlines the entire handling of frozen-hydrated samples from the vitrification process to low temperature imaging for scanning transmission electron microscopy and transmission electron microscopy. A template for cryo-electron microscopy and multimodal cryo-imaging approaches with numerous sample transfer steps is presented. PMID:26910419

Three-dimensional coherent X-ray diffractive imaging of whole frozen-hydrated cells

PubMed Central

Rodriguez, Jose A.; Xu, Rui; Chen, Chien-Chun; Huang, Zhifeng; Jiang, Huaidong; Chen, Allan L.; Raines, Kevin S.; Pryor Jr, Alan; Nam, Daewoong; Wiegart, Lutz; Song, Changyong; Madsen, Anders; Chushkin, Yuriy; Zontone, Federico; Bradley, Peter J.; Miao, Jianwei

2015-01-01

A structural understanding of whole cells in three dimensions at high spatial resolution remains a significant challenge and, in the case of X-rays, has been limited by radiation damage. By alleviating this limitation, cryogenic coherent diffractive imaging (cryo-CDI) can in principle be used to bridge the important resolution gap between optical and electron microscopy in bio-imaging. Here, the first experimental demonstration of cryo-CDI for quantitative three-dimensional imaging of whole frozen-hydrated cells using 8 keV X-rays is reported. As a proof of principle, a tilt series of 72 diffraction patterns was collected from a frozen-hydrated Neospora caninum cell and the three-dimensional mass density of the cell was reconstructed and quantified based on its natural contrast. This three-dimensional reconstruction reveals the surface and internal morphology of the cell, including its complex polarized sub-cellular structure. It is believed that this work represents an experimental milestone towards routine quantitative three-dimensional imaging of whole cells in their natural state with spatial resolutions in the tens of nanometres. PMID:26306199

Three-dimensional coherent X-ray diffractive imaging of whole frozen-hydrated cells

DOE PAGES

Rodriguez, Jose A.; Xu, Rui; Chen, Chien -Chun; ...

2015-09-01

Here, a structural understanding of whole cells in three dimensions at high spatial resolution remains a significant challenge and, in the case of X-rays, has been limited by radiation damage. By alleviating this limitation, cryogenic coherent diffractive imaging (cryo-CDI) can in principle be used to bridge the important resolution gap between optical and electron microscopy in bio-imaging. Here, the first experimental demonstration of cryo-CDI for quantitative three-dimensional imaging of whole frozen-hydrated cells using 8 Kev X-rays is reported. As a proof of principle, a tilt series of 72 diffraction patterns was collected from a frozen-hydrated Neospora caninum cell and themore » three-dimensional mass density of the cell was reconstructed and quantified based on its natural contrast. This three-dimensional reconstruction reveals the surface and internal morphology of the cell, including its complex polarized sub-cellular structure. Finally, it is believed that this work represents an experimental milestone towards routine quantitative three-dimensional imaging of whole cells in their natural state with spatial resolutions in the tens of nanometres.« less

Three-dimensional coherent X-ray diffractive imaging of whole frozen-hydrated cells.

PubMed

Rodriguez, Jose A; Xu, Rui; Chen, Chien-Chun; Huang, Zhifeng; Jiang, Huaidong; Chen, Allan L; Raines, Kevin S; Pryor, Alan; Nam, Daewoong; Wiegart, Lutz; Song, Changyong; Madsen, Anders; Chushkin, Yuriy; Zontone, Federico; Bradley, Peter J; Miao, Jianwei

2015-09-01

A structural understanding of whole cells in three dimensions at high spatial resolution remains a significant challenge and, in the case of X-rays, has been limited by radiation damage. By alleviating this limitation, cryogenic coherent diffractive imaging (cryo-CDI) can in principle be used to bridge the important resolution gap between optical and electron microscopy in bio-imaging. Here, the first experimental demonstration of cryo-CDI for quantitative three-dimensional imaging of whole frozen-hydrated cells using 8 keV X-rays is reported. As a proof of principle, a tilt series of 72 diffraction patterns was collected from a frozen-hydrated Neospora caninum cell and the three-dimensional mass density of the cell was reconstructed and quantified based on its natural contrast. This three-dimensional reconstruction reveals the surface and internal morphology of the cell, including its complex polarized sub-cellular structure. It is believed that this work represents an experimental milestone towards routine quantitative three-dimensional imaging of whole cells in their natural state with spatial resolutions in the tens of nanometres.

Chemistry and Spectroscopy of Frozen Chloride Salts on Icy Bodies

NASA Astrophysics Data System (ADS)

Johnson, P. V.; Thomas, E. C.; Hodyss, R. P.; Vu, T. H.; Choukroun, M.

2016-12-01

Understanding the habitability of Europa's ocean is of great interest to astrobiology and is the focus of missions currently being considered to explore Europa. Currently, our best means of constraining the subsurface ocean composition and its subsequent habitability is by further study of Europa's surface chemical composition. Analysis of existing (and future) remote sensing data is limited by the availability of spectral libraries of candidate materials under relevant conditions (temperature, thermal/radiation history, etc.). Geochemical predictions of Europa's ocean composition suggest that chloride salts are likely to exist on the surface of Europa as well as other ocean worlds. We have conducted a study of frozen chloride-salt brines prepared at temperatures, pressures and radiation conditions (UV) in order to simulate conditions on the surface of Europa and other airless bodies. Hydration states of various chloride salts as a function of temperature were determined using Raman spectroscopy. Near IR reflectance spectra of identically prepared samples were measured to provide reference spectra of the identified hydrated salts. We find that the freezing of NaCl at temperatures ranging from 80 K to 233 K forms hydrohalite. In contrast, KCl hydrates are not formed from the freezing of KCl brines. In addition, a stable hexahydrate forms from the freezing of MgCl2 solutions, while a hexahydrate, a tetrahydrate, and a dihydrate, form upon freezing of CaCl2 solutions. Salts were observed to dehydrated with increasing temperatures, leading to a succession of hydration states in the case of CaCl2. Irradiation with vacuum ultraviolet light was observed to lead to dehydration as well.

Chemistry and Spectroscopy of Frozen Chloride Salts on Icy Bodies

NASA Astrophysics Data System (ADS)

Johnson, Paul; Thomas, Elena C.; Hodyss, Robert; Vu, Tuan; Choukroun, Mathieu

2016-10-01

Currently, our understanding of the chemical composition of Europa's surface is our best means of inferring constraints on the subsurface ocean composition and its subsequent habitability. The bulk of our knowledge of Europa surface chemistry can be traced to near infrared spectra recorded by the Near Infrared Mapping Spectrometer on the Galileo spacecraft. However, the usefulness of this and other remote sensing data is limited by the availability of spectral libraries of candidate materials under relevant conditions (temperature, thermal/radiation history, etc.). Chloride salts are expected to exist on the surface of Europa, and other icy bodies, based on geochemical predictions of the ocean composition. In order to help improve our understanding of Europa's surface composition, we have conducted a study of frozen chloride-salt brines prepared under simulated Europa surface conditions (vacuum, temperature, and UV irradiation) using both near IR and Raman spectroscopies. Specifically, Raman spectroscopy was used to determine the hydration states of various chloride salts as a function of temperature. Near IR spectroscopy of identically prepared samples was used to provide reference reflectance spectra of the identified hydrated salts. Our results indicate that at temperatures ranging from 80 K to 233 K, hydrohalite is formed from the freezing of NaCl brines, while the freezing of KCl solutions does not form KCl hydrates. In addition, the freezing of MgCl2 solutions forms a stable hexahydrate, and the freezing of CaCl2 solutions forms a hexahydrate, a tetrahydrate, and a dihydrate. Dehydration of the salts was observed as temperatures were increased, leading to a succession of hydration states in the case of CaCl2.

Cryogenic X-Ray Diffraction Microscopy for Biological Samples

NASA Astrophysics Data System (ADS)

Lima, Enju; Wiegart, Lutz; Pernot, Petra; Howells, Malcolm; Timmins, Joanna; Zontone, Federico; Madsen, Anders

2009-11-01

X-ray diffraction microscopy (XDM) is well suited for nondestructive, high-resolution biological imaging, especially for thick samples, with the high penetration power of x rays and without limitations imposed by a lens. We developed nonvacuum, cryogenic (cryo-) XDM with hard x rays at 8 keV and report the first frozen-hydrated imaging by XDM. By preserving samples in amorphous ice, the risk of artifacts associated with dehydration or chemical fixation is avoided, ensuring the imaging condition closest to their natural state. The reconstruction shows internal structures of intact D. radiodurans bacteria in their natural contrast.

The innovation of cryo-SEM freeze-fracturing methodology demonstrated on high pressure frozen biofilm.

PubMed

Hrubanova, Kamila; Nebesarova, Jana; Ruzicka, Filip; Krzyzanek, Vladislav

2018-07-01

In this study we present an innovative method for the preparation of fully hydrated samples of microbial biofilms of cultures Staphylococcus epidermidis, Candida parapsilosis and Candida albicans. Cryo-scanning electron microscopy (cryo-SEM) and high-pressure freezing (HPF) rank among cutting edge techniques in the electron microscopy of hydrated samples such as biofilms. However, the combination of these techniques is not always easily applicable. Therefore, we present a method of combining high-pressure freezing using EM PACT2 (Leica Microsystems), which fixes hydrated samples on small sapphire discs, with a high resolution SEM equipped with the widely used cryo-preparation system ALTO 2500 (Gatan). Using a holder developed in house, a freeze-fracturing technique was applied to image and investigate microbial cultures cultivated on the sapphire discs. In our experiments, we focused on the ultrastructure of the extracellular matrix produced during cultivation and the relationships among microbial cells in the biofilm. The main goal of our investigations was the detailed visualization of areas of the biofilm where the microbial cells adhere to the substrate/surface. We show the feasibility of this technique, which is clearly demonstrated in experiments with various freeze-etching times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Gas hydrate in nature

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

Effect of aging and ice structuring proteins on the morphology of frozen hydrated gluten networks.

PubMed

Kontogiorgos, Vassilis; Goff, H Douglas; Kasapis, Stefan

2007-04-01

The present investigation constitutes an attempt to rationalize the effect of aging and ice structuring proteins (ISPs) on the network morphology of frozen hydrated gluten. In doing so, it employs differential scanning calorimetry, time-domain NMR, dynamic oscillation on shear, creep testing, and electron microscopy. Experimentation and first principles modeling allows identification and description of the processes of ice formation and recrystallization in molecular terms. It is demonstrated that in the absence of a readily discernible glass transition temperature in gluten-ice composites, the approach of considering the melting point and aging at constant or fluctuating temperature conditions in the vicinity of this point can provide a valid index of functional quality. A theoretical framework supporting the concept of capillary confined frozen water in the gluten matrix was advanced, and it was found that ISPs were effective in controlling recrystallization both within these confines and within ice in the bulk.

Hydrated salt minerals on Ganymede's surface: evidence of an ocean below.

PubMed

McCord, T B; Hansen, G B; Hibbitts, C A

2001-05-25

Reflectance spectra from Galileo's near-infrared mapping spectrometer (NIMS) suggests that the surface of Ganymede, the largest satellite of Jupiter, contains hydrated materials. These materials are interpreted to be similar to those found on Europa, that is, mostly frozen magnesium sulfate brines that are derived from a subsurface briny layer of fluid.

Low-temperature and conventional scanning electron microscopy of human urothelial neoplasms.

PubMed

Hopkins, D M; Morris, J A; Oates, K; Huddart, H; Staff, W G

1989-05-01

The appearance of neoplastic human urothelium viewed by low-temperature scanning electron microscopy (LTSEM) and conventional scanning electron microscopy (CSEM) was compared. Fixed, dehydrated neoplastic cells viewed by CSEM had well-defined, often raised cell junctions; no intercellular gaps; and varying degrees of pleomorphic surface microvilli. The frozen hydrated material viewed by LTSEM, however, was quite different. The cells had a flat or dimpled surface, but no microvilli. There were labyrinthine lateral processes which interdigitated with those of adjacent cells and outlined large intercellular gaps. The process of fixation and dehydration will inevitably distort cell contours and on theoretical grounds, the images of frozen hydrated material should more closely resemble the in vivo appearance.

Variability of measurements of sweat sodium using the regional absorbent-patch method.

PubMed

Dziedzic, Christine E; Ross, Megan L; Slater, Gary J; Burke, Louise M

2014-09-01

There is interest in including recommendations for the replacement of the sodium lost in sweat in individualized hydration plans for athletes. Although the regional absorbent-patch method provides a practical approach to measuring sweat sodium losses in field conditions, there is a need to understand the variability of estimates associated with this technique. Sweat samples were collected from the forearms, chest, scapula, and thigh of 12 cyclists during 2 standardized cycling time trials in the heat and 2 in temperate conditions. Single measure analysis of sodium concentration was conducted immediately by ion-selective electrodes (ISE). A subset of 30 samples was frozen for reanalysis of sodium concentration using ISE, flame photometry (FP), and conductivity (SC). Sweat samples collected in hot conditions produced higher sweat sodium concentrations than those from the temperate environment (P = .0032). A significant difference (P = .0048) in estimates of sweat sodium concentration was evident when calculated from the forearm average (mean ± 95% CL; 64 ± 12 mmol/L) compared with using a 4-site equation (70 ± 12 mmol/L). There was a high correlation between the values produced using different analytical techniques (r2 = .95), but mean values were different between treatments (frozen FP, frozen SC > immediate ISE > frozen ISE; P < .0001). Whole-body sweat sodium concentration estimates differed depending on the number of sites included in the calculation. Environmental testing conditions should be considered in the interpretation of results. The impact of sample freezing and subsequent analytical technique was small but statistically significant. Nevertheless, when undertaken using a standardized protocol, the regional absorbent-patch method appears to be a relatively robust field test.

Ultrastructure in frozen/etched saline solutions: on the internal cleansing of ice.

PubMed

Menger, Fredric M; Galloway, Ashley L; Chlebowski, Mary E; Apkarian, Robert P

2004-05-19

Seawater, with its 3.5% salt content, freezes into hexagonal ice (Ih) that encloses concentrated brine within its matrix. When unsubmerged sea ice reaches a certain height and temperature, the brine drains downward through narrow channels. This mechanism was now modeled by frozen 2-3.5% saline as investigated by cryo-etch high-resolution secondary electron microscopy. Thus, saline was either plunge-frozen in liquid ethane at -183 degrees C or else high-pressure frozen to -105 degrees C in 5-6 ms. Ice from a freshly exposed surface was then subjected to a high-vacuum sublimation ("etching"), a procedure that removes pure bulk ice in preference to ice from frozen hydrated salt. After chromium-coating the etched surface with a 2-nm film, the sample was examined by cryo-HRSEM. Granular icy "fences" were seen surrounding empty areas where amorphous ice had originally resided. Since the fences, about 1-2 mum high, survived the etching, it is likely that they consist of frozen brine. The presence of such fences suggests that, during freezing, saline can purge itself of salt with remarkable speed (5-6 ms). Alternatively, channels (perhaps routed around submicroscopic crystallites of cubic ice (Ic) embedded in the amorphous ice at -105 degrees C) can guide the migration of salt to the periphery of ice patches. Macromolecules fail to form fences because they diffuse too slowly or because they are too large to pass through the channels.

Magnetic Hysteresis Parameters and Day-Plot Analysis to Delineate Diagenetic Alteration in Gas Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Enkin, R. J.; Baker, J.; Nourgaliev, D.; Iassonov, P.

2005-12-01

Gas hydrates are naturally occurring cage structures of ice found in continental slope and permafrost sediments. They contain vast quantities of methane which is important both as a climate driver and an energy resource. Hydrate formation alters the redox potential of interstitial fluids which can in turn alter magnetic minerals. Thus magnetic methods can help delineate diagenetic pathways, provide a proxy method to map out past hydrate occurrences, and eventually lead to new remote sensing methods in prospecting for gas hydrates. We present data acquired using a J-Meter Coercivity Spectrometer. Induced and remanent magnetism are simultaneously measured on 1.5 cc samples as they spin on a 50 cm diameter disk, 20 times per second. The applied field ramps between ± 500 mT to produce a hysteresis loop in 7 minutes. Sub-second viscous decay is measured to provide a proxy for the amount of superparamagnetism present. The rapid and simple measurements made possible by this robust machine are ideal for core logging. Measurements made on frozen core from the Mallik permafrost gas hydrate field in Canada's Northwest Territories demonstrates that the magnetic properties are dependent on the concentration of gas hydrate present. Day-plots of magnetic hysteresis parameter ratios distinguish the magnetic carriers in gas hydrate rich sediments. The original magnetite is often reduced to sulphide when gas hydrate concentration exceeds 40%. In other high-concentration gas hydrate horizons, fine single-domain (SD) grains of magnetite apparently dissolve leaving nothing but large multi-domain (MD) magnetite grains. Independently measured superparamagnetism is shown to push hysteresis ratios off the hyperbola expected for SD-MD mixtures, as predicted by Dunlop [JGR, 10.10291/2001JB000486, 2002]. Magnetic study of host sediments in gas hydrate systems provides a powerful core-logging tool, offers a window into the processes of gas hydrate formation, and forms the basis for quantitative analysis of magnetic surveys over gas hydrate fields.

Quantum rotations in natural methane-clathrates from the Pacific sea-floor

NASA Astrophysics Data System (ADS)

Gutt, C.; Asmussen, B.; Press, W.; Merkl, C.; Casalta, H.; Greinert, J.; Bohrmann, G.; Tse, J. S.; Hüller, A.

1999-11-01

We report inelastic neutron scattering experiments from natural methane hydrates sampled from the Pacific sea-floor during an expedition of the research ship SONNE. The experiments verify directly the content of methane by measuring the rotational spectrum of the CH4 molecules. The existence of almost free rotational levels excludes off-center positions of the molecules in the cages. In addition we could assign the observed peaks in the energy regime up to 5 meV to rotational excitations only. The observed relative sharp excitations prove a surprisingly good crystallinity of the geological sample. The finite width is attributed to frozen-in hydrogen disorder of the ice cages.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Initiation of Martian Outflow Channels: Related to the Dissociation of Gas Hydrate?

NASA Technical Reports Server (NTRS)

Max, Michael D.; Clifford, Stephen M.

2001-01-01

We propose that the disruption of subpermafrost aquifers on Mars by the thermal- or pressure-induced dissociation of methane hydrate may have been a frequent trigger for initiating outflow channel activity. This possibility is raised by recent work that suggests that significant amounts of methane and gas hydrate may have been produced within and beneath the planet's cryosphere. On Earth, the build-up of overpressured water and gas by the decomposition of hydrate deposits has been implicated in the formation of large blowout features on the ocean floor. These features display a remarkable resemblance (in both morphology and scale) to the chaotic terrain found at the source of many Martian channels. The destabilization of hydrate can generate pressures sufficient to disrupt aquifers confined by up to 5 kilometers of frozen ground, while smaller discharges may result from the water produced by the decomposition of near-surface hydrate alone.

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

Deng, Junjing; Vine, David J.; Chen, Si

X-ray microscopy can be used to image whole, unsectioned cells in their native hydrated state. It complements the higher resolution of electron microscopy for submicrometer thick specimens, and the molecule-specific imaging capabilites of fluorescence light microscopy. We describe here the first use of fast, continuous x-ray scanning of frozen hydrated cells for simultaneous sub-20 nm resolution ptychographic transmission imaging with high contrast, and sub-100 nm resolution deconvolved x-ray fluorescence imaging of diffusible and bound ions at native concentrations, without the need to add specific labels. Here, by working with cells that have been rapidly frozen without the use of chemicalmore » fixatives, and imaging them under cryogenic conditions, we are able to obtain images with well preserved structural and chemical composition, and sufficient stability against radiation damage to allow for multiple images to be obtained with no observable change.« less

Assessment of different sample preparation routes for mass spectrometric monitoring and imaging of lipids in bone cells via ToF-SIMS

PubMed Central

Schaepe, Kaija; Kokesch-Himmelreich, Julia; Rohnke, Marcus; Wagner, Alena-Svenja; Schaaf, Thimo; Wenisch, Sabine; Janek, Jürgen

2015-01-01

In ToF-SIMS analysis, the experimental outcome from cell experiments is to a great extent influenced by the sample preparation routine. In order to better judge this critical influence in the case of lipid analysis, a detailed comparison of different sample preparation routines is performed—aiming at an optimized preparation routine for systematic lipid imaging of cell cultures. For this purpose, human mesenchymal stem cells were analyzed: (a) as chemically fixed, (b) freeze-dried, and (c) frozen-hydrated. For chemical fixation, different fixatives, i.e., glutaraldehyde, paraformaldehyde, and a mixture of both, were tested with different postfixative handling procedures like storage in phosphate buffered saline, water or critical point drying. Furthermore, secondary lipid fixation via osmium tetroxide was taken into account and the effect of an ascending alcohol series with and without this secondary lipid fixation was evaluated. Concerning freeze-drying, three different postprocessing possibilities were examined. One can be considered as a pure cryofixation technique while the other two routes were based on chemical fixation. Cryofixation methods known from literature, i.e., freeze-fracturing and simple frozen-hydrated preparation, were also evaluated to complete the comparison of sample preparation techniques. Subsequent data evaluation of SIMS spectra in both, positive and negative, ion mode was performed via principal component analysis by use of peak sets representative for lipids. For freeze-fracturing, these experiments revealed poor reproducibility making this preparation route unsuitable for systematic investigations and statistic data evaluation. Freeze-drying after cryofixation showed improved reproducibility and well preserved lipid contents while the other freeze-drying procedures showed drawbacks in one of these criteria. In comparison, chemical fixation techniques via glutar- and/or paraformaldehyde proved most suitable in terms of reproducibility and preserved lipid contents, while alcohol and osmium treatment led to the extraction of lipids and are therefore not recommended. PMID:25791294

Assessment of different sample preparation routes for mass spectrometric monitoring and imaging of lipids in bone cells via ToF-SIMS.

PubMed

Schaepe, Kaija; Kokesch-Himmelreich, Julia; Rohnke, Marcus; Wagner, Alena-Svenja; Schaaf, Thimo; Wenisch, Sabine; Janek, Jürgen

2015-03-19

In ToF-SIMS analysis, the experimental outcome from cell experiments is to a great extent influenced by the sample preparation routine. In order to better judge this critical influence in the case of lipid analysis, a detailed comparison of different sample preparation routines is performed-aiming at an optimized preparation routine for systematic lipid imaging of cell cultures. For this purpose, human mesenchymal stem cells were analyzed: (a) as chemically fixed, (b) freeze-dried, and (c) frozen-hydrated. For chemical fixation, different fixatives, i.e., glutaraldehyde, paraformaldehyde, and a mixture of both, were tested with different postfixative handling procedures like storage in phosphate buffered saline, water or critical point drying. Furthermore, secondary lipid fixation via osmium tetroxide was taken into account and the effect of an ascending alcohol series with and without this secondary lipid fixation was evaluated. Concerning freeze-drying, three different postprocessing possibilities were examined. One can be considered as a pure cryofixation technique while the other two routes were based on chemical fixation. Cryofixation methods known from literature, i.e., freeze-fracturing and simple frozen-hydrated preparation, were also evaluated to complete the comparison of sample preparation techniques. Subsequent data evaluation of SIMS spectra in both, positive and negative, ion mode was performed via principal component analysis by use of peak sets representative for lipids. For freeze-fracturing, these experiments revealed poor reproducibility making this preparation route unsuitable for systematic investigations and statistic data evaluation. Freeze-drying after cryofixation showed improved reproducibility and well preserved lipid contents while the other freeze-drying procedures showed drawbacks in one of these criteria. In comparison, chemical fixation techniques via glutar- and/or paraformaldehyde proved most suitable in terms of reproducibility and preserved lipid contents, while alcohol and osmium treatment led to the extraction of lipids and are therefore not recommended.

Electron cryo-tomography captures macromolecular complexes in native environments.

PubMed

Baker, Lindsay A; Grange, Michael; Grünewald, Kay

2017-10-01

Transmission electron microscopy has a long history in cellular biology. Fixed and stained samples have been used for cellular imaging for over 50 years, but suffer from sample preparation induced artifacts. Electron cryo-tomography (cryoET) instead uses frozen-hydrated samples, without chemical modification, to determine the structure of macromolecular complexes in their native environment. Recent developments in electron microscopes and associated technologies have greatly expanded our ability to visualize cellular features and determine the structures of macromolecular complexes in situ. This review highlights the technological improvements and the new areas of biology these advances have made accessible. We discuss the potential of cryoET to reveal novel and significant biological information on the nanometer or subnanometer scale, and directions for further work. Copyright © 2017. Published by Elsevier Ltd.

Controlled formation of cyclopentane hydrate suspensions via capillary-driven jet break-up

NASA Astrophysics Data System (ADS)

Geri, Michela; McKinley, Gareth

2017-11-01

Clathrate hydrates are crystalline compounds that form when a lattice of hydrogen-bonded water molecules is filled by guest molecules sequestered from an adjacent gas or liquid phase. Being able to rapidly produce and transport synthetic hydrates is of great interest given their significant potential as a clean energy source and safe option for hydrogen storage. We propose a new method to rapidly produce cyclopentane hydrate suspensions at ambient pressure with tunable particle size distribution by taking advantage of the Rayleigh-Plateau instability to form a mono-disperse stream of droplets during the controlled break-up of a water jet. The droplets are immediately frozen into ice particles through immersion in a subcooled reservoir and converted into hydrates with a dramatic reduction in the nucleation induction time. By measuring the evolution of the rheological properties with time, we monitor the process of hydrates formation via surface crystallization and agglomeration with different droplet size distributions. This new method enables us to gain new insights into hydrate formation and transport which was previously hindered by uncontrolled droplet formation and hydrate nucleation processes. MITei Chevron Fellowship.

ON THE FREEZING AND IDENTIFICATION OF LIPID MONOLAYER 2-D ARRAYS FOR CRYOELECTRON MICROSCOPY

PubMed Central

Taylor, Dianne W.; Kelly, Deborah F.; Cheng, Anchi; Taylor, Kenneth A.

2008-01-01

Lipid monolayers provide a convenient vehicle for the crystallization of biological macromolecules for 3-D electron microscopy. Although numerous examples of 3-D images from 2-D protein arrays have been described from negatively stained specimens, only six structures have been done from frozen hydrated specimens. We describe here a method that makes high quality frozen-hydrated specimens of lipid monolayer arrays for cryoelectron microscopy. The method uses holey carbon films with patterned holes for monolayer recovery, blotting and plunge freezing to produce thin aqueous films which cover >90% of the available grid area. With this method, even specimens with relatively infrequent crystals can be screened using automated data collection techniques. Though developed for microscopic examination of 2-D arrays, the method may have wider application to the preparation of single particle specimens for 3-D image reconstruction. PMID:17561414

Preparation and Supercooling Modification of Salt Hydrate Phase Change Materials Based on CaCl₂·2H₂O/CaCl₂.

PubMed

Xu, Xiaoxiao; Dong, Zhijun; Memon, Shazim Ali; Bao, Xiaohua; Cui, Hongzhi

2017-06-23

Salt hydrates have issues of supercooling when they are utilized as phase change materials (PCMs). In this research, a new method was adopted to prepare a salt hydrate PCM (based on a mixture of calcium chloride dihydrate and calcium chloride anhydrous) as a novel PCM system to reduce the supercooling phenomenon existing in CaCl₂·6H₂O. Six samples with different compositions of CaCl₂ were prepared. The relationship between the performance and the proportion of calcium chloride dihydrate (CaCl₂·2H₂O) and calcium chloride anhydrous (CaCl₂) was also investigated. The supercooling degree of the final PCM reduced with the increase in volume of CaCl₂·2H₂O during its preparation. The PCM obtained with 66.21 wt % CaCl₂·2H₂O reduced the supercooling degree by about 96.8%. All six samples, whose ratio of CaCl₂·2H₂O to (CaCl₂ plus CaCl₂·2H₂O) was 0%, 34.03%, 53.82%, 76.56%, 90.74%, and 100% respectively, showed relatively higher enthalpy (greater than 155.29 J/g), and have the possibility to be applied in buildings for thermal energy storage purposes. Hence, CaCl₂·2H₂O plays an important role in reducing supercooling and it can be helpful in adjusting the solidification enthalpy. Thereafter, the influence of adding different percentages of Nano-SiO₂ (0.1 wt %, 0.3 wt %, 0.5 wt %) in reducing the supercooling degree of some PCM samples was investigated. The test results showed that the supercooling of the salt hydrate PCM in Samples 6 and 5 reduced to 0.2 °C and 0.4 °C respectively. Finally, the effect of the different cooling conditions, including frozen storage (-20 °C) and cold storage (5 °C), that were used to prepare the salt hydrate PCM was considered. It was found that both cooling conditions are effective in reducing the supercooling degree of the salt hydrate PCM. With the synergistic action of the two materials, the performance and properties of the newly developed PCM systems were better especially in terms of reducing the supercooling degree of the PCM. The novel composite PCMs are promising candidates for thermal energy storage applications.

Preface to the special issue on gas hydrate drilling in the Eastern Nankai Trough

USGS Publications Warehouse

Yamamoto, Koji; Ruppel, Carolyn D.

2015-01-01

Methane hydrate traps enormous amounts of methane in frozen deposits in continental margin sediments, and these deposits have long been targeted for studies investigating their potential as an energy resource. As a concentrated form of methane that occurs at shallower depths than conventional and most unconventional gas reservoirs, methane hydrates could be a readily accessible source of hydrocarbons for countries hosting deposits within their Exclusive Economic Zones. Japan is one such country, and since 2001 the Research Consortium for Methane Hydrate Resources in Japan (referred to as MH21) has conducted laboratory, modeling, and field-based programs to study methane hydrates as an energy resource. The MH21 consortium is funded by the Japanese Ministry of Trade and Industry (METI) and led by the Japan Oil, Gas and Metals National Oil Corporation (JOGMEC) and the National Institute of Advanced Industrial Science and Technology (AIST).

Cryo-scanning electron microscopy investigation of the Octopus Vulgaris arm structures for the design of an octopus-like arm artefact.

PubMed

Minnocci, Antonio; Cianchetti, Matteo; Mazzolai, Barbara; Sebastiani, Luca; Laschi, Cecilia

2015-12-01

Octopus vulgaris is a cephalopod of the Octopodidae family. It has four pairs of arms and two rows of suckers which perform many functions, including bending and elongation. For this reason the octopus was chosen as model to develop a new generation of soft-body robots. In order to explain some of the fine structures of the octopus arm in relation to its specific ability, we examined the external and internal structures of O. vulgaris arms in a frozen-hydrated state using cryo-scanning electron microscopy. The arms showed skin with a very complex design that is useful to elongation, and a pore pattern distribution on their surface which is functional to cutaneous oxygen uptake. The analysis of freeze-fractured frozen-hydrated arm samples allowed us to describe the developmental differences in the relative proportion of the areas of axial nerve cord, intrinsic and extrinsic musculature, in relation to the growth of the arms and of the increase in functional capability. In the suckers, we analyzed the shedding mechanisms in the outer part of the infundibulum and described the outer and inner characteristics of the denticles, showing in detail their pore system, which is fundamental for their ability to explore the environment. These results are discussed by considering their possible application in the design of new octopus-like artefacts, which will be able to take advantage of some of these ultrastructure characteristics and achieve advanced bioinspired functionalities. © 2015 Wiley Periodicals, Inc.

In-situ integrity control of frozen-hydrated, vitreous lamellas prepared by the cryo-focused ion beam-scanning electron microscope.

PubMed

de Winter, D A Matthijs; Mesman, Rob J; Hayles, Michael F; Schneijdenberg, Chris T W M; Mathisen, Cliff; Post, Jan A

2013-07-01

Recently a number of new approaches have been presented with the intention to produce electron beam transparent cryo-sections (lamellas in FIB-SEM terminology) from hydrated vitreously frozen cryo samples with a Focused Ion Beam (FIB) system, suitable for cryo-Transmission Electron Microscopy (cryo-TEM). As the workflow is still challenging and time consuming, it is important to be able to determine the integrity and suitability (cells vs. no cells; vitreous vs. crystalline) of the lamellas. Here we present an in situ method that tests both conditions by using the cryo-Scanning Electron Microscope (cryo-SEM) in transmission mode (TSEM; Transmission Scanning Electron Microscope) once the FIB-made lamella is ready. Cryo-TSEM imaging of unstained cells yields strong contrast, enabling direct imaging of material present in the lamellas. In addition, orientation contrast is shown to be suitable for distinguishing crystalline lamellas from vitreous lamellas. Tilting the stage a few degrees results in changes of contrast between ice grains as a function of the tilt angle, whereas the contrast of areas with vitreous ice remains unchanged as a function of the tilt angle. This orientation contrast has subsequently been validated by cryo-Electron BackScattered Diffraction (EBSD) in transmission mode. Integration of the presented method is discussed and the role it can play in future developments for a new and innovative all-in-one cryo-FIB-SEM life sciences instrument. Copyright © 2013 Elsevier Inc. All rights reserved.

Cryopreservation of boar semen. III: Ultrastructure of boar spermatozoa frozen ultra-rapidly at various stages of conventional freezing and thawing.

PubMed

Bwanga, C O; Ekwall, H; Rodriguez-Martinez, H

1991-01-01

Ejaculated boar spermatozoa subjected to a conventional freezing and thawing process, were ultra-rapidly fixed, freeze-substituted and examined by electron microscopy to monitor the presence of real or potential intracellular ice and the degree of cell protection attained with the different extenders used during the process. Numerous ice crystal marks representing the degree of hydration of the cells were located in the perinuclear space of those spermatozoa not in proper contact with the extender containing glycerol (i.e. prior to freezing). The spermatozoa which were in proper contact with the extenders presented a high degree of preservation of the acrosomes, plasma membranes as well as the nuclear envelopes. No ice marks were detected in acrosomes before thawing, indicating that the conventional assayed cryopreservation method provided a good protection against cryoinjury. The presence of acrosomal changes (internal vesiculization, hydration and swelling) in thawed samples however, raises serious questions about the thawing procedure employed.

OMNY—A tOMography Nano crYo stage

NASA Astrophysics Data System (ADS)

Holler, M.; Raabe, J.; Diaz, A.; Guizar-Sicairos, M.; Wepf, R.; Odstrcil, M.; Shaik, F. R.; Panneels, V.; Menzel, A.; Sarafimov, B.; Maag, S.; Wang, X.; Thominet, V.; Walther, H.; Lachat, T.; Vitins, M.; Bunk, O.

2018-04-01

For many scientific questions gaining three-dimensional insight into a specimen can provide valuable information. We here present an instrument called "tOMography Nano crYo (OMNY)," dedicated to high resolution 3D scanning x-ray microscopy at cryogenic conditions via hard X-ray ptychography. Ptychography is a lens-less imaging method requiring accurate sample positioning. In OMNY, this in achieved via dedicated laser interferometry and closed-loop position control reaching sub-10 nm positioning accuracy. Cryogenic sample conditions are maintained via conductive cooling. 90 K can be reached when using liquid nitrogen as coolant, and 10 K is possible with liquid helium. A cryogenic sample-change mechanism permits measurements of cryogenically fixed specimens. We compare images obtained with OMNY with older measurements performed using a nitrogen gas cryo-jet of stained, epoxy-embedded retina tissue and of frozen-hydrated Chlamydomonas cells.

Modeling of acoustic wave dissipation in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Guerin, Gilles; Goldberg, David

2005-07-01

Recent sonic and seismic data in gas hydrate-bearing sediments have indicated strong waveform attenuation associated with a velocity increase, in apparent contradiction with conventional wave propagation theory. Understanding the reasons for such energy dissipation could help constrain the distribution and the amounts of gas hydrate worldwide from the identification of low amplitudes in seismic surveys. A review of existing models for wave propagation in frozen porous media, all based on Biot's theory, shows that previous formulations fail to predict any significant attenuation with increasing hydrate content. By adding physically based components to these models, such as cementation by elastic shear coupling, friction between the solid phases, and squirt flow, we are able to predict an attenuation increase associated with gas hydrate formation. The results of the model agree well with the sonic logging data recorded in the Mallik 5L-38 Gas Hydrate Research Well. Cementation between gas hydrate and the sediment grains is responsible for the increase in shear velocity. The primary mode of energy dissipation is found to be friction between gas hydrate and the sediment matrix, combined with an absence of inertial coupling between gas hydrate and the pore fluid. These results predict similar attenuation increase in hydrate-bearing formations over most of the sonic and seismic frequency range.

The infrared spectral properties of frozen volatiles. [in cometary nuclei

NASA Technical Reports Server (NTRS)

Fink, U.; Sill, G. T.

1982-01-01

Since Whipple's dirty snowball model of comet nuclei, it has been generally accepted that volatile ices help to explain cometary phenomena. The infrared spectral properties of many substances that are potential candidates for frozen volatiles in the solar system are being pursued; indeed some of these frozen materials have been found in the solar system: H2O, CO2, and SO2. A review of laboratory spectra in the range 1 to 20 microns of H2O, CO2, SO2, CH4, NH3, H2S, CO, NH4HS and NH3.H2O is presented. Both reflection spectra of thick frosts and transmission spectra of thin films are shown, and their main characteristics are described. Hydrates, clathrates, and composite spectra are discussed. When it is possible to observe the nuclei of comets at close range, it may be possible to identify frozen volatiles by their infrared spectra.

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

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

Deng, Junjing; Vine, David J.; Chen, Si

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and ~90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. Finally, this combined approach offers a way to study the role of trace elements in their structural context.« less

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

DOE PAGES

Deng, Junjing; Vine, David J.; Chen, Si; ...

2015-02-24

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and ~90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. Finally, this combined approach offers a way to study the role of trace elements in their structural context.« less

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

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

Deng, Junjing; Vine, David J.; Chen, Si

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and similar to 90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. This combined approach offers a way to study the role of trace elements in their structural context.« less

Ultraviolet germicidal irradiation and its effects on elemental distributions in mouse embryonic fibroblast cells in x-ray fluorescence microanalysis

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

Jin, Qiaoling; Vogt, Stefan; Lai, Barry

Rapidly-frozen hydrated (cryopreserved) specimens combined with cryo-scanning x-ray fluorescence microscopy provide an ideal approach for investigating elemental distributions in biological cells and tissues. However, because cryopreservation does not deactivate potentially infectious agents associated with Risk Group 2 biological materials, one must be concerned with contamination of expensive and complicated cryogenic x-ray microscopes when working with such materials. We employed ultraviolet germicidal irradiation to decontaminate previously cryopreserved cells under liquid nitrogen, and then investigated its effects on elemental distributions under both frozen hydrated and freeze dried states with x-ray fluorescence microscopy. We show that the contents and distributions of most biologicallymore » important elements remain nearly unchanged when compared with non-ultraviolet-irradiated counterparts, even after multiple cycles of ultraviolet germicidal irradiation and cryogenic x-ray imaging. This provides a potential pathway for rendering Risk Group 2 biological materials safe for handling in multiuser cryogenic x-ray microscopes without affecting the fidelity of the results.« less

Ultraviolet germicidal irradiation and its effects on elemental distributions in mouse embryonic fibroblast cells in x-ray fluorescence microanalysis

DOE PAGES

Jin, Qiaoling; Vogt, Stefan; Lai, Barry; ...

2015-02-23

Rapidly-frozen hydrated (cryopreserved) specimens combined with cryo-scanning x-ray fluorescence microscopy provide an ideal approach for investigating elemental distributions in biological cells and tissues. However, because cryopreservation does not deactivate potentially infectious agents associated with Risk Group 2 biological materials, one must be concerned with contamination of expensive and complicated cryogenic x-ray microscopes when working with such materials. We employed ultraviolet germicidal irradiation to decontaminate previously cryopreserved cells under liquid nitrogen, and then investigated its effects on elemental distributions under both frozen hydrated and freeze dried states with x-ray fluorescence microscopy. We show that the contents and distributions of most biologicallymore » important elements remain nearly unchanged when compared with non-ultraviolet-irradiated counterparts, even after multiple cycles of ultraviolet germicidal irradiation and cryogenic x-ray imaging. This provides a potential pathway for rendering Risk Group 2 biological materials safe for handling in multiuser cryogenic x-ray microscopes without affecting the fidelity of the results.« less

Development of Alaskan gas hydrate resources: Annual report, October 1986--September 1987

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

Sharma, G.D.; Kamath, V.A.; Godbole, S.P.

1987-10-01

Solid ice-like mixtures of natural gas and water in the form of natural gas hydrated have been found immobilized in the rocks beneath the permafrost in Arctic basins and in muds under the deep water along the American continental margins, in the North Sea and several other locations around the world. It is estimated that the arctic areas of the United States may contain as much as 500 trillion SCF of natural gas in the form of gas hydrates (Lewin and Associates, 1983). While the US Arctic gas hydrate resources may have enormous potential and represent long term future sourcemore » of natural gas, the recovery of this resource from reservoir frozen with gas hydrates has not been commercialized yet. Continuing study and research is essential to develop technologies which will enable a detailed characterization and assessment of this alternative natural gas resource, so that development of cost effective extraction technology.« less

The interaction of climate change and methane hydrates

USGS Publications Warehouse

Ruppel, Carolyn D.; Kessler, John D.

2017-01-01

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

The interaction of climate change and methane hydrates

NASA Astrophysics Data System (ADS)

Ruppel, Carolyn D.; Kessler, John D.

2017-03-01

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

The interaction of climate change and methane hydrates

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

Ruppel, Carolyn D.; Kessler, John D.

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

The interaction of climate change and methane hydrates

DOE PAGES

Ruppel, Carolyn D.; Kessler, John D.

2016-12-14

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

Optical properties of cells with melanin

NASA Astrophysics Data System (ADS)

Rohde, Barukh; Coats, Israel; Krueger, James; Gareau, Dan

2014-02-01

The optical properties of pigmented lesions have been studied using diffuse reflectance spectroscopy in a noninvasive configuration on optically thick samples such as skin in vivo. However, it is difficult to un-mix the effects of absorption and scattering with diffuse reflectance spectroscopy techniques due to the complex anatomical distributions of absorbing and scattering biomolecules. We present a device and technique that enables absorption and scattering measurements of tissue volumes much smaller than the optical mean-free path. Because these measurements are taken on fresh-frozen sections, they are direct measurements of the optical properties of tissue, albeit in a different hydration state than in vivo tissue. Our results on lesions from 20 patients including melanomas and nevi show the absorption spectrum of melanin in melanocytes and basal keratinocytes. Our samples consisted of fresh frozen sections that were unstained. Fitting the spectrum as an exponential decay between 500 and 1100 nm [mua = A*exp(-B*(lambda-C)) + D], we report on the fit parameters of and their variation due to biological heterogeneity as A = 4.20e4 +/- 1.57e5 [1/cm], B = 4.57e-3 +/- 1.62e-3 [1/nm], C = 210 +/- 510 [nm] , D = 613 +/- 534 [1/cm]. The variability in these results is likely due to highly heterogeneous distributions of eumelanin and pheomelanin.

Effects of protein conformational flexibilities and electrostatic interactions on the low-frequency vibrational spectrum of hydration water.

PubMed

Pal, Somedatta; Bandyopadhyay, Sanjoy

2013-05-16

The conformational flexibility of a protein and its ability to form hydrogen bonds with water are expected to influence the microscopic properties of water layer hydrating the protein. Detailed molecular dynamics simulations with an aqueous solution of the globular protein barstar have been carried out to explore such influence on the low-frequency vibrational spectrum of the hydration water molecules. The calculations reveal that enhanced degree of confinement at the protein surface on freezing its local motions leads to increasingly restricted oscillatory motions of the hydration water molecules as evident from larger blue shifts of the corresponding band. Interestingly, conformational fluctuations of the protein and electrostatic component of its interaction with the solvent have been found to affect the transverse and longitudinal oscillations of hydration water molecules in a nonuniform manner. It is further noticed that the distributions of the low-frequency modes for the water molecules hydrogen bonded to the residues of different segments of the protein are heterogeneously altered. The effect is more around the frozen protein matrix and agrees well with slower protein-water hydrogen bond relaxations.

Two Mechanisms for Methane Release at the Paleocene/Eocene Boundary

NASA Astrophysics Data System (ADS)

Katz, M. E.; Cramer, B. S.; Mountain, G. S.; Mountain, G. S.; Katz, S.; Miller, K. G.; Miller, K. G.

2001-12-01

The rapid global warming of the Paleocene/Eocene thermal maximum (PETM) has been attributed to a massive methane release from marine gas hydrate reservoirs. Two mechanisms have been proposed for this methane release. The first relies on a deepwater circulation change and water temperature increase that was sufficiently large and rapid to trigger massive thermal dissociation of gas hydrate frozen beneath the seafloor (Dickens et al., 1995). The second relies on slope failure (via erosion or seismic activity) of the oversteepened continental margins of the western North Atlantic to allow methane to escape from gas reservoirs trapped between the hydrate-bearing sediments and the underlying reef front (Katz et al., in press). We evaluate thermal dissociation by modeling heat flow through the sediments to show the effect of the temperature change on the gas hydrate stability zone through time. We use Paleocene bottom water temperatures (constrained by isotope records) and assume an instantaneous water temperature increase (i.e., no time allotted for ocean circulation change and water mass mixing). This yields an end-member minimum estimate of >2350 years necessary to melt all gas hydrate at locations shallower than 1570m; gas hydrates at greater depths remain frozen. We also use this model to predict the amount of C12-enriched methane that could have contributed to the carbon isotope excursion (CIE). Using reasonable methane distributions within sediments, we conclude that thermal dissociation alone cannot account for the full magnitude of the CIE. We propose that thermal dissociation did not initiate the CIE; rather, a different mechanism injected a large amount of carbon into the atmosphere, causing global greenhouse warming that could have led to subsequent thermal dissociation. Methane remains a plausible source for this initial carbon injection; however, initial release would have resulted from mechanical disruption of sediments rather than thermal dissociation. Seismic evidence tied to borehole data shows that methane may have been released from the U.S. continental slope in areas proximal to a buried Mesozoic reef, in contrast to the broader depth range predicted for methane release via thermal dissociation.

Cryo-transmission electron microscopy of frozen-hydrated sections of Escherichia coli and Pseudomonas aeruginosa.

PubMed

Matias, Valério R F; Al-Amoudi, Ashraf; Dubochet, Jacques; Beveridge, Terry J

2003-10-01

High-pressure freezing of Escherichia coli K-12 and Pseudomonas aeruginosa PAO1 in the presence of cryoprotectants provided consistent vitrification of cells so that frozen-hydrated sections could be cut, providing approximately 2-nm resolution of structure. The size and shape of the bacteria, as well as their surface and cytoplasmic constituents, were nicely preserved and compared well with other published high-resolution techniques. Cells possessed a rich cytoplasm containing a diffuse dispersion of ribosomes and genetic material. Close examination of cells revealed that the periplasmic space was compressed during cryosectioning, a finding which provided supporting evidence that this space is filled by a compressible gel. Since the outer membrane and peptidoglycan layer are bonded together via lipoproteins, the space between them (although still part of the periplasmic space) was not as compacted. Even when this cryosectioning compression was taken into account, there was still substantial variability in the width of the periplasmic space. It is possible that the protoplast has some capacity to float freely within the periplasm.

Methane gas hydrate effect on sediment acoustic and strength properties

USGS Publications Warehouse

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

2007-01-01

To improve our understanding of the interaction of methane gas hydrate with host sediment, we studied: (1) the effects of gas hydrate and ice on acoustic velocity in different sediment types, (2) effect of different hydrate formation mechanisms on measured acoustic properties (3) dependence of shear strength on pore space contents, and (4) pore pressure effects during undrained shear.A wide range in acoustic p-wave velocities (Vp) were measured in coarse-grained sediment for different pore space occupants. Vp ranged from less than 1 km/s for gas-charged sediment to 1.77–1.94 km/s for water-saturated sediment, 2.91–4.00 km/s for sediment with varying degrees of hydrate saturation, and 3.88–4.33 km/s for frozen sediment. Vp measured in fine-grained sediment containing gas hydrate was substantially lower (1.97 km/s). Acoustic models based on measured Vp indicate that hydrate which formed in high gas flux environments can cement coarse-grained sediment, whereas hydrate formed from methane dissolved in the pore fluid may not.The presence of gas hydrate and other solid pore-filling material, such as ice, increased the sediment shear strength. The magnitude of that increase is related to the amount of hydrate in the pore space and cementation characteristics between the hydrate and sediment grains. We have found, that for consolidation stresses associated with the upper several hundred meters of sub-bottom depth, pore pressures decreased during shear in coarse-grained sediment containing gas hydrate, whereas pore pressure in fine-grained sediment typically increased during shear. The presence of free gas in pore spaces damped pore pressure response during shear and reduced the strengthening effect of gas hydrate in sands.

Cryogenic coherent X-ray diffraction imaging of biological samples at SACLA: a correlative approach with cryo-electron and light microscopy.

PubMed

Takayama, Yuki; Yonekura, Koji

2016-03-01

Coherent X-ray diffraction imaging at cryogenic temperature (cryo-CXDI) allows the analysis of internal structures of unstained, non-crystalline, whole biological samples in micrometre to sub-micrometre dimensions. Targets include cells and cell organelles. This approach involves preparing frozen-hydrated samples under controlled humidity, transferring the samples to a cryo-stage inside a vacuum chamber of a diffractometer, and then exposing the samples to coherent X-rays. Since 2012, cryo-coherent diffraction imaging (CDI) experiments have been carried out with the X-ray free-electron laser (XFEL) at the SPring-8 Ångstrom Compact free-electron LAser (SACLA) facility in Japan. Complementary use of cryo-electron microscopy and/or light microscopy is highly beneficial for both pre-checking samples and studying the integrity or nature of the sample. This article reports the authors' experience in cryo-XFEL-CDI of biological cells and organelles at SACLA, and describes an attempt towards reliable and higher-resolution reconstructions, including signal enhancement with strong scatterers and Patterson-search phasing.

Sampling the oxidative weathering products and the potentially acidic permafrost on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1988-01-01

Large areas of Mars' surface are covered by oxidative weathering products containing ferric and sulfate ions having analogies to terrestrial gossans derived from sulfide mineralization associated with iron-rich basalts. Chemical weathering of such massive and disseminated pyrrhotite-pentlandite assemblages and host basaltic rocks in the Martian environment could have produced metastable gossaniferous phases (limonite containing poorly crystalline hydrated ferric sulfates and oxyhydroxides, clay silicates and opal). Underlying groundwater, now permafrost on Mars, may still be acidic due to incomplete buffering reactions by wall-rock alteration of unfractured host rock. Such acidic solutions stabilize temperature-sensitive complex ions and sols which flocculate to colloidal precipitates at elevated temperatures. Sampling procedures of Martian regolith will need to be designed bearing in mind that the frozen permafrost may be corrosive and be stabilizing unique complex ions and sols of Fe, Al, Mg, Ni and other minor elements.

Studies on X-ray diffraction microscopy

NASA Astrophysics Data System (ADS)

Miao, Huijie

This dissertation includes three main parts: studies on coherence requirements for the diffraction microscopy experiments, ice formation on frozen-hydrated sample during data collection, and centering of the diffraction data sets. These three subjects are all in support of our groups overall goal of high resolution 3D imaging of frozen hydrated eukaryotic cells via x-ray diffraction microscopy. X-ray diffraction microscopy requires coherent illumination. However, the actual degree of coherence at some beamlines has never been tested. In research on coherence, our first aim is to determine the transverse coherence width at the sample plane at BL 9.0.1 at the Advanced Light Source in Lawrence Berkeley National Laboratory. An analytical calculation of the coherence at the sample plane is presented. Experimental diffraction patterns of pinhole-pair samples were also taken at the beamline to determine the coherence. Due to the irregular shape of the pinholes and other optics complexity, it was very difficult to fit the data with known theoretical equations as it was traditionally done with 1D data. However, we found out that the auto-correlation function shows clearly three spots. Theoretical calculation have been carried out to show that the degree of coherence can be obtained from the intensities of the three spots. These results are compared with the results from the analytical calculation. We then perform a simulation, showing the required transverse coherence width for reconstructing samples with a given size. Ice accumulation has been a major problem in X-ray diffraction microscopy with frozen hydrated samples. Since the ice structure is different from point to point, we cannot subtract the scattering from ice, nor assume a completely "empty" region outside the finite support constraint area as required for reconstruction. Ice forms during the sample preparation and transfer. However, from the tests we did in September 2007, we found that the ice layer thickens significantly during the data collecting process. One of the tests we did was putting a dry room-temperature grid into the beam, cooling it down to liquid nitrogen temperature, and then collecting the diffraction pattern of it over time. This test showed that, after the cold grid remained in the chamber for a while, a ring could be observed in the diffraction pattern. The time necessary for this ring to be visible is highly dependent on the pressure and vacuum history of the chamber. We will discuss how the chamber pressure influences the ice accumulation rate, how an anti-contamination device can help to reduce the rate, and how this ring forms. The last part of the research is based on simulations and a real data set collected on beamline 9.0.1 at the ALS in Berkeley. In X-ray diffraction microscopy, one of the major challenges when processing the data is to accurately determine the true center of the recorded data; that is, the zero spatial frequency position. Simulations of reconstructing shifted data show that if the center of a 2D diffraction pattern is shifted by more than 3 pixels from its true center, the positivity constraint to the phase, which otherwise might be applied to improve the convergence of the reconstruction algorithm, cannot be imposed. Moreover, the phase unwrapping problem may appear during the reconstruction. These issues undermine the quality of the reconstruction of 2D data. Furthermore, the individual shift in each 2D pattern will lead to errors when assembling a 3D diffraction data cube, making the 3D reconstruction very difficult. We developed a method which uses power spectra of the partial diffraction pattern to pre-align the data. A reconstruction without severe phase unwrapping can then be obtained from the pre-aligned data. Next, the precise zero spatial frequency position can be found by examining the linear ramp present in the reconstructed phase. This method was applied to a freeze-dried yeast data set to show that this approach is effective with experimental data.

Dynamic nuclear polarization methods in solids and solutions to explore membrane proteins and membrane systems.

PubMed

Cheng, Chi-Yuan; Han, Songi

2013-01-01

Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments.

KOTOBUKI-1 apparatus for cryogenic coherent X-ray diffraction imaging.

PubMed

Nakasako, Masayoshi; Takayama, Yuki; Oroguchi, Tomotaka; Sekiguchi, Yuki; Kobayashi, Amane; Shirahama, Keiya; Yamamoto, Masaki; Hikima, Takaaki; Yonekura, Koji; Maki-Yonekura, Saori; Kohmura, Yoshiki; Inubushi, Yuichi; Takahashi, Yukio; Suzuki, Akihiro; Matsunaga, Sachihiro; Inui, Yayoi; Tono, Kensuke; Kameshima, Takashi; Joti, Yasumasa; Hoshi, Takahiko

2013-09-01

We have developed an experimental apparatus named KOTOBUKI-1 for use in coherent X-ray diffraction imaging experiments of frozen-hydrated non-crystalline particles at cryogenic temperature. For cryogenic specimen stage with small positional fluctuation for a long exposure time of more than several minutes, we here use a cryogenic pot cooled by the evaporation cooling effect for liquid nitrogen. In addition, a loading device is developed to bring specimens stored in liquid nitrogen to the specimen stage in vacuum. The apparatus allows diffraction data collection for frozen-hydrated specimens at 66 K with a positional fluctuation of less than 0.4 μm and provides an experimental environment to easily exchange specimens from liquid nitrogen storage to the specimen stage. The apparatus was developed and utilized in diffraction data collection of non-crystalline particles with dimensions of μm from material and biological sciences, such as metal colloid particles and chloroplast, at BL29XU of SPring-8. Recently, it has been applied for single-shot diffraction data collection of non-crystalline particles with dimensions of sub-μm using X-ray free electron laser at BL3 of SACLA.

Design of the soft x-ray tomography beamline at Taiwan photon source

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

Su, Yi-Jr, E-mail: su.yj@nsrrc.org.tw; Fu, Huang-Wen; Chung, Shih-Chun

2016-07-27

The optical design of the varied-line-spacing plane-grating monochromator for transmission full-field imaging of frozen-hydrated biological samples at NSRRC is presented. This monochromator consists of a plane mirror and three interchangeable gratings with groove densities 600, 1200 and 2400 l/mm to cover the energy range 260 – 2600 eV. The groove parameters of the varied-line-spacing plane gratings are designed to minimize the effect of coma and spherical aberration to maintain the exit slit in focus for any value of incident angle. All parameters of optical components at the beamline are verified with a ray-tracing method. In the beamline design, the calculatedmore » results from the ray-tracing codes and the expected performances are discussed.« less

[Origin of the oxygen detected by the Viking stations in an analysis of Mars soil].

PubMed

Imshenetskiĭ, A A; Murzakov, B G; Dorofeeva, I K

1978-01-01

Reactions between the mineral limonite and hydrogen peroxide were studied and gases produced thereupon were analysed by gas chromatography. Oxygen did not evolve if limonite was added to hydrogen peroxide frozen at a temperature of dry ice. However, at room temperature, a vigorous chemical reaction occurred and a large amount of oxygen evolved. Apparently, the ground of Mars contains not only hydrated iron oxides but also frozen hydrogen peroxide whose thawing in the incubation chamber of Viking resulted in its catalytic degradation under the action of iron ions. The evidence thus obtained and its comparison with the data of American scientists account for considerable evolution of oxygen detected by Viking upon analysis of the Mars ground.

Hydrohalite spatial distribution in frozen cell cultures measured using confocal Raman microscopy.

PubMed

Kreiner-Møller, Asger; Stracke, Frank; Zimmermann, Heiko

2014-08-01

Hydrohalite, a crystalline rock salt hydrate, (NaCl·2H2O), can form in cryopreservation samples under certain circumstances changing the local chemical environment of the preserved cells. Evidence of this crystalline phase was recently found by microspectroscopy measurements, and believed to form exclusively extracellular. We have studied the spatial distribution of hydrohalite in frozen mouse fibroblast cell samples by means of confocal Raman scanning microscopy (CRM). Hydrohalite has a unique Raman spectrum with several bands in the high frequency tail of the OH-stretching band which can be used for unambiguous identification. Hydrohalite can only form through eutectic crystallization in saline solutions without any cryoprotective agents and the spatial distribution thus gives a more detailed view on this crystallization process. This is important since eutectic crystallization has been empirically correlated to cell death, but the exact injury mechanism is unclear. By the means of colocalization of Raman bands we show that hydrohalite can indeed form intracellularly and is not a strictly extracellular phenomenon. We furthermore found that intracellular ice and intracellular hydrohalite very often coincide. Finally we show that the addition of 0.5 wt.% dimethyl sulfoxide (Me2SO) inhibits formation of hydrohalite. This study shows how Raman microscopy and successive analysis can be employed non-invasively within cryobiology to give additional chemical and structural information compared to conventional imaging techniques. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Effect of storage conditions on carbon-centered radicals in soy protein products.

PubMed

Boatright, William L; Lei, Qingxin; Shah Jahan, M

2009-09-09

Using electron paramagnetic resonance (EPR) spectroscopy, the levels of carbon-centered radicals in retail samples of isolated soy protein (ISP), soy protein concentrate (SPC), and powdered soy milk were estimated to contain from 6.12 x 10(14) to 1.98 x 10(15) spins/g of soy product. Roasted soy nuts contained about 5.70 x 10(15) spins/g. The peak to peak line width of the carbon-centered radicals from soy nuts was about 10 gauss, whereas ISP samples with a similar peak height had a peak to peak line width of about 8 gauss. Retail snack bars containing ISP, SPC, and/or roasted soy nuts with a total protein content of either 13, 21, or 29% contained 5.32 x 10(14), 6.67 x 10(14), and 5.74 x 10(14) spins/g of snack bar, respectively. Levels of carbon-centered radicals in newly prepared samples of ISP were much lower than levels in the retail soy protein products and levels previously reported for commercial ISP and laboratory ISP samples. The levels of radicals in ISP samples increased over a 12-25 week period of storage in the dark at 22 degrees C and exposed to air from about 8.00 x 10(13) spins/g immediately after preparation to 9.95 x 10(14) spins/g of ISP. Storing the ISP samples under nitrogen at 22 degrees C greatly reduced the increase in radical content, whereas storing the ISP in 99.9% oxygen at 40 degrees C accelerated the formation of stable carbon-centered radicals. ISP samples hydrated at either 22 or 92 degrees C, rapidly frozen, and dried lost about 92% of the trapped radicals. The level of carbon-centered radicals in these same ISP samples immediately began to increase during subsequent storage exposed to the air and gradually returned to similar levels obtained before they were hydrated.

Effect of freezing on the rheological, chemical and colour properties of Serpa cheese.

PubMed

Alvarenga, Nuno; Canada, João; Sousa, Isabel

2011-02-01

The effect of freezing on the properties of a raw ewes'-milk semi-soft cheese (Serpa cheese) was studied using small amplitude oscillatory (SAOS) and texture measurements, colour and chemical parameters. The freezing was introduced at three different stages of the ripening process (28, 35 and 42 days), and the cheeses were maintained frozen for 12 months. Cheeses were submitted to a slow or fast freezing method, and to different storage temperatures: -10 and -20°C (three replicates for each set conditions). Chemical data showed that only the proteolysis indicators exhibited differences between frozen and non-frozen samples; frozen samples showed higher values of NPN than the non-frozen samples, indicating that the freezing process did not prevent the secondary proteolysis of cheese. Frozen samples showed a significantly (P<0·05) stronger structure than the non-frozen, as indicated by hardness. However, the differences between the frozen and non-frozen samples were not significantly for storage modulus (G' 1Hz) and loss tangent (tan δ 1Hz) (P>0·05). Freezing affected mainly colour parameters: frozen samples were more luminous, and more yellow-green. The results allowed us to conclude that the damages caused by freezing to cheese properties could be minimized if this type of storage is introduced at the end of ripening (42 d) using a freezing temperature of -20°C.

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

NASA Astrophysics Data System (ADS)

Seol, Yongkoo; Kneafsey, Timothy J.

2011-08-01

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

Benefits and Limitations of Low-kV Macromolecular Imaging of Frozen-Hydrated Biological Samples

PubMed Central

Majorovits, Endre; Angert, Isabel; Kaiser, Ute; Schröder, Rasmus R.

2016-01-01

Object contrast is one of the most important parameters of macromolecular imaging. Low-voltage transmission electron microscopy has shown an increased atom contrast for carbon materials, indicating that amplitude contrast contributions increase at a higher rate than phase contrast and inelastic scattering. Here, we studied image contrast using ice-embedded tobacco mosaic virus particles as test samples at 20–80 keV electron energy. The particles showed the expected increase in contrast for lower energies, but at the same time the 2.3-nm-resolution measure decayed more rapidly. We found a pronounced signal loss below 60 keV, and therefore we conclude that increased inelastic scattering counteracts increased amplitude contrast. This model also implies that as long as the amplitude contrast does not increase with resolution, beam damage and multiple scattering will always win over increased contrast at the lowest energies. Therefore, we cannot expect that low-energy imaging of conventionally prepared samples would provide better data than state-of-the-art 200–300 keV imaging. PMID:26910420

Thinning of Large Biological Cells for Cryo-TEM Characterization by Cryo-FIB Milling

PubMed Central

Strunk, Korrinn M.; Ke, Danxia; Gray, Jennifer L.; Zhang, Peijun

2013-01-01

SUMMARY Focused ion beam milling at cryogenic temperatures (cryo-FIB) is a valuable tool that can be used to thin vitreous biological specimens for subsequent imaging and analysis in a cryo-transmission electron microscope (cryo-TEM) in their frozen-hydrated state. This technique offers the potential benefit of eliminating the mechanical artifacts that are typically found with cryo-ultramicrotomy. However, due to the additional complexity in transferring samples in and out of the FIB, contamination and devitrification of the amorphous ice is commonly encountered. In order to address these problems, we have designed a new sample cryo-shuttle that specifically accepts Polara TEM cartridges directly in order to simplify the transfer process between the FIB and TEM. We used the quality of the ice in the sample as an indicator to test various parameters used the process, and demonstrated with successful milling of large mammalian cells. By comparing the results from larger HeLa cells to those from E. coli cells, we discuss some of the artifacts and challenges we have encountered using this technique. PMID:22906009

Proceedings of the fifth international offshore mechanics and Arctic engineering (OMAE) symposium. Volume 4

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

Lunardini, V.J.; Wang, Y.S.; Ayorinde, O.A.

1986-01-01

This book presents the papers given at a symposium on offshore platforms. Topics considered at the symposium included climates, Arctic regions, hydrate formation, the buckling of heated oil pipelines in frozen ground, icebergs, concretes, air cushion vehicles, mobile offshore drilling units, tanker ships, ice-induced dynamic loads, adfreeze forces on offshore platforms, and multiyear ice floe collision with a massive offshore structure.

TOF-SIMS imaging of chlorhexidine-digluconate transport in frozen hydrated biofilms of the fungus Candida albicans

NASA Astrophysics Data System (ADS)

Tyler, Bonnie J.; Rangaranjan, Srinath; Möller, Jörg; Beumer, Andre'; Arlinghaus, Heinrich F.

2006-07-01

The diffusion of the anti-microbial chlorhexidine digluconate (CHG) has been studied in C. albicans biofilms by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). C. albicans has been shown to become resistant to common anti-microbial agents, including CHG, when growing as a biofilm. Mass transport resistance within biofilms has commonly been suggested as a resistance mechanism, but measurement of transport for most anti-microbial agents in biofilms has proven extremely difficult because of the heterogeneity of the biofilms and the difficulty in detecting these agents within an intact biofilm. In this study, TOF-SIMS has been used to study the transport of CHG and glucose in a frozen hydrated biofilm. The TOF-SIMS images reveal a progression of CHG from the top of the biofilm to its base with time. Images suggest that there are channels within the biofilm and show preferential binding of CHG to cellular components of the biofilm. Additionally, both living and dead cells can be identified in the TOF-SIMS images by the sequestration of K + and the presence of cell markers. This study demonstrates that TOF-SIMS has the unique potential to simultaneously observe the presence of an antimicrobial agent, concentration of nutrients, and the viability of the cell population.

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

USGS Publications Warehouse

Winters, W.J.

1999-01-01

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

Influence of freezing and thawing on the hydration characteristics, quality, and consumer acceptance of whole muscle beef injected with solutions of salt and phosphate.

PubMed

Pietrasik, Z; Janz, J A M

2009-03-01

Effects of salt/phosphate injection level (112% or 125% pump), salt level (0.5% or 1.5% salt), and freezing/thawing on hydration characteristics, quality, and consumer acceptance of beef semitendinosus were investigated. All enhancement treatments decreased shear force by 25-35%, but negatively affected colour. Increased salt concentration yielded lower purge and cooking losses, and higher water holding capacity. The higher injection level reduced water binding properties, however, the loss in functionality with higher water addition was overcome with increased salt content. Freezing and subsequent thawing was generally detrimental to colour and water binding properties and tended to increase shear force. Freezing and subsequent thawing did not affect fluid release in steaks held for 1 day before analysis, but resulted in decreased water retention in samples held for 7 days. Holding vacuum packaged steaks for 7 days generally increased package purge and negatively affected colour parameters, although water binding characteristics were improved. Consumer panel results demonstrated a negative effect on juiciness and tenderness where meat subject to low salt/high injection was frozen then thawed - the low salt level was insufficient to maintain any positive effect of injection treatment. In general, salt/phosphate injection improved product acceptability and increased willingness to purchase.

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

NASA Astrophysics Data System (ADS)

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

2005-10-01

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

Efficient Recovery of Fluoroquinolone-Susceptible and Fluoroquinolone-Resistant Escherichia coli Strains From Frozen Samples

PubMed Central

Lautenbach, Ebbing; Santana, Evelyn; Lee, Abby; Tolomeo, Pam; Black, Nicole; Babson, Andrew; Perencevich, Eli N.; Harris, Anthony D.; Smith, Catherine A.; Maslow, Joel

2010-01-01

We assessed the rate of recovery of fluoroquinolone-resistant and fluoroquinolone-susceptible Escherichia coli isolates from culture of frozen perirectal swab samples compared with the results for culture of the same specimen before freezing. Recovery rates for these 2 classes of E. coli were 91% and 83%, respectively. The majority of distinct strains recovered from the initial sample were also recovered from the frozen sample. The strains that were not recovered were typically present only in low numbers in the initial sample. These findings emphasize the utility of frozen surveillance samples. PMID:18279070

Efficient recovery of fluoroquinolone-susceptible and fluoroquinolone-resistant Escherichia coli strains from frozen samples.

PubMed

Lautenbach, Ebbing; Santana, Evelyn; Lee, Abby; Tolomeo, Pam; Black, Nicole; Babson, Andrew; Perencevich, Eli N; Harris, Anthony D; Smith, Catherine A; Maslow, Joel

2008-04-01

We assessed the rate of recovery of fluoroquinolone-resistant and fluoroquinolone-susceptible Escherichia coli isolates from culture of frozen perirectal swab samples compared with the results for culture of the same specimen before freezing. Recovery rates for these 2 classes of E. coli were 91% and 83%, respectively. The majority of distinct strains recovered from the initial sample were also recovered from the frozen sample. The strains that were not recovered were typically present only in low numbers in the initial sample. These findings emphasize the utility of frozen surveillance samples.

Entropic Anomaly Observed in Lipid Polymorphisms Induced by Surfactant Peptide SP-B(1-25).

PubMed

Tran, Nhi; Kurian, Justin; Bhatt, Avni; McKenna, Robert; Long, Joanna R

2017-10-05

The N-terminal 25 amino-acid residues of pulmonary surfactant protein B (SP-B 1-25 ) induces unusual lipid polymorphisms in a model lipid system, 4:1 DPPC/POPG, mirroring the lipid composition of native pulmonary surfactant. It is widely suggested that SP-B 1-25 -induced lipid polymorphisms within the alveolar aqueous subphase provide a structural platform for rapid lipid adsorption to the air-water interface. Here, we characterize in detail the phase behavior of DPPC and POPG in hydrated lipid assemblies containing therapeutic levels of SP-B 1-25 using 2 H and 31 P solid state NMR spectroscopy. The appearance of a previously observed isotropic lipid phase is found to be highly dependent on the thermal cycling of the samples. Slow heating of frozen samples leads to phase separation of DPPC into a lamellar phase whereas POPG lipids interact with the peptide to form an isotropic phase at physiologic temperature. Rapid heating of frozen samples to room temperature leads to strongly isotropic phase behavior for both DPPC and POPG lipids, with DPPC in exchange between isotropic and interdigitated phases. 31 P T 2 relaxation times confirm the isotropic phase to be consistent with a lipid cubic phase. The observed phases exhibit thermal stability up to physiologic temperature (37 °C) and are consistent with the formation of a ripple phase containing a large number of peptide-induced membrane structural defects enabling rapid transit of lipids between lipid lamellae. The coexistance of a lipid cubic phase with interdigitated lipids suggests a specific role for the highly conserved N-terminus of SP-B in stabilizing this unusual lipid polymorphism.

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.

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

USGS Publications Warehouse

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

2011-01-01

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

A Limited Survey of Heavy Metal Concentrations in Fresh and Frozen Cuttlefish Ink and Mantle Used As Food.

PubMed

Conficoni, Daniele; Alberghini, Leonardo; Bissacco, Elisa; Contiero, Barbara; Giaccone, Valerio

2018-02-01

Cuttlefish ink is consumed as a delicacy worldwide. The current study is the first assessment of heavy metal concentrations in cuttlefish ink versus mantle under different storage methods. A total of 212 samples (64 of fresh mantle, 42 of frozen mantle, 64 of fresh ink, and 42 of frozen ink) were analyzed for the detection of the following heavy metals: arsenic (As), chromium (Cr), iron (Fe), lead (Pb), mercury (Hg), and cadmium (Cd). The median As concentrations were 12.9 mg/kg for fresh mantle, 8.63 mg/kg for frozen mantle, 10.8 mg/kg for frozen ink, and 0.41 mg/kg for fresh ink. The median Cr concentrations were 0.06 mg/kg for fresh mantle and frozen ink, 0.03 mg/kg for frozen mantle, and below the limit of quantification (LOQ) for fresh ink. The median Fe concentrations were 4.08 mg/kg for frozen ink, 1.51 mg/kg for fresh mantle, 0.73 mg/kg for frozen mantle, and below the LOQ for fresh ink. The median Pb concentrations of almost all samples were below the LOQ; only two frozen ink, one fresh ink, one frozen mantle, and one fresh mantle sample exceeded the limit stipulated by the European Union. The Hg concentrations were statistically similar among the four categories of samples; the median Hg concentrations were below the LOQ, and the maximum concentrations were found in frozen ink, at 1.62 mg/kg. The median Cd concentrations were 0.69 mg/kg for frozen ink and 0.11 mg/kg for frozen mantle, fresh mantle and fresh ink concentrations were below the LOQ, and in 11.3% of the tested samples, Cd concentrations were higher than the European Union limit. The probability of samples having a Cd concentration above the legal limit was 35.75 times higher in frozen than in fresh products. Fresh ink had significantly lower concentrations of As, Cr, Fe, and Cd, but the concentrations of Hg and Pb were not significantly different from those of other products. Frozen ink had significantly higher concentrations of Cd, Cr, and Fe, but concentrations of As were lower than those in fresh mantle, pointing out a possible role for the freezing process and for different fishing zones as risk factors for heavy metal contamination.

Effect of different cooking methods on color, phytochemical concentration, and antioxidant capacity of raw and frozen brassica vegetables.

PubMed

Pellegrini, Nicoletta; Chiavaro, Emma; Gardana, Claudio; Mazzeo, Teresa; Contino, Daniele; Gallo, Monica; Riso, Patrizia; Fogliano, Vincenzo; Porrini, Marisa

2010-04-14

This study evaluated the effect of common cooking practices (i.e., boiling, microwaving, and basket and oven steaming) on the phytochemical content (carotenoids, chlorophylls, glucosinolates, polyphenols, and ascorbic acid), total antioxidant capacity (TAC), and color changes of three generally consumed Brassica vegetables analyzed fresh and frozen. Among cooking procedures, boiling determined an increase of fresh broccoli carotenoids and fresh Brussels sprout polyphenols, whereas a decrease of almost all other phytochemicals in fresh and frozen samples was observed. Steaming procedures determined a release of polyphenols in both fresh and frozen samples. Microwaving was the best cooking method for maintaining the color of both fresh and frozen vegetables and obtaining a good retention of glucosinolates. During all cooking procedures, ascorbic acid was lost in great amount from all vegetables. Chlorophylls were more stable in frozen samples than in fresh ones, even though steaming methods were able to better preserve these compounds in fresh samples than others cooking methods applied. The overall results of this study demonstrate that fresh Brassica vegetables retain phytochemicals and TAC better than frozen samples.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Effects of core retrieval, handling, and preservation on hydrate-bearing samples

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Lu, H.; Winters, W. J.; Hunter, R. B.

2009-12-01

Recovery, preservation, storage, and transport of samples containing natural gas hydrate cause changes in the stress conditions, temperature, pressure, and hydrate saturation of samples. Sample handling at the ground surface and sample preservation, either by freezing in liquid nitrogen (LN) or repressurization using methane, provides additional time and driving forces for sample alteration. The extent to which these disturbances alter the properties of the hydrate bearing sediments (HBS) depend on specific sample handling techniques, as well as on the sample itself. HBS recovered during India’s National Gas Hydrate Program (NGHP) Expedition 01 and the 2007 BP Exploration Alaska - Department of Energy - U.S. Geological Survey (BP-DOE-USGS) Mount Elbert (ME) gas hydrate well on the Alaskan North Slope provide comparisons of sample alterations induced by multiple handling techniques. HBS samples from the NGHP and the ME projects were examined using x-ray computed tomography. Mount Elbert sand samples initially preserved in LN have non-uniform short “crack-like” low-density zones in the center that probably do not extend to the outside perimeter. Samples initially preserved by repressurization show fewer “crack-like” features and higher densities. Two samples were analyzed in detail by Lu and coworkers showing reduced hydrate saturations approaching the outer surface, while substantial hydrate remained in the central region. Non-pressure cored NGHP samples show relatively large altered regions approaching the core surface, while pressure-cored-liquid-nitrogen preserved samples have much less alteration.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Lunar and Planetary Science XXXVI, Part 6

NASA Technical Reports Server (NTRS)

2005-01-01

Contents include the following: A Model for Multiple Populations of Presolar Diamonds. Characterization of Martian North Polar Geologic Units Using Mars Odyssey THEMIS Data. Effect of Flow on the Internal Structure of the Martian North Polar Layered Deposits. Elemental Abundance Distributions in Basalt Clays and Meteorites: Is It a Biosignature? Early Results on the Saturn System from the Composite Infrared Spectrometer. NanoSIMS D/H Imaging of Isotopically Primitive Interplanetary Dust Particles. Presolar (Circumstellar and Interstellar) Phases in Renazzo: The Effects of Parent Body Processing. Catastrophic Disruption of Hydrated Targets: Implications for the Hydrated Asteroids and for the Production of Interplanetary Dust Particles. Chemical and Mineralogical Analyses of Particles from the Stratospheric Collections Coinciding with the 2002 Leonid Storm and the 2003 Comet Grigg-Skjellerup Trail Passage. An Analysis of the Solvus in the CaS-MnS System. ESA s SMART-1 Mission at the Moon: First Results, Status and Next Steps. Europa Analog Ice-splitting Measurements and Experiments with Ice-Hunveyor on the Frozen Balaton-Lake, Hungary. Chromium on Eros: Further Evidence of Ordinary Chondrite Composition. Dust Devil Tracks on Mars: Observation and Analysis from Orbit and the Surface. Spatial Variation of Methane and Other Trace Gases Detected on Mars: Interpretation with a General Circulation Model. Mars Water Ice and Carbon Dioxide Seasonal Polar Caps: GCM Modeling and Comparison with Mars Express Omega Observations. Component Separation of OMEGA Spectra with ICA. Clathrate Formation in the Near-Surface Environment of Titan. Space Weathering: A Proposed Laboratory Approach to Explaining the Sulfur Depletion on Eros. Sample Collection from Small Airless Bodies: Examination of Temperature Constraints for the TGIP. Sample Collector for the Hera Near-Earth Asteroid Sample Return Mission. A Rugged Miniature Mass-Spectrometer for Measuring Aqueous Geochemistry on Mars. Martian and Lunar Pyroxene Microstructures Studied by Single-Crystal X-Ray Diffraction.

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

USGS Publications Warehouse

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

2004-01-01

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

Detection and Characterization of Circulating Tumour Cells from Frozen Peripheral Blood Mononuclear Cells

PubMed Central

Lu, David; Graf, Ryon P.; Harvey, Melissa; Madan, Ravi A.; Heery, Christopher; Marte, Jennifer; Beasley, Sharon; Tsang, Kwong Y.; Krupa, Rachel; Louw, Jessica; Wahl, Justin; Bales, Natalee; Landers, Mark; Marrinucci, Dena; Schlom, Jeffrey; Gulley, James L.; Dittamore, Ryan

2015-01-01

Retrospective analysis of patient tumour samples is a cornerstone of clinical research. CTC biomarker characterization offers a non-invasive method to analyse patient samples. However, current CTC technologies require prospective blood collection, thereby reducing the ability to utilize archived clinical cohorts with long-term outcome data. We sought to investigate CTC recovery from frozen, archived patient PBMC pellets. Matched samples from both mCRPC patients and mock samples, which were prepared by spiking healthy donor blood with cultured prostate cancer cell line cells, were processed “fresh” via Epic CTC Platform or from “frozen” PBMC pellets. Samples were analysed for CTC enumeration and biomarker characterization via immunofluorescent (IF) biomarkers, fluorescence in-situ hybridization (FISH) and CTC morphology. In the frozen patient PMBC samples, the median CTC recovery was 18%, compared to the freshly processed blood. However, abundance and localization of cytokeratin (CK) and androgen receptor (AR) protein, as measured by IF, were largely concordant between the fresh and frozen CTCs. Furthermore, a FISH analysis of PTEN loss showed high concordance in fresh vs. frozen. The observed data indicate that CTC biomarker characterization from frozen archival samples is feasible and representative of prospectively collected samples. PMID:28936240

Fresh vs Frozen Samples and Ambient Temperature Have Little Effect on Detection of Colorectal Cancer or Adenomas by a Fecal Immunochemical Test in a Colorectal Cancer Screening Cohort in Germany.

PubMed

Chen, Hongda; Werner, Simone; Brenner, Hermann

2017-10-01

Fecal immunochemical tests (FITs) are used in colorectal cancer (CRC) screening. We compared detection of CRCs and colorectal neoplasms by FITs using fresh samples (collected into buffer-filled tubes) vs frozen samples, and we assessed the effects of seasonal variations in ambient temperature on test performance. We performed a prospective study of 3466 individuals (50% male; mean age, 62 years) undergoing screening colonoscopies at 20 gastroenterology practices in southern Germany from November 2008 through September 2014. Frozen stool samples (collected and frozen by patients through February 2012, n = 1644) and fresh stool samples (collected by patients into buffer-filled tubes after February 2012, n = 1822) were obtained; hemoglobin (Hgb) concentrations were measured by using a commercial, quantitative FIT (cutoff value for positive result, 17 μg Hgb/g feces). Colonoscopy results were used as the gold standard, with results categorized as CRC, advanced adenoma, non-advanced adenoma, or no colorectal neoplasm. Differences in detection of colorectal neoplasms with fresh vs frozen samples were compared by using Wilcoxon rank sum test (continuous variables) and Fisher exact test (categorical variables). We also compared test performance when samples were collected during different seasons (based on outdoor temperature less than 8°, 8°-15°, or more than 15°). Of the samples analyzed by FIT, 12.8% of frozen stool samples (95% confidence interval [CI], 11.3%-14.5%) and 8.7% of fresh stool samples (95% CI, 7.5%-10.1%) had positive results (P value for difference < .001). When adjusting the Hgb cutoff value to produce the same percentage of positive results for fresh and frozen samples (10% and 5%), FIT with frozen vs fresh samples detected colorectal neoplasms with similar levels of sensitivity and specificity. For example, at cutoff values that produced 5% positive results for each sample type, FIT detected advanced neoplasms with 27.8% sensitivity when frozen samples were used (95% CI, 21.4%-35.1%) and 25.6% sensitivity when fresh samples were used (95% CI, 19.8%-32.1%). Specificity values were 97.7% when frozen samples were used (95% CI, 96.8%-98.4%) and 97.6% when fresh samples were used (95% CI, 96.7%-98.3%). We did not observe any differences in detection of neoplasms during different seasons that were based on outdoor temperature. In a prospective study of 3466 individuals who underwent screening colonoscopies and received FITs, we found that use of fresh vs frozen samples slightly affected positivity rates and the proportions of CRCs or adenomas detected at the recommended Hgb cutoff value. However, after we adjusted Hgb cutoff values to produce equal proportions of positive results for fresh vs frozen samples, the performance of the FIT was similar with each sample type. Season of sample collection (based on outdoor temperature) did not affect detection of CRC using either sample type in this study from Middle Europe. Copyright © 2017 AGA Institute. Published by Elsevier Inc. All rights reserved.

Examination of Hydrate Formation Methods: Trying to Create Representative Samples

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

Kneafsey, T.J.; Rees, E.V.L.; Nakagawa, S.

2011-04-01

Forming representative gas hydrate-bearing laboratory samples is important so that the properties of these materials may be measured, while controlling the composition and other variables. Natural samples are rare, and have often experienced pressure and temperature changes that may affect the property to be measured [Waite et al., 2008]. Forming methane hydrate samples in the laboratory has been done a number of ways, each having advantages and disadvantages. The ice-to-hydrate method [Stern et al., 1996], contacts melting ice with methane at the appropriate pressure to form hydrate. The hydrate can then be crushed and mixed with mineral grains under controlledmore » conditions, and then compacted to create laboratory samples of methane hydrate in a mineral medium. The hydrate in these samples will be part of the load-bearing frame of the medium. In the excess gas method [Handa and Stupin, 1992], water is distributed throughout a mineral medium (e.g. packed moist sand, drained sand, moistened silica gel, other porous media) and the mixture is brought to hydrate-stable conditions (chilled and pressurized with gas), allowing hydrate to form. This method typically produces grain-cementing hydrate from pendular water in sand [Waite et al., 2004]. In the dissolved gas method [Tohidi et al., 2002], water with sufficient dissolved guest molecules is brought to hydrate-stable conditions where hydrate forms. In the laboratory, this is can be done by pre-dissolving the gas of interest in water and then introducing it to the sample under the appropriate conditions. With this method, it is easier to form hydrate from more soluble gases such as carbon dioxide. It is thought that this method more closely simulates the way most natural gas hydrate has formed. Laboratory implementation, however, is difficult, and sample formation is prohibitively time consuming [Minagawa et al., 2005; Spangenberg and Kulenkampff, 2005]. In another version of this technique, a specified quantity of gas is placed in a sample, then the sample is flooded with water and cooled [Priest et al., 2009]. We have performed a number of tests in which hydrate was formed and the uniformity of the hydrate formation was examined. These tests have primarily used a variety of modifications of the excess gas method to make the hydrate, although we have also used a version of the excess water technique. Early on, we found difficulties in creating uniform samples with a particular sand/ initial water saturation combination (F-110 Sand, {approx} 35% initial water saturation). In many of our tests we selected this combination intentionally to determine whether we could use a method to make the samples uniform. The following methods were examined: Excess gas, Freeze/thaw/form, Freeze/pressurize/thaw, Excess gas followed by water saturation, Excess water, Sand and kaolinite, Use of a nucleation enhancer (SnoMax), and Use of salt in the water. Below, each method, the underlying hypothesis, and our results are briefly presented, followed by a brief conclusion. Many of the hypotheses investigated are not our own, but were presented to us. Much of the data presented is from x-ray CT scanning our samples. The x-ray CT scanner provides a three-dimensional density map of our samples. From this map and the physics that is occurring in our samples, we are able to gain an understanding of the spatial nature of the processes that occur, and attribute them to the locations where they occur.« less

Laboratory formation of non-cementing, methane hydrate-bearing sands

USGS Publications Warehouse

Waite, William F.; Bratton, Peter M.; Mason, David H.

2011-01-01

Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

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

USGS Publications Warehouse

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

2008-01-01

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

Lensless Tomographic Imaging of Near Surface Structures of Frozen Hydrated Malaria-Infected Human Erythrocytes by Coherent X-Ray Diffraction Microscopy.

PubMed

Frank, Viktoria; Chushkin, Yuriy; Fröhlich, Benjamin; Abuillan, Wasim; Rieger, Harden; Becker, Alexandra S; Yamamoto, Akihisa; Rossetti, Fernanda F; Kaufmann, Stefan; Lanzer, Michael; Zontone, Federico; Tanaka, Motomu

2017-10-26

Lensless, coherent X-ray diffraction microscopy has been drawing considerable attentions for tomographic imaging of whole human cells. In this study, we performed cryogenic coherent X-ray diffraction imaging of human erythrocytes with and without malaria infection. To shed light on structural features near the surface, "ghost cells" were prepared by the removal of cytoplasm. From two-dimensional images, we found that the surface of erythrocytes after 32 h of infection became much rougher compared to that of healthy, uninfected erythrocytes. The Gaussian roughness of an infected erythrocyte surface (69 nm) is about two times larger than that of an uninfected one (31 nm), reflecting the formation of protein knobs on infected erythrocyte surfaces. Three-dimensional tomography further enables to obtain images of the whole cells with no remarkable radiation damage, whose accuracy was estimated using phase retrieval transfer functions to be as good as 64 nm for uninfected and 80 nm for infected erythrocytes, respectively. Future improvements in phase retrieval algorithm, increase in degree of coherence, and higher flux in combination with complementary X-ray fluorescence are necessary to gain both structural and chemical details of mesoscopic architectures, such as cytoskeletons, membraneous structures, and protein complexes, in frozen hydrated human cells, especially under diseased states.

The use of frozen plasma samples in thromboelastometry.

PubMed

Schoergenhofer, Christian; Buchtele, Nina; Schwameis, Michael; Bartko, Johann; Jilma, Bernd; Jilma-Stohlawetz, Petra

2017-11-01

Thromboelastometry is increasingly used in the clinical and scientific setting. The use of frozen plasma samples may be useful in overcoming certain limitations such as local and timely availability. Whole blood (WB) samples of 20 healthy volunteers were obtained, and plasma was generated. NATEM (n = 20), EXTEM (n = 20) and INTEM (n = 8) analyses were performed in WB, fresh plasma and frozen and thawed plasma. Dabigatran (500, 1000 ng/ml), rivaroxaban (100, 200 ng/ml) or alteplase (333 ng/ml) were added ex vivo to WB, and thromboelastometry was performed in WB and in frozen and thawed plasma samples. Clot formation time, mean clot firmness and the area under the curve were significantly altered in plasma compared to WB. In INTEM and EXTEM analysis, clotting time (CT) was comparable between WB (100%) and fresh (INTEM 114% and EXTEM 93%, ratio of the means) and frozen plasma samples (85 and 99%), whereas in NATEM analysis, the CT increased in fresh (193%) and frozen plasma samples (130%). Dabigatran dose-dependently increased the CT approximately 5- and 9-fold in WB and even more pronounced 10- and 26-fold in plasma. Accordingly, rivaroxaban dose-dependently increased the CT 2- and 2.7-fold in WB, and 3.5- and 4-fold in plasma samples. Hyperfibrinolysis was achieved by addition of alteplase in all WB samples and was reproducible in plasma samples. In conclusion, thromboelastometry, especially INTEM and EXTEM analyses, is possible using frozen and stored plasma samples with comparable results to the corresponding whole blood samples.

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

PubMed

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

2012-06-21

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

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Cyclic formation and dissociation of methane hydrate within partially water saturated sand

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Nakagawa, S.

2010-12-01

For partially water-saturated sediments, laboratory experiments have shown that methane hydrate forms heterogeneously within a sample at the core scale. The heterogeneous distribution of hydrate in combination with grain-scale hydrate location (eg. grain cementing, load bearing, and pore filling), determines the overall mechanical properties of hydrate-bearing sediments including shear strength and seismic properties. For this reason, understanding the heterogeneity of hydrate-bearing sample is essential when the bulk properties of the sample are examined in the laboratory. We present a series of laboratory methane hydrate formation and dissociation experiments with concurrent x-ray CT imaging and low-frequency (near 1 kHz) seismic measurements. The seismic measurements were conducted using a new acoustic resonant bar technique called the Split Hopkinson Resonant Bar method, which allows using a small sediment core (3.75 cm diameter, 7.5 cm length). The experiment was conducted using a jacketed, pre-compacted, fine-grain silica sand sample with a 40% distilled water saturation. Under isotropic confining stress of 6.9 MPa and a temperature 4 oC, the hydrate was formed in the sample by injecting pure methane gas at 5.6 MPa. Once the hydrate formed, it was dissociated by reducing the pore pressure to 2.8 MPa. This cycle was repeated by three times (dissociation test for the third cycle was not done) to examine the resulting changes in the hydrate distribution and seismic signatures. The repeated formation of hydrate resulted in significant changes in its distribution, which resulted in differences in the overall elastic properties of the sample, determined from the seismic measurements. Interestingly, the time intervals between the dissociation and subsequent formation of hydrate affected the rate of hydrate formation, shorter intervals resulting in faster formation. This memory effect, possibly caused by the presence of residual “seed crystals” in the pore water providing nucleation points for hydrate formation, did not result in rapid formation at all locations in the sample. In spite of heterogeneity, observed seismic properties were very similar for the two measurements during dissociation.

Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

NASA Astrophysics Data System (ADS)

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

2002-12-01

We compare dissolution rates of pure, porous, compacted, and oil-contaminated sI methane hydrate and sII methane-ethane hydrate to rates measured previously on pure, compacted, sI methane hydrate and sI carbon dioxide hydrate (Rehder et al., Fall AGU 2001). Laboratory-synthesized test specimens were used in both studies, allowing characterization of test materials prior to their transport and exposure to seawater at 1030-meter depth on the Monterey Canyon seafloor, off coastal Moss Landing, CA. Although pressure and temperature (P-T) conditions at this site are within the nominal P-T equilibrium fields of all gas hydrates tested here, the seawater is undersaturated with respect to the hydrate-forming gas species. Hence, samples dissolve with time, at a rate dependent on water current flow. Four samples were deployed in this second experiment: (1) pure, 30% porous methane hydrate; (2) pure, compacted methane hydrate; (3) pure methane hydrate compacted and then contaminated with a low-T mineral oil; and (4) pure, compacted sII methane-ethane hydrate with methane:ethane molar ratio 0.72. Samples were transferred by pressure vessel at 0 ° C and 15 MPa to the seafloor observatory via the MBARI remotely operated vehicle Ventana. Samples were then exposed to the deep ocean environment and monitored by HDTV camera for several hours at the beginning and end of a 25-hour period. Local current speed and direction were also measured throughout the experiment. Those samples that did not undergo complete dissolution after 25 h were successfully recovered to the laboratory for subsequent analysis by scanning electron microscopy (SEM). Previously, video analysis showed dissolution rates corresponding to 4.0 +/- 0.5 mmole CO2/m2 s for compacted CO2 hydrate samples, and 0.37 +/- 0.03 mmole CH4/m2s for compacted methane hydrate samples (Rehder et al, AGU 2001). The ratio of dissolution rates fits a simple diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

Recent changes to the Gulf Stream causing widespread gas hydrate destabilization.

PubMed

Phrampus, Benjamin J; Hornbach, Matthew J

2012-10-25

The Gulf Stream is an ocean current that modulates climate in the Northern Hemisphere by transporting warm waters from the Gulf of Mexico into the North Atlantic and Arctic oceans. A changing Gulf Stream has the potential to thaw and convert hundreds of gigatonnes of frozen methane hydrate trapped below the sea floor into methane gas, increasing the risk of slope failure and methane release. How the Gulf Stream changes with time and what effect these changes have on methane hydrate stability is unclear. Here, using seismic data combined with thermal models, we show that recent changes in intermediate-depth ocean temperature associated with the Gulf Stream are rapidly destabilizing methane hydrate along a broad swathe of the North American margin. The area of active hydrate destabilization covers at least 10,000 square kilometres of the United States eastern margin, and occurs in a region prone to kilometre-scale slope failures. Previous hypothetical studies postulated that an increase of five degrees Celsius in intermediate-depth ocean temperatures could release enough methane to explain extreme global warming events like the Palaeocene-Eocene thermal maximum (PETM) and trigger widespread ocean acidification. Our analysis suggests that changes in Gulf Stream flow or temperature within the past 5,000 years or so are warming the western North Atlantic margin by up to eight degrees Celsius and are now triggering the destabilization of 2.5 gigatonnes of methane hydrate (about 0.2 per cent of that required to cause the PETM). This destabilization extends along hundreds of kilometres of the margin and may continue for centuries. It is unlikely that the western North Atlantic margin is the only area experiencing changing ocean currents; our estimate of 2.5 gigatonnes of destabilizing methane hydrate may therefore represent only a fraction of the methane hydrate currently destabilizing globally. The transport from ocean to atmosphere of any methane released--and thus its impact on climate--remains uncertain.

Effect of gamma-irradiation on frozen shrimps for decontamination of pathogenic bacteria

NASA Astrophysics Data System (ADS)

Ito, Hitoshi; Rashid, Harun Or; Sangthong, Naruemon; Adulyatham, Pitaya; Rattagool, Pongpen; Ishigaki, Isao

1993-07-01

Twelve samples of imported frozen shrimps were used in this study. The total aerobic bacteria were at 2 × 10 4 to 6 × 10 6 per gram. A few of Vibrio parahaemolyticus, V. mimicus, V. alginolyticus, V. vulnificus, V. fluvialis and Listeria monocytogenes were isolated from many samples. However, Salmonella was not detected in any of the samples. After exposure to 4-5 kGy of gamma-rays, the total aerobic bacteria in frozen shrimps were reduced by approximately 2-3 log cycles. The dose necessary to reduce the vibrio isolates and Aeromonas hydrophila at a level of below 10 -4 per gram was about 3 kGy in frozen shrimps, whereas about 3.5 kGy was required for L. monocytogenes and Salmonella typhimurium. In this study, unpleasant off-odor was clearly detected in the non-frozen shrimps irradiated at 2.5 kGy. On the other hand, off-odor was negligible in the frozen product below 5 kGy irradiation. No remarkable changes of peroxide values were also obtained up to 9 kGy of irradiation in the frozen shrimps. However peroxide values of non-frozen shrimps were clearly increased even irradiated at 4 kGy. Trimethylamine content was not changed at doses below 10 kGy in both of frozen and non-frozen shrimps. Shelf-life of defrosted shrimps were extended ca. 2 times under non-frozen market conditions.

Structural and elemental changes in glioblastoma cells in situ: complementary imaging with high resolution visible light- and X-ray microscopy

DOE PAGES

Ducic, Tanja; Paunesku, Tatjana; Chen, Si; ...

2016-12-09

The glioblastoma (GBM) is characterized by a short median survival and an almost 100% tumor related mortality. GBM cells exhibit highly invasive behavior whose mechanisms are not yet fully understood. The present study explores application of X-ray and visible light microscopy to display the elemental and structural images of cells from 3 patient derived GMB samples and an established GMB cell line. Slight differences in elemental concentrations, in actin cytoskeleton organization and cell morphology were noted between all cells types by X-ray fluorescence and full field soft X-ray microscopy, as well as the Structured Illumination Super-resolution Microscope (SIM). Different samplemore » preparation approaches were used to match each imaging technique. While preparation for SIM included cell fixation and staining, intact frozen hydrated cells were used for the trace element imaging by hard X-ray fluorescence and exploration of the structural features by soft X-ray absorption tomography. In conclusion, each technique documented differences between samples with regard to morphology and elemental composition and underscored the importance of use of multiple patient derived samples for detailed GBM study.« less

Structural and elemental changes in glioblastoma cells in situ: complementary imaging with high resolution visible light- and X-ray microscopy

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

Ducic, Tanja; Paunesku, Tatjana; Chen, Si

The glioblastoma (GBM) is characterized by a short median survival and an almost 100% tumor related mortality. GBM cells exhibit highly invasive behavior whose mechanisms are not yet fully understood. The present study explores application of X-ray and visible light microscopy to display the elemental and structural images of cells from 3 patient derived GMB samples and an established GMB cell line. Slight differences in elemental concentrations, in actin cytoskeleton organization and cell morphology were noted between all cells types by X-ray fluorescence and full field soft X-ray microscopy, as well as the Structured Illumination Super-resolution Microscope (SIM). Different samplemore » preparation approaches were used to match each imaging technique. While preparation for SIM included cell fixation and staining, intact frozen hydrated cells were used for the trace element imaging by hard X-ray fluorescence and exploration of the structural features by soft X-ray absorption tomography. In conclusion, each technique documented differences between samples with regard to morphology and elemental composition and underscored the importance of use of multiple patient derived samples for detailed GBM study.« less

The effects of soy on freezable bread dough: a magnetic resonance study.

PubMed

Simmons, Amber L; Vodovotz, Yael

2012-11-15

Hygroscopic soy ingredients were hypothesised to slow the rate of water migration in unleavened bread dough during frozen storage. Thawed soy (18% dry weight) and wheat dough samples were assessed using non-destructive nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) for up to 8 wks frozen storage time. MRI suggested a spatially homogeneous, net increase in proton mobility with frozen storage and, with solution state proton NMR, distinct "free" and "bound" states were discerned. T(2) relaxation times of the majority proton population suggested increased mobility with frozen storage time, and statistical difference from the fresh sample was seen later for the soy samples than the wheat samples. As seen by (13)C-solid state NMR, the crystallinity of the starch was not affected by either soy addition or frozen storage. In conclusion, addition of soy to bakery products led to slightly enhanced preservation of "fresh" characteristics of the dough during frozen storage. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effect of sugar and acid on the acceptability of frozen yogurt to a student population.

PubMed

Guinard, J X; Little, C; Marty, C; Palchak, T R

1994-05-01

One hundred and forty-one college students tasted and rated on a nine-point hedonic scale their degree of liking for nine samples of vanilla frozen yogurt varying in sugar and lactic acid. Subjects were also asked to complete a questionnaire about consumption of frozen yogurt and other dairy products. Degree of liking differed significantly among samples, and the samples best liked were those with the lowest acidity, .23 to .29%, independent of sugar concentration. Degree of liking of frozen yogurt failed to correlate with dairy product consumption or hunger at the time of testing. No significant difference existed between male and female students for overall degree of liking of frozen yogurt or overall dairy product intake, yet the questionnaire revealed a significantly higher consumption of frozen yogurt among female students. The results of this study suggest that, for the student population tested, frozen yogurt should combine the sensory properties of ice cream (low acidity) with the nutritional properties of yogurt (low fat, active enzyme culture).

Frozen section analysis of margins for head and neck tumor resections: reduction of sampling errors with a third histologic level.

PubMed

Olson, Stephen M; Hussaini, Mohammad; Lewis, James S

2011-05-01

Frozen section analysis is an essential tool for assessing margins intra-operatively to assure complete resection. Many institutions evaluate surgical defect edge tissue provided by the surgeon after the main lesion has been removed. With the increasing use of transoral laser microsurgery, this method is becoming even more prevalent. We sought to evaluate error rates at our large academic institution and to see if sampling errors could be reduced by the simple method change of taking an additional third section on these specimens. All head and neck tumor resection cases from January 2005 through August 2008 with margins evaluated by frozen section were identified by database search. These cases were analyzed by cutting two levels during frozen section and a third permanent section later. All resection cases from August 2008 through July 2009 were identified as well. These were analyzed by cutting three levels during frozen section (the third a 'much deeper' level) and a fourth permanent section later. Error rates for both of these periods were determined. Errors were separated into sampling and interpretation types. There were 4976 total frozen section specimens from 848 patients. The overall error rate was 2.4% for all frozen sections where just two levels were evaluated and was 2.5% when three levels were evaluated (P=0.67). The sampling error rate was 1.6% for two-level sectioning and 1.2% for three-level sectioning (P=0.42). However, when considering only the frozen section cases where tumor was ultimately identified (either at the time of frozen section or on permanent sections) the sampling error rate for two-level sectioning was 15.3 versus 7.4% for three-level sectioning. This difference was statistically significant (P=0.006). Cutting a single additional 'deeper' level at the time of frozen section identifies more tumor-bearing specimens and may reduce the number of sampling errors.

X-ray Computed Tomography Observation of Methane Hydrate Dissociation

USGS Publications Warehouse

Tomutsa, L.; Freifeld, B.; Kneafsey, T.J.; Stern, L.A.

2002-01-01

Deposits of naturally occurring methane hydrate have been identified in permafrost and deep oceanic environments with global reserves estimated to be twice the total amount of energy stored in fossil fuels. The fundamental behavior of methane hydrate in natural formations, while poorly understood, is of critical importance if the economic recovery of methane from hydrates is to be accomplished. In this study, computed X-ray tomography (CT) scanning is used to image an advancing dissociation front in a heterogeneous gas hydrate/sand sample at 0.1 MPa. The cylindrical methane hydrate and sand aggregate, 2.54 cm in diameter and 6.3 cm long, was contained in a PVC sample holder that was insulated on all but one end. At the uninsulated end, the dissociated gas was captured and the volume of gas monitored. The sample was initially imaged axially using X-ray CT scanning within the methane hydrate stability zone by keeping the sample temperature at 77??K. Subsequently, as the sample warmed through the methane hydrate dissociation point at 194??K and room pressure, gas was produced and the temperature at the bottom of the sample plug was monitored while CT images were acquired. The experiment showed that CT imaging can resolve the reduction in density (as seen by a reduction in beam attenuation) of the hydrate/sand aggregate due to the dissociation of methane hydrate. In addition, a comparison of CT images with gas flow and temperature measurements reveals that the CT scanner is able to resolve accurately and spatially the advancing dissociation front. Future experiments designed to better understand the thermodynamics of hydrate dissociation are planned to take advantage of the temporal and spatial resolution that the CT scanner provides.

A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

PubMed Central

Jo, Byung-Wan; Chakraborty, Sumit

2015-01-01

To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

Offshore gas hydrate sample database with an overview and preliminary analysis

USGS Publications Warehouse

Booth, James S.; Rowe, Mary M.; Fisher, Kathleen M.

1996-01-01

Synopsis -- A database of offshore gas hydrate samples was constructed from published observations and measurements. More than 90 samples from 15 distinct regions are represented in 13 data categories. This database has permitted preliminary description of gas hydrate (chiefly methane hydrate) tendencies and associations with respect to their geological environment. Gas hydrates have been recovered from offshore sediment worldwide and from total depths (water depth plus subseabed depth) ranging from 500 m to nearly 6,000 m. Samples have come from subbottom depths ranging from 0 to 400 m. Various physiographic provinces are represented in the data set including second order landforms such as continental margins and deep-sea trenches, and third order forms such as submarine canyons, continental slopes, continental margin ridges and intraslope basins. There is a clear association between fault zones and other manifestations of local, tectonic-related processes, and hydrate-bearing sediment. Samples of gas hydrate frequently consist of individual grains or particles. These types of hydrates are often further described as inclusions or disseminated in the sediment. Moreover, hydrates occur as a cement, as nodules, or as layers (mostly laminae) or in veins. The preponderance of hydrates that could be characterized as 2- dimensional (planar) were associated with fine sediment, either as intercalated layers or in fractures. Hydrate cements were commonly associated with coarser sediment. Hydrates have been found in association with grain sizes ranging from clay through gravel. More hydrates are associated with the more abundant finer-grained sediment than with coarser sediment, and many were discovered in the presence of both fine (silt and clay) and coarse sediment. The thickness of hydrate zones (i. e., sections of hydrate-bearing sediment) varies from a few centimeters to as much as 30 m. In contrast, the thickness of layers of pure hydrate or the dimensions of individual hydrate grains were most often characterized in terms of millimeters or centimeters, although a pure hydrate layer discovered in the Middle America Trench off Guatemala was as much as 3-4-m-thick. The data suggest that grains, or thin veins or laminae of pure gas hydrate may be ubiquitous in many hydrate zones but that typically they may only comprise a minor component of the thicker zones. In more than 80 percent of the hydrate samples the methane was of biogenic origin. The methane in the remainder was either classified as (or may be at least part) thermogenic. Each site where thermogenic gas was identified is characterized by faults or other manifestions of a dynamic geological environment (e.g., diapirs, mud volcanoes, gas seeps). Every sample in the database came from within the zone of theoretical methane hydrate stability, as determined on the basis of assumed regional pressure and temperature gradients. Most show that they were situated --- expressed in terms of depth --- well above the phase boundary and about 70% of the samples were located more than 100 m above the assumed regional position of that boundary. The calculated subseabed positions of the phase boundaries and the BSRs (bottom simulating reflector) are essentially identical. This may be taken as general corroboration of the regional phase boundary calculations and the concept of the BSR. Three provocative aspects of marine gas hydrates have been disclosed by the database: gas hydrates are frequently situated at much shallower subseabed depths than the assumed contemporary position of the regional phase boundary hydrates are often found in areas typified by faults or other indicators of a dynamic geological environment zones of gas hydrate-bearing sediment tend to be tens of centimeters to tens of meters thick but the hydrate within the thicker zones tends to be only a minor constituent. Whether existing as dispersed particles, cements, or pure layers or vein

Biological imaging by soft X-ray diffraction microscopy

NASA Astrophysics Data System (ADS)

Shapiro, David

We have developed a microscope for soft x-ray diffraction imaging of dry or frozen hydrated biological specimens. This lensless imaging system does not suffer from the resolution or specimen thickness limitations that other short wavelength microscopes experience. The microscope, currently situated at beamline 9.0.1 of the Advanced Light Source, can collect diffraction data to 12 nm resolution with 750 eV photons and 17 nm resolution with 520 eV photons. The specimen can be rotated with a precision goniometer through an angle of 160 degrees allowing for the collection of nearly complete three-dimensional diffraction data. The microscope is fully computer controlled through a graphical user interface and a scripting language automates the collection of both two-dimensional and three-dimensional data. Diffraction data from a freeze-dried dwarf yeast cell, Saccharomyces cerevisiae carrying the CLN3-1 mutation, was collected to 12 run resolution from 8 specimen orientations spanning a total rotation of 8 degrees. The diffraction data was phased using the difference map algorithm and the reconstructions provide real space images of the cell to 30 nm resolution from each of the orientations. The agreement of the different reconstructions provides confidence in the recovered, and previously unknown, structure and indicates the three dimensionality of the cell. This work represents the first imaging of the natural complex refractive contrast from a whole unstained cell by the diffraction microscopy method and has achieved a resolution superior to lens based x-ray tomographic reconstructions of similar specimens. Studies of the effects of exposure to large radiation doses were also carried out. It was determined that the freeze-dried cell suffers from an initial collapse, which is followed by a uniform, but slow, shrinkage. This structural damage to the cell is not accompanied by a diminished ability to see small features in the specimen. Preliminary measurements on frozen-hydrated yeast indicate that the frozen specimens do not exhibit these changes even with doses as high as 5 x 109 Gray.

Effect of blanching treatments on antioxidant activity of frozen green capsicum (Capsicum annuum L. var bell pepper) using radical scavenging activity (DPPH) assay

NASA Astrophysics Data System (ADS)

Azizzuddin, Norafida; Abdullah, Aminah

2016-11-01

Blanching treatments are needed to deactivate enzymes in frozen vegetables. Antioxidant activity using DPPH radical scavenging activity assay were evaluated in steaming, boiling water, and microwave blanching at different temperature, time and microwave power level on frozen green capsicum. Green capsicum was chosen for frozen treatment compared to other capsicum with different maturity index because of the firm texture. The objective of this study was to compare the antioxidant activity of frozen green capsicum between conventional and Oxi Count Kit® assay for DPPH radical scavenging activity. Results showed frozen green capsicum blanched using microwave at high level/90 seconds (sample J) contained higher level of DPPH in both conventional method and Oxi Count Kit® compared to other treatments. However, there were no significant differences between sample J and fresh sample (sample A). Overall, the sequences from highest to lowest in blanching treatments for both DPPH conventional method, and DPPH Oxi Count Kit® were J (microwave high level/90 seconds) > A (Fresh) > H (Microwave Medium Level/120 seconds) > D (Boiling Water 80°C/150 seconds) > K (Microwave High Level/120 seconds) > I (Microwave Medium Level/150 seconds) > F (Microwave Low Level/150 seconds)> B (Steam 100°C/150 seconds) > E (Boiling Water 100°C /120 seconds) > G (Microwave Low Level /180 seconds)> C (Steam 100°C/180 seconds). Almost all frozen green capsicum samples showed no significant differences for comparison between test using DPPH conventional method and Oxi Count Kit®. Frozen storage for 0, and 3rd months showed no significant differences which indicate no changes on antioxidant activity during frozen storage at -18°C.

Characterization of methane hydrate host sediments using synchrotron-computed microtomography (CMT)

USGS Publications Warehouse

Jones, K.W.; Feng, H.; Tomov, S.; Winters, W.J.; Prodanovic, M.; Mahajan, D.

2007-01-01

The hydrate-sediment interaction is an important aspect of gas hydrate studies that needs further examination. We describe here the applicability of the computed microtomography (CMT) technique that utilizes an intense X-ray synchrotron source to characterize sediment samples, two at various depths from the Blake Ridge area (a well-known hydrate-prone region) and one from Georges Bank, that once contained methane trapped as hydrates. Detailed results of the tomographic analysis performed on the deepest sample (667??m) from Blake Ridge are presented as 2-D and 3-D images which show several mineral constituents, the internal grain/pore microstructure, and, following segmentation into pore and grain space, a visualization of the connecting pathways through the pore-space of the sediment. Various parameters obtained from the analysis of the CMT data are presented for all three sediment samples. The micro-scale porosity values showed decreasing trend with increasing depth for all three samples that is consistent with the previously reported bulk porosity data. The 3-D morphology, pore-space pathways, porosity, and permeability values are also reported for all three samples. The application of CMT is now being expanded to the laboratory-formed samples of hydrate in sediments as well as field samples of methane hydrate bearing sediments.

Effect of the Protein Hydrolysate from Shrimp Head on Freeze-Induced Denaturation of Fish Myofibrillar Protein

NASA Astrophysics Data System (ADS)

Ruttanapornvareesakul, Yaowalux; Hara, Kenji; Osatomi, Kiyoshi; Nozaki, Yukinori; Osako, Kazufumi; Kongpun, Orawan

Three species of shrimp heads from commercial industry waste were hydrolyzed by enzymatic treatment using protease. Shrimp head protein hydrolysate (SHPH) was added to wanieso lizardfish myofibrils at 5% (dry weight/wet weight) as natural cryoprotectant. The effects of SHPH on the state of water and the freeze denaturation of wanieso lizardfish myotibrils during frozen storage at-25°C were evaluated by determining the amount of unfreezable water and Ca-ATPase activity. Their effects were compared with those of sodium glutamate (Na-Glu) and without additive as the control. The amount of unfreezable water of myofibri1s with SHPH was higher than that of the control throughout the frozen storage for 120 days. Ca-ATPase activity of myofibrils with SHPH decreased slowly compared to that of the control, although the suppressive effects of SHPH were less than that of Na-Glu. The suppressive effects of SHPH were irrespective of shrimp species. Close correlation between the amount of unfreezable water and Ca-ATPase activity was observed. These results suggested that SHPH could prevent the freeze-induced denaturation of fish myofibrils during frozen storage by stabilizing hydration water surrounding myofibrils.

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

NASA Astrophysics Data System (ADS)

Sparrow, K. J.; Kessler, J. D.

2017-12-01

In response to climate change, methane can be released to ocean sediments and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown if methane derived from these massive stores of frozen, ancient carbon reaches the atmosphere. We quantified the fraction of methane sourced from ancient carbon in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. While the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that modern sources of methane predominate in surface waters of relatively shallow mid-outer shelf stations. These results suggest that even if there is a heightened liberation of ancient methane as climate change proceeds, oceanic dispersion and oxidation processes can strongly limit its emission to the atmosphere.

Thermal regime of a continental permafrost associated gas hydrate occurrence a continuous temperature profile record after drilling

NASA Astrophysics Data System (ADS)

Henninges, J.; Huenges, E.; Mallik Working Group

2003-04-01

Both the size and the distribution of natural methane hydrate occurrences, as well as the release of gaseous methane through the dissociation of methane hydrate, are affected by the subsurface pressure and temperature conditions. During a field experiment, which was carried out in the Mackenzie Delta, NWT, Canada, within the framework of the Mallik 2002 Production Research Well Program*, the variation of temperature within three 40 m spaced, 1200 m deep wells was measured deploying the Distributed Temperature Sensing (DTS) technology. An innovative experimental design for the monitoring of spatial and temporal variations of temperature along boreholes was developed and successfully applied under extreme arctic conditions. A special feature is the placement of the fibre-optic sensor cable inside the cement annulus between the casing and the wall of the borehole. Temperature profiles were recorded with a sampling interval of 0.25 m and 5 min, and temperatures can be determined with a resolution of 0.3 °C. The observed variation of temperature over time shows the decay of the thermal disturbances caused by the drilling and construction of the wells. An excellent indicator for the location of the base of the ice-bonded permafrost layer, which stands out as a result of the latent heat of the frozen pore fluid, is a sharp rise in temperature at 604 m depth during the period of equilibration. A similar effect can be detected in the depth interval between 1105 m and 1110 m, which is interpreted as an indicator for the depth to the base of the methane hydrate stability zone. Nine months after the completion of the wells the measured borehole temperatures are close to equilibrium. The mean temperature gradient rises from 9.4 K/km inside the permafrost to 25.4 K/km in the ice-free sediment layers underneath. The zone of the gas hydrate occurrences between 900 m and 1100 m shows distinct variations of the geothermal gradient, which locally rises up to 40 K/km. At the lower boundary of the methane hydrate stability zone a temperature of 12.2 °C was measured. (*) The program participants include 8 partners; The Geological Survey of Canada (GSC), The Japan National Oil Corporation (JNOC), GeoForschungsZentrum Potsdam (GFZ), United States Geological Survey (USGS), United States Department of the Energy (USDOE), India Ministry of Petroleum and Natural Gas (MOPNG)/Gas Authority of India (GAIL) and the Chevron-BP-Burlington joint venture group.

Scanning electron microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates

USGS Publications Warehouse

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

2004-01-01

Scanning electron microscopy (SEM) was used to investigate grain texture and pore structure development within various compositions of pure sI and sII gas hydrates synthesized in the laboratory, as well as in natural samples retrieved from marine (Gulf of Mexico) and permafrost (NW Canada) settings. Several samples of methane hydrate were also quenched after various extents of partial reaction for assessment of mid-synthesis textural progression. All laboratory-synthesized hydrates were grown under relatively high-temperature and high-pressure conditions from rounded ice grains with geometrically simple pore shapes, yet all resulting samples displayed extensive recrystallization with complex pore geometry. Growth fronts of mesoporous methane hydrate advancing into dense ice reactant were prevalent in those samples quenched after limited reaction below and at the ice point. As temperatures transgress the ice point, grain surfaces continue to develop a discrete "rind" of hydrate, typically 5 to 30 ??m thick. The cores then commonly melt, with rind microfracturing allowing migration of the melt to adjacent grain boundaries where it also forms hydrate. As the reaction continues under progressively warmer conditions, the hydrate product anneals to form dense and relatively pore-free regions of hydrate grains, in which grain size is typically several tens of micrometers. The prevalence of hollow, spheroidal shells of hydrate, coupled with extensive redistribution of reactant and product phases throughout reaction, implies that a diffusion-controlled shrinking-core model is an inappropriate description of sustained hydrate growth from melting ice. Completion of reaction at peak synthesis conditions then produces exceptional faceting and euhedral crystal growth along exposed pore walls. Further recrystallization or regrowth can then accompany even short-term exposure of synthetic hydrates to natural ocean-floor conditions, such that the final textures may closely mimic those observed in natural samples of marine origin. Of particular note, both the mesoporous and highly faceted textures seen at different stages during synthetic hydrate growth were notably absent from all examined hydrates recovered from a natural marine-environment setting.

Even with rehydration, preservation in ethanol influences the mechanical properties of bone and how bone responds to experimental manipulation.

PubMed

Vesper, Evan O; Hammond, Max A; Allen, Matthew R; Wallace, Joseph M

2017-04-01

Typically, bones are harvested at the time of animal euthanasia and stored until mechanical testing. However, storage methods are not standardized, and differential effects on mechanical properties are possible between methods. The goal of this study was to investigate the effects that two common preservation methods (freezing wrapped in saline-soaked gauze and refrigerating ethanol fixed samples) have on bone mechanical properties in the context of an in vitro ribosylation treatment designed to modify mechanical integrity. It was hypothesized that there would be an interactive effect between ribose treatment and preservation method. Tibiae from twenty five 11week old female C57BL/6 mice were separated into 2 preservation groups. Micro-CT scans of contralateral pairs assessed differences in geometry prior to storage. After 7weeks of storage, bones in each pair of tibiae were soaked in a solution containing either 0M or 0.6M ribose for 1week prior to 4 point bending tests. There were no differences in any cortical geometric parameters between contralateral tibiae. There was a significant main effect of ethanol fixation on displacement to yield (-16.3%), stiffness (+24.5%), strain to yield (-13.9%), and elastic modulus (+18.5%) relative to frozen specimens. There was a significant main effect of ribose treatment for yield force (+13.9%), ultimate force (+9.2%), work to yield (+22.2%), yield stress (+14.1%), and resilience (+21.9%) relative to control-soaked bones. Postyield displacement, total displacement, postyield work, total work, total strain, and toughness were analyzed separately within each preservation method due to significant interactions. For samples stored frozen, all six properties were lower in the ribose-soaked group (49%-68%) while no significant effects of ribose were observed in ethanol fixed bones. Storage in ethanol likely caused changes to the collagen matrix which prevented or masked the embrittling effects of ribosylation that were seen in samples stored frozen wrapped in saline-soaked gauze. These data illustrate the clear importance of maintaining hydration if the eventual goal is to use bones for mechanical assessments and further show that storage in ethanol can alter potential to detect effects of experimental manipulation (in this case ribosylation). Copyright © 2017 Elsevier Inc. All rights reserved.

Survey of Salmonella and Campylobacter contamination of whole, raw poultry on retail sale in Wales in 2003.

PubMed

Meldrum, R J; Tucker, I D; Smith, R M M; Edwards, C

2005-07-01

A survey of the Salmonella and Campylobacter contamination of raw, whole chickens available to consumers in Wales was performed between March and December 2003. In total, 736 samples were taken, and overall contamination rates of 73.1% for Campylobacter and 5.7% for Salmonella were found. This survey follows a survey performed during 2001 to 2002 by Welsh local authorities and the National Public Health Service for Wales that established updated baseline rates for both pathogens in raw, whole chicken available to consumers in Wales. This survey indicated no difference in Campylobacter rates between fresh and frozen samples or between samples taken from retailers and local butchers, but significant differences existed in Salmonella rates between fresh and frozen samples and between those sampled from retailers and butchers, with frozen chickens and samples taken from retailers having significantly higher rates. However, the difference in Salmonella isolation rate between retailers and butchers was found to be due to the differences in the proportions of fresh and frozen chickens sampled from these locations, with a significantly higher number of frozen chickens (with a higher Salmonella rate) being sampled from retailers.

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in concentrations too low to be detected by the current DORISS instrument. In situ analyses of the hydrates show them to be structure I hydrates with methane as the primary guest molecule; the data compare well to laboratory data.

Methane Hydrate Fformation in a Coarse-Grained, Brine-Saturated Sample Through the Induction of a Propagating Gas Front

NASA Astrophysics Data System (ADS)

Meyer, D.

2016-12-01

We generate methane hydrate in a coarse-grained, brine-saturated, vertically-oriented sample through gas injection. From 0 - 80 hours, we estimate a hydrate saturation of 0.56 behind the formation front, using mass balance, indicating that hydrate formation is limited by locally-elevated salinity creating three-phase equilibrium conditions. After 80 hours, the hydrate phase saturation drops to 0.50 and the magnitude of the pressure drop-rebound cycles increases, suggesting temporary reductions in permeability and the development of heterogeneous distributions of free gas in the sample. The sample consists of an industrial, fine sand mixed with a 0.5 wt% fraction of natural, smectitic clay from the Eugene Island region in the Gulf of Mexico (5.08cm diameter, 11.79cm length). The sample is initially saturated with a 7 wt% sodium chloride brine, pressurized to 12.24 MPa, and cooled to 1 degree Celsius, to bring the sample into the hydrate stability zone. Syringe pumps filled with methane gas and brine are connected to the top and bottom of the sample, respectively, to control fluid flow. We withdraw from the base of the sample at a rate of 0.0005 mL/min and inject methane to maintain a constant pressure, initiating hydrate formation. We analyze this experiment, as well as a gas flood experiment executed under the same conditions, using computed-tomography scans and an analytical solution to investigate the formation behavior and thermodynamic state of hydrate in gas-rich, coarse-grained reservoirs.

Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311: indications for heterogeneous compositions in hydrate crystals.

PubMed

Schicks, J M; Ziemann, M A; Lu, H; Ripmeester, J A

2010-12-01

Natural gas hydrates usually are found in the form of structure I, encasing predominantly methane in the hydrate lattices as guest molecules, sometimes also minor amount of higher hydrocarbons, CO2 or H2S. Raman spectroscopy is an approved tool to determine the composition of the hydrate phase. Thus, in this study Raman spectroscopic analyses have been applied to hydrate samples obtained from Integrated Ocean Drilling Program (IODP) Expedition 311 in two different approaches: studying the samples randomly taken from the hydrate core, and--as a new application--mapping small areas on the surface of clear hydrate crystals. The results obtained imply that the gas composition of hydrate, in terms of relative concentrations of CH4 and H2S, is not homogeneous over a core or even within a crystal. The mapping method yielded results with very high lateral resolution, indicating the coexistence of different phases with the same structure but different compositions within a hydrate crystal. Copyright © 2010 Elsevier B.V. All rights reserved.

Rheological properties and bread quality of frozen yeast-dough with added wheat fiber.

PubMed

Adams, Vivian; Ragaee, Sanaa M; Abdel-Aal, El-Sayed M

2017-01-01

The rheological characteristics of frozen dough are of great importance in bread-making quality. The effect of addition of commercial wheat aleurone and bran on rheological properties and final bread quality of frozen dough was studied. Wheat aleurone (A) and bran (B) containing 240 g kg -1 and 200 g kg -1 arabinoxylan (AX), respectively, were incorporated into refined wheat flour at 150 g kg -1 substitution level (composite A and B, respectively). Dough samples of composite A and B in addition to two reference dough samples, refined flour (ref A) and whole wheat flour (ref B) were stored at -18°C for 9 weeks. Frozen stored composite dough samples contained higher amounts of bound water, less freezable water and exhibited fewer modifications in gluten network during frozen storage based on data from differential scanning calorimetry and nuclear magnetic resonance spectroscopy. Bread made from composite frozen dough had higher loaf volume compared to ref A or ref B throughout the storage period. The incorporation of wheat fiber into refined wheat flour produced dough with minimum alterations in its rheological properties during 9 weeks of frozen storage compared to refined and 100% wheat flour dough samples. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Probing methane hydrate nucleation through the forward flux sampling method.

PubMed

Bi, Yuanfei; Li, Tianshu

2014-11-26

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

High quality copy number and genotype data from FFPE samples using Molecular Inversion Probe (MIP) microarrays

PubMed Central

Wang, Yuker; Carlton, Victoria EH; Karlin-Neumann, George; Sapolsky, Ronald; Zhang, Li; Moorhead, Martin; Wang, Zhigang C; Richardson, Andrea L; Warren, Robert; Walther, Axel; Bondy, Melissa; Sahin, Aysegul; Krahe, Ralf; Tuna, Musaffe; Thompson, Patricia A; Spellman, Paul T; Gray, Joe W; Mills, Gordon B; Faham, Malek

2009-01-01

Background A major challenge facing DNA copy number (CN) studies of tumors is that most banked samples with extensive clinical follow-up information are Formalin-Fixed Paraffin Embedded (FFPE). DNA from FFPE samples generally underperforms or suffers high failure rates compared to fresh frozen samples because of DNA degradation and cross-linking during FFPE fixation and processing. As FFPE protocols may vary widely between labs and samples may be stored for decades at room temperature, an ideal FFPE CN technology should work on diverse sample sets. Molecular Inversion Probe (MIP) technology has been applied successfully to obtain high quality CN and genotype data from cell line and frozen tumor DNA. Since the MIP probes require only a small (~40 bp) target binding site, we reasoned they may be well suited to assess degraded FFPE DNA. We assessed CN with a MIP panel of 50,000 markers in 93 FFPE tumor samples from 7 diverse collections. For 38 FFPE samples from three collections we were also able to asses CN in matched fresh frozen tumor tissue. Results Using an input of 37 ng genomic DNA, we generated high quality CN data with MIP technology in 88% of FFPE samples from seven diverse collections. When matched fresh frozen tissue was available, the performance of FFPE DNA was comparable to that of DNA obtained from matched frozen tumor (genotype concordance averaged 99.9%), with only a modest loss in performance in FFPE. Conclusion MIP technology can be used to generate high quality CN and genotype data in FFPE as well as fresh frozen samples. PMID:19228381

Characterization and physical properties of hydrate bearing sediments

NASA Astrophysics Data System (ADS)

Terzariol, M.; Santamarina, C.

2016-12-01

The amount of carbon trapped in hydrates is estimated to be larger than in conventional oil and gas reservoirs, thus methane hydrate is a promising energy resource. The high water pressure and the relatively low temperature needed for hydrate stability restrict the distribution of methane hydrates to continental shelves and permafrost regions. Stability conditions add inherent complexity to coring, sampling, handling, testing and data interpretation, have profound implications on potential production strategies. Thus a novel technology is developed for handling, transferring, and testing of natural hydrate bearing sediments without depressurization in order to preserve the sediment structure. Results from the first deployment of these tools on natural samples from Nankai Trough, Japan will also be summarized. Finally, to avoid consequences of poor sampling, a new multi-sensor in-situ characterization tool will be introduced.

Physical property studies in the USGS GHASTLI Laboratory

USGS Publications Warehouse

Winters, William J.; Waite, William F.; Hutchinson, Deborah R.; Mason, David H.

2008-01-01

One of the many challenges in studying methane hydrate is that it is unstable at typical surface pressure and temperature conditions. To enable methane hydrates and hydrate-bearing sediments to be formed, analyzed, and experimented with, the National Energy Technology Laboratory (NETL), and the U.S. Geological Survey (USGS) in Woods Hole, MA collaborated in the development of the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI). Over the past decade, the USGS has been operating GHASTLI and collaborating in the development of new sample handling tools and procedures, in an effort to improve our ability to analyze methane hydrate in the lab. These tools will enable hydrate researchers to more confidently link field studies (for example geophysics or drilling) with theoretical and predictive studies, leading to a better understanding of the geological conditions and processes that control the growth and concentration of natural gas hydrates, how hydrates affect the properties of the host sediments, and how the hydrate-sediment system changes when hydrate dissociates and releases the previously bound gas. To date, GHASTLI has been used to measure natural samples from ODP Leg 164 (Blake Ridge off the U.S. southeast Atlantic margin), Leg 204 (Hydrate Ridge off the Pacific Northwest margin) and the Mallik well (Mackenzie Delta in northwestern Canada). Additional samples in the queue for analysis are from the Chevron Joint Industry Project Experiment in the Gulf of Mexico and most recently, from IODP Leg 311 off Vancouver Island. Several foreign nations have asked whether GHASTLI will be available to analyze samples that might be recovered during national drilling programs. The ability to perform lab testing of hydrates within sediments is one of the unique capabilities of GHASTLI that separates it from other simulators at NETL and elsewhere.

Asynchronous data acquisition and on-the-fly analysis of dose fractionated cryoEM images by UCSFImage

PubMed Central

Li, Xueming; Zheng, Shawn; Agard, David A.; Cheng, Yifan

2015-01-01

Newly developed direct electron detection cameras have a high image output frame rate that enables recording dose fractionated image stacks of frozen hydrated biological samples by electron cryomicroscopy (cryoEM). Such novel image acquisition schemes provide opportunities to analyze cryoEM data in ways that were previously impossible. The file size of a dose fractionated image stack is 20 ~ 60 times larger than that of a single image. Thus, efficient data acquisition and on-the-fly analysis of a large number of dose-fractionated image stacks become a serious challenge to any cryoEM data acquisition system. We have developed a computer-assisted system, named UCSFImage4, for semi-automated cryo-EM image acquisition that implements an asynchronous data acquisition scheme. This facilitates efficient acquisition, on-the-fly motion correction, and CTF analysis of dose fractionated image stacks with a total time of ~60 seconds/exposure. Here we report the technical details and configuration of this system. PMID:26370395

3D Structure Determination of Native Mammalian Cells using Cryo-FIB and Cryo-electron Tomography

PubMed Central

Wang, Ke; Strunk, Korrinn; Zhao, Gongpu; Gray, Jennifer L.; Zhang, Peijun

2012-01-01

Cryo-electron tomography (cryo-ET) has enabled high resolution three-dimensional (3D) structural analysis of virus and host cell interactions and many cell signaling events; these studies, however, have largely been limited to very thin, peripheral regions of eukaryotic cells or to small prokaryotic cells. Recent efforts to make thin, vitreous sections using cryo-ultramicrotomy have been successful, however, this method is technically very challenging and with many artifacts. Here, we report a simple and robust method for creating in situ, frozen-hydrated cell lamellas using a focused ion beam at cryogenic temperature (cryo-FIB), allowing access to any interior cellular regions of interest. We demonstrate the utility of cryo-FIB with high resolution 3D cellular structures from both bacterial cells and large mammalian cells. The method will not only facilitate high-throughput 3D structural analysis of biological specimens, but is also broadly applicable to sample preparation of thin films and surface materials without the need for FIB “lift-out”. PMID:22796867

Frozen Section Evaluation of Margin Status in Primary Squamous Cell Carcinomas of the Head and Neck: A Correlation Study of Frozen Section and Final Diagnoses.

PubMed

Layfield, Eleanor M; Schmidt, Robert L; Esebua, Magda; Layfield, Lester J

2018-06-01

Frozen section is routinely used for intraoperative margin evaluation in carcinomas of the head and neck. We studied a series of frozen sections performed for margin status of head and neck tumors to determine diagnostic accuracy. All frozen sections for margin control of squamous carcinomas of the head and neck were studied from a 66 month period. Frozen and permanent section diagnoses were classified as negative or malignant. Correlation of diagnoses was performed to determine accuracy. One thousand seven hundred and ninety-six pairs of frozen section and corresponding permanent section diagnoses were obtained. Discordances were found in 55 (3.1%) pairs. In 35 pairs (1.9%), frozen section was reported as benign, but permanent sections disclosed carcinoma. In 21 cases, the discrepancy was due to sampling and in the remaining cases it was an interpretive error. In 20 cases (1.1%), frozen section was malignant, but the permanent section was interpreted as negative. Frozen section is an accurate method for evaluation of operative margins for head and neck carcinomas with concordance between frozen and permanent results of 97%. Most errors are false negative results with the majority of these being due to sampling issues.

RNA-Seq-based toxicogenomic assessment of fresh frozen and formalin-fixed tissues yields similar mechanistic insights.

PubMed

Auerbach, Scott S; Phadke, Dhiral P; Mav, Deepak; Holmgren, Stephanie; Gao, Yuan; Xie, Bin; Shin, Joo Heon; Shah, Ruchir R; Merrick, B Alex; Tice, Raymond R

2015-07-01

Formalin-fixed, paraffin-embedded (FFPE) pathology specimens represent a potentially vast resource for transcriptomic-based biomarker discovery. We present here a comparison of results from a whole transcriptome RNA-Seq analysis of RNA extracted from fresh frozen and FFPE livers. The samples were derived from rats exposed to aflatoxin B1 (AFB1 ) and a corresponding set of control animals. Principal components analysis indicated that samples were separated in the two groups representing presence or absence of chemical exposure, both in fresh frozen and FFPE sample types. Sixty-five percent of the differentially expressed transcripts (AFB1 vs. controls) in fresh frozen samples were also differentially expressed in FFPE samples (overlap significance: P < 0.0001). Genomic signature and gene set analysis of AFB1 differentially expressed transcript lists indicated highly similar results between fresh frozen and FFPE at the level of chemogenomic signatures (i.e., single chemical/dose/duration elicited transcriptomic signatures), mechanistic and pathology signatures, biological processes, canonical pathways and transcription factor networks. Overall, our results suggest that similar hypotheses about the biological mechanism of toxicity would be formulated from fresh frozen and FFPE samples. These results indicate that phenotypically anchored archival specimens represent a potentially informative resource for signature-based biomarker discovery and mechanistic characterization of toxicity. Copyright © 2014 John Wiley & Sons, Ltd.

Structural changes and preferential cage occupancy of ethane hydrate and methane-ethane mixed gas hydrate under very high pressure.

PubMed

Hirai, Hisako; Takahara, Naoya; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

2008-12-14

High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.

CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.; Durham, W.B.; Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Ishii, Y.

2003-01-01

Structure I (sI) carbon dioxide (CO2) hydrate exhibits markedly different dissociation behavior from sI methane (CH4) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H2O melting point (273.15 K). The CO2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO2??nH2O = CO2(g) + nH2O(1 to s) is measurably distinct from the pure H2O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO2 hydrate was synthesized from CO2 liquid and H2O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 ??m diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the hydrate structure are filled such that n ??? 5.75.

Biobanking of fresh frozen tissue from clinical surgical specimens: transport logistics, sample selection, and histologic characterization.

PubMed

Botling, Johan; Micke, Patrick

2011-01-01

Access to high-quality fresh frozen tissue is critical for translational cancer research and molecular -diagnostics. Here we describe a workflow for the collection of frozen solid tissue samples derived from fresh human patient specimens after surgery. The routines have been in operation at Uppsala University Hospital since 2001. We have integrated cryosection and histopathologic examination of each biobank sample into the biobank manual. In this way, even small, macroscopically ill-defined lesions can be -procured without a diagnostic hazard due to the removal of uncharacterized tissue from a clinical -specimen. Also, knowledge of the histomorphology of the frozen tissue sample - tumor cell content, stromal components, and presence of necrosis - is pivotal before entering a biobank case into costly molecular profiling studies.

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.

Thermal conductivity of hydrate-bearing sediments

USGS Publications Warehouse

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

2009-01-01

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

Gas hydrate concentration estimated from P- and S-wave velocities

NASA Astrophysics Data System (ADS)

Carcione, J. M.; Gei, D.

2003-04-01

We estimate the concentration of gas hydrate at the Mallik 2L-38 research site, Mackenzie Delta, Canada, using P- and S-wave velocities obtained from well logging and vertical seismic profiles (VSP). The theoretical velocities are obtained from a poro-viscoelastic model based on a Biot-type approach. It considers the existence of two solids (grains and gas hydrate) and a fluid mixture and is based on the assumption that hydrate fills the pore space and shows interconnection. The moduli of the matrix formed by gas hydrate are obtained from the percolation model described by Leclaire et al., (1994). An empirical mixing law introduced by Brie et al., (1995) provides the effective bulk modulus of the fluid phase, giving Wood's modulus at low frequency and Voigt's modulus at high frequencies. The dry-rock moduli are estimated from the VSP profile where the rock is assumed to be fully saturated with water, and the quality factors are obtained from the velocity dispersion observed between the sonic and VSP velocities. Attenuation is described by using a constant-Q model for the dry rock moduli. The amount of dissipation is estimated from the difference between the seismic velocities and the sonic-log velocities. We estimate the amount of gas hydrate by fitting the sonic-log and seismic velocities to the theoretical velocities, using the concentration of gas hydrate as fitting parameter. We obtain hydrate concentrations up to 75 %, average values of 43 and 47 % from the VSP P- and S-wave velocities, respectively, and 47 and 42 % from the sonic-log P- and S-wave velocities, respectively. These averages are computed from 897 to 1110 m, excluding the zones where there is no gas hydrate. We found that modeling attenuation is important to obtain reliable results. largeReferences} begin{description} Brie, A., Pampuri, F., Marsala A.F., Meazza O., 1995, Shear Sonic Interpretation in Gas-Bearing Sands, SPE Annual Technical Conference and Exhibition, Dallas, 1995. Carcione, J.M. and Gei, D., Gas hydrate concentration estimated from P- and S-wave velocities at the Mallik 2L-38 research well, Mackenzie Delta, Canada, submitted to Geophysics. Gei, D. and Carcione, J.M., Acoustic properties of sediments saturated with gas hydrate, free gas and water, Geophysical Prospecting, in press. Leclarie, Ph., Cohen-Tenoudji, F., and Aguirre-Puente, J., 1994, Extension of Biot's theory of wave propagation to frozen porous media, J. Acoust. Soc. Am., 96, 6, 3753-3768.

Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

USGS Publications Warehouse

Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

2010-01-01

Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

Sample storage-induced changes in the quantity and quality of soil labile organic carbon

PubMed Central

Sun, Shou-Qin; Cai, Hui-Ying; Chang, Scott X.; Bhatti, Jagtar S.

2015-01-01

Effects of sample storage methods on the quantity and quality of labile soil organic carbon are not fully understood even though their effects on basic soil properties have been extensively studied. We studied the effects of air-drying and frozen storage on cold and hot water soluble organic carbon (WSOC). Cold- and hot-WSOC in air-dried and frozen-stored soils were linearly correlated with those in fresh soils, indicating that storage proportionally altered the extractability of soil organic carbon. Air-drying but not frozen storage increased the concentrations of cold-WSOC and carbohydrate in cold-WSOC, while both increased polyphenol concentrations. In contrast, only polyphenol concentration in hot-WSOC was increased by air-drying and frozen storage, suggesting that hot-WSOC was less affected by sample storage. The biodegradability of cold- but not hot-WSOC was increased by air-drying, while both air-drying and frozen storage increased humification index and changed specific UV absorbance of both cold- and hot-WSOC, indicating shifts in the quality of soil WSOC. Our results suggest that storage methods affect the quantity and quality of WSOC but not comparisons between samples, frozen storage is better than air-drying if samples have to be stored, and storage should be avoided whenever possible when studying the quantity and quality of both cold- and hot-WSOC. PMID:26617054

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

USGS Publications Warehouse

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

2008-01-01

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

Methods of human body odor sampling: the effect of freezing.

PubMed

Lenochova, Pavlina; Roberts, S Craig; Havlicek, Jan

2009-02-01

Body odor sampling is an essential tool in human chemical ecology research. However, methodologies of individual studies vary widely in terms of sampling material, length of sampling, and sample processing. Although these differences might have a critical impact on results obtained, almost no studies test validity of current methods. Here, we focused on the effect of freezing samples between collection and use in experiments involving body odor perception. In 2 experiments, we tested whether axillary odors were perceived differently by raters when presented fresh or having been frozen and whether several freeze-thaw cycles affected sample quality. In the first experiment, samples were frozen for 2 weeks, 1 month, or 4 months. We found no differences in ratings of pleasantness, attractiveness, or masculinity between fresh and frozen samples. Similarly, almost no differences between repeatedly thawed and fresh samples were found. We found some variations in intensity; however, this was unrelated to length of storage. The second experiment tested differences between fresh samples and those frozen for 6 months. Again no differences in subjective ratings were observed. These results suggest that freezing has no significant effect on perceived odor hedonicity and that samples can be reliably used after storage for relatively long periods.

Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

USGS Publications Warehouse

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

2009-01-01

We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

Gas hydrate property measurements in porous sediments with resonant ultrasound spectroscopy

NASA Astrophysics Data System (ADS)

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

2007-05-01

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

Long-term frozen storage of urine samples: a trouble to get PCR results in Schistosoma spp. DNA detection?

PubMed

Fernández-Soto, Pedro; Velasco Tirado, Virginia; Carranza Rodríguez, Cristina; Pérez-Arellano, José Luis; Muro, Antonio

2013-01-01

Human schistosomiasis remains a serious worldwide public health problem. At present, a sensitive and specific assay for routine diagnosis of schistosome infection is not yet available. The potential for detecting schistosome-derived DNA by PCR-based methods in human clinical samples is currently being investigated as a diagnostic tool with potential application in routine schistosomiasis diagnosis. Collection of diagnostic samples such as stool or blood is usually difficult in some populations. However, urine is a biological sample that can be collected in a non-invasive method, easy to get from people of all ages and easy in management, but as a sample for PCR diagnosis is still not widely used. This could be due to the high variability in the reported efficiency of detection as a result of the high variation in urine samples' storage or conditions for handling and DNA preservation and extraction methods. We evaluate different commercial DNA extraction methods from a series of long-term frozen storage human urine samples from patients with parasitological confirmed schistosomiasis in order to assess the PCR effectiveness for Schistosoma spp. detection. Patients urine samples were frozen for 18 months up to 7 years until use. Results were compared with those obtained in PCR assays using fresh healthy human urine artificially contaminated with Schistosoma mansoni DNA and urine samples from mice experimentally infected with S. mansoni cercariae stored frozen for at least 12 months before use. PCR results in fresh human artificial urine samples using different DNA based extraction methods were much more effective than those obtained when long-term frozen human urine samples were used as the source of DNA template. Long-term frozen human urine samples are probably not a good source for DNA extraction for use as a template in PCR detection of Schistosoma spp., regardless of the DNA method of extraction used.

Low-cost cryo-light microscopy stage fabrication for correlated light/electron microscopy.

PubMed

Carlson, David B; Evans, James E

2011-06-05

The coupling of cryo-light microscopy (cryo-LM) and cryo-electron microscopy (cryo-EM) poses a number of advantages for understanding cellular dynamics and ultrastructure. First, cells can be imaged in a near native environment for both techniques. Second, due to the vitrification process, samples are preserved by rapid physical immobilization rather than slow chemical fixation. Third, imaging the same sample with both cryo-LM and cryo-EM provides correlation of data from a single cell, rather than a comparison of "representative samples". While these benefits are well known from prior studies, the widespread use of correlative cryo-LM and cryo-EM remains limited due to the expense and complexity of buying or building a suitable cryogenic light microscopy stage. Here we demonstrate the assembly, and use of an inexpensive cryogenic stage that can be fabricated in any lab for less than $40 with parts found at local hardware and grocery stores. This cryo-LM stage is designed for use with reflected light microscopes that are fitted with long working distance air objectives. For correlative cryo-LM and cryo-EM studies, we adapt the use of carbon coated standard 3-mm cryo-EM grids as specimen supports. After adsorbing the sample to the grid, previously established protocols for vitrifying the sample and transferring/handling the grid are followed to permit multi-technique imaging. As a result, this setup allows any laboratory with a reflected light microscope to have access to direct correlative imaging of frozen hydrated samples.

Curation of Frozen Samples

NASA Technical Reports Server (NTRS)

Fletcher, L. A.; Allen, C. C.; Bastien, R.

2008-01-01

NASA's Johnson Space Center (JSC) and the Astromaterials Curator are charged by NPD 7100.10D with the curation of all of NASA s extraterrestrial samples, including those from future missions. This responsibility includes the development of new sample handling and preparation techniques; therefore, the Astromaterials Curator must begin developing procedures to preserve, prepare and ship samples at sub-freezing temperatures in order to enable future sample return missions. Such missions might include the return of future frozen samples from permanently-shadowed lunar craters, the nuclei of comets, the surface of Mars, etc. We are demonstrating the ability to curate samples under cold conditions by designing, installing and testing a cold curation glovebox. This glovebox will allow us to store, document, manipulate and subdivide frozen samples while quantifying and minimizing contamination throughout the curation process.

Effect of Freezing Conditions on Distances and Their Distributions Derived from Double Electron Electron Resonance (DEER): A Study of Doubly-Spin-Labeled T4 Lysozyme

PubMed Central

Georgieva, Elka R.; Roy, Aritro S.; Grigoryants, Vladimir M.; Borbat, Petr P.; Earle, Keith A.; Scholes, Charles P.; Freed, Jack H.

2012-01-01

Pulsed dipolar ESR spectroscopy, DEER and DQC, require frozen samples. An important issue in the biological application of this technique is how the freezing rate and concentration of cryoprotectant could possibly affect the conformation of biomacromolecule and/or spin-label. We studied in detail the effect of these experimental variables on the distance distributions obtained by DEER from a series of doubly spin-labeled T4 lysozyme mutants. We found that the rate of sample freezing affects mainly the ensemble of spin-label rotamers, but the distance maxima remain essentially unchanged. This suggests that proteins frozen in a regular manner in liquid nitrogen faithfully maintain the distance-dependent structural properties in solution. We compared the results from rapidly freeze-quenched (≤100 μs) samples to those from commonly shock-frozen (slow freeze, 1s or longer) samples. For all the mutants studied we obtained inter-spin distance distributions, which were broader for rapidly frozen samples than for slowly frozen ones. We infer that rapid freezing trapped a larger ensemble of spin label rotamers; whereas, on the time-scale of slower freezing the protein and spin-label achieve a population showing fewer low-energy conformers. We used glycerol as a cryoprotectant in concentrations of 10% and 30% by weight. With 10% glycerol and slow freezing, we observed an increased slope of background signals, which in DEER is related to increased local spin concentration, in this case due to insufficient solvent vitrification, and therefore protein aggregation. This effect was considerably suppressed in slowly frozen samples containing 30% glycerol and rapidly frozen samples containing 10% glycerol. The assignment of bimodal distributions to tether rotamers as opposed to protein conformations is aided by comparing results using MTSL and 4-Bromo MTSL spin-labels. The latter usually produce narrower distance distributions. PMID:22341208

Long-Term Frozen Storage of Urine Samples: A Trouble to Get PCR Results in Schistosoma spp. DNA Detection?

PubMed Central

Fernández-Soto, Pedro; Velasco Tirado, Virginia; Carranza Rodríguez, Cristina; Pérez-Arellano, José Luis; Muro, Antonio

2013-01-01

Background Human schistosomiasis remains a serious worldwide public health problem. At present, a sensitive and specific assay for routine diagnosis of schistosome infection is not yet available. The potential for detecting schistosome-derived DNA by PCR-based methods in human clinical samples is currently being investigated as a diagnostic tool with potential application in routine schistosomiasis diagnosis. Collection of diagnostic samples such as stool or blood is usually difficult in some populations. However, urine is a biological sample that can be collected in a non-invasive method, easy to get from people of all ages and easy in management, but as a sample for PCR diagnosis is still not widely used. This could be due to the high variability in the reported efficiency of detection as a result of the high variation in urine samples’ storage or conditions for handling and DNA preservation and extraction methods. Methodology/Principal Findings We evaluate different commercial DNA extraction methods from a series of long-term frozen storage human urine samples from patients with parasitological confirmed schistosomiasis in order to assess the PCR effectiveness for Schistosoma spp. detection. Patientś urine samples were frozen for 18 months up to 7 years until use. Results were compared with those obtained in PCR assays using fresh healthy human urine artificially contaminated with Schistosoma mansoni DNA and urine samples from mice experimentally infected with S. mansoni cercariae stored frozen for at least 12 months before use. PCR results in fresh human artificial urine samples using different DNA based extraction methods were much more effective than those obtained when long-term frozen human urine samples were used as the source of DNA template. Conclusions/Significance Long-term frozen human urine samples are probably not a good source for DNA extraction for use as a template in PCR detection of Schistosoma spp., regardless of the DNA method of extraction used. PMID:23613907

An Array-Based Analysis of MicroRNA Expression Comparing Matched Frozen and Formalin-Fixed Paraffin-Embedded Human Tissue Samples

PubMed Central

Zhang, Xiao; Chen, Jiamin; Radcliffe, Tom; LeBrun, Dave P.; Tron, Victor A.; Feilotter, Harriet

2008-01-01

MicroRNAs (miRNAs) are small, noncoding RNAs that suppress gene expression at the posttranscriptional level via an antisense RNA-RNA interaction. miRNAs used for array-based profiling are generally purified from either snap-frozen or fresh samples. Because tissues found in most pathology departments are available only in formalin-fixed and paraffin-embedded (FFPE) states, we sought to evaluate miRNA derived from FFPE samples for microarray analysis. In this study, miRNAs extracted from matched snap-frozen and FFPE samples were profiled using the Agilent miRNA array platform (Agilent, Santa Clara, CA). Each miRNA sample was hybridized to arrays containing probes interrogating 470 human miRNAs. Seven cases were compared in either duplicate or triplicate. Intrachip and interchip analyses demonstrated that the processes of miRNA extraction, labeling, and hybridization from both frozen and FFPE samples are highly reproducible and add little variation to the results; technical replicates showed high correlations with one another (Kendall tau, 0.722 to 0.853; Spearman rank correlation coefficient, 0.891 to 0.954). Our results showed consistent high correlations between matched frozen and FFPE samples (Kendall tau, 0.669 to 0.815; Spearman rank correlation coefficient, 0.847 to 0.948), supporting the use of FFPE-derived miRNAs for array-based, gene expression profiling. PMID:18832457

Flow cytometric sorting of fresh and frozen-thawed spermatozoa in the western lowland gorilla (Gorilla gorilla gorilla).

PubMed

O'Brien, J K; Stojanov, T; Crichton, E G; Evans, K M; Leigh, D; Maxwell, W M C; Evans, G; Loskutoff, N M

2005-08-01

We adapted flow cytometry technology for high-purity sorting of X chromosome-bearing spermatozoa in the western lowland gorilla (Gorilla gorilla gorilla). Our objectives were to develop methodologies for liquid storage of semen prior to sorting, sorting of liquid-stored and frozen-thawed spermatozoa, and assessment of sorting accuracy. In study 1, the in vitro sperm characteristics of gorilla ejaculates from one male were unchanged (P > 0.05) after 8 hr of liquid storage at 15 degrees C in a non-egg yolk diluent (HEPES-buffered modified Tyrode's medium). In study 2, we examined the efficacy of sorting fresh and frozen-thawed spermatozoa using human spermatozoa as a model for gorilla spermatozoa. Ejaculates from one male were split into fresh and frozen aliquots. X-enriched samples derived from both fresh and frozen-thawed human semen were of high purity, as determined by fluorescence in situ hybridization (FISH; 90.7%+/-2.3%, overall), and contained a high proportion of morphologically normal spermatozoa (86.0%+/-1.0%, overall). In study 3, we processed liquid-stored semen from two gorillas for sorting using a modification of methods for human spermatozoa. The sort rate for enrichment of X-bearing spermatozoa was 7.3+/-2.5 spermatozoa per second. The X-enriched samples were of high purity (single-sperm PCR: 83.7%) and normal morphology (79.0%+/-3.9%). In study 4 we examined frozen-thawed gorilla semen, and the sort rate (8.3+/-2.9 X-bearing sperm/sec), purity (89.7%), and normal morphology (81.4%+/-3.4%) were comparable to those of liquid-stored semen. Depending on the male and the type of sample used (fresh or frozen-thawed), 0.8-2.2% of gorilla spermatozoa in the processed ejaculate were present in the X-enriched sample. These results demonstrate that fresh or frozen-thawed gorilla spermatozoa can be flow cytometrically sorted into samples enriched for X-bearing spermatozoa. Copyright 2005 Wiley-Liss, Inc.

Depressurization-induced fines migration in hydrate-bearing clayey sands: X-ray CT imaging and quantification

NASA Astrophysics Data System (ADS)

Han, G.; Kwon, T. H.; Lee, J. Y.

2016-12-01

As gas and water flows induced by depressurization of hydrate-bearing sediments exert seepage forces on fines in sediments, such as clay particles, depressurization is reported to accompany the transport of fine particles through sediment pores, i.e., fines migration. Because such fines migration can cause pore clogging, the fines migration is considered as one of the critical phenomena contributing to the transport of fluids among various pore-scale processes associated with depressurization. However, quantification of fines migration during depressurization still remains poorly understood. This study thus investigated fines migration caused by depressurization using X-ray computerized tomography(X-ray CT) imaging. A host sediment was prepared by mixing fine sand with kaolinite clay minerals to achieve 10% mass fraction of fines (less than 75 um). Then, methane hydrate was synthesized in the host clayey sand, and thereafter water was injected to saturate the hydrate-bearing sediment sample. Step-wise depressurization was applied while the produced gas was collected through an outlet fluid port. X-ray CT imaging was conducted on the sediment sample over the courses of the experiment to monitor the sample preparation, hydrate formation, depressurization, and fines migration. Based on the calibration tests, the amount and locations of methane hydrate formed in the sample was estimated, and the gas migration path was also identified. Finally, the spatial distribution of fines after completion of depressurization was first assessed using the obtained X-ray images and then compared with the post-mortem mine-back results.Notably, we found that the middle part of the sample was clogged possibly by fines or by re-formed hydrate, leading to a big pressure difference between the inlet and outlet fluid port of the sample by 3 MPa. Owing to this clogging and the lost in pressure communication, hydrate dissociation first occurred at the bottom half and the hydrate dissociation in the top half part followed later. Our study demonstrates that X-ray CT imaging can be a useful tool to visualize and quantify the fines migration during hydrate depressurization, and our results present an experimental evidence that depressurization can cause pore clogging in sediments containing more than 10% fines fraction.

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

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

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

DOE PAGES

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.; ...

2016-01-15

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Cryopreservation of human spermatozoa. I. Effects of holding procedure and seeding on motility, fertilizability, and acrosome reaction.

PubMed

Critser, J K; Huse-Benda, A R; Aaker, D V; Arneson, B W; Ball, G D

1987-04-01

Three experiments were conducted to evaluate effects of holding semen at +5.0 degrees C for 30 minutes or -5.0 degrees C for 10 minutes and ice crystal induction (seeding) on frozen-thawed human spermatozoa. In experiment 1, spermatozoa were frozen, and postthaw motility was evaluated immediately (0 hour) and 24 hours later. At both 0 and 24 hours, nonfrozen control samples had higher motility than all other treatment groups. At 0 hour postthaw, motility was higher in samples held at -5.0 degrees C for 10 minutes with no significant effect of seeding. At 24 hours, samples held at -5.0 degrees C for 10 minutes and seeded, but not samples held at -5.0 degrees C and not seeded, had higher motility than samples held at +5.0 degrees C. In experiment 2, semen samples were frozen, and fertilizability was evaluated in a zona-free hamster egg penetration assay. Seeded samples had a higher frequency of sperm penetration than either nonfrozen or nonseeded samples. In experiment 3, nonfrozen controls and frozen treatment groups were evaluated for the frequency of survival and acrosomal integrity. Seeded samples had higher frequencies of survival and loss of acrosomal integrity than nonseeded samples. All frozen-thawed samples had a lower frequency of survival and a higher frequency of loss of acrosomal integrity than nonfrozen controls. Although altered patterns of fertilizability and acrosomal integrity are induced, collectively these data suggest that incorporating a holding temperature of -5.0 degrees C for 10 minutes and seeding may result in a superior protocol for freezing human spermatozoa.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Free energy landscape and molecular pathways of gas hydrate nucleation.

PubMed

Bi, Yuanfei; Porras, Anna; Li, Tianshu

2016-12-07

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

Free energy landscape and molecular pathways of gas hydrate nucleation

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

Bi, Yuanfei; Porras, Anna; Li, Tianshu, E-mail: tsli@gwu.edu

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p{sub B} histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage ordermore » parameter (H-COP) which we developed for driving FFS, through conducting the p{sub B} histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.« less

Image sampling in static telepathology for frozen section diagnosis.

PubMed

Della Mea, V; Cataldi, P; Boi, S; Finato, N; Dalla Palma, P; Beltrami, C A

1999-10-01

A frozen section diagnostic service is often not directly available in small rural or mountain hospitals. In these cases, it could be possible to provide frozen section diagnosis through telepathology systems. Telepathology is based on two main methods: static and dynamic. The former is less expensive, but involves the crucial problem of image sampling. To characterise the differences in image sampling for static telepathology when undertaken by pathologists with different experience. As a test field, a previously studied telepathology method based on multimedia email was adopted. Using this method, three pathologists with different levels of experience sampled images from 155 routine frozen sections and sent them to a distant pathology institute, where diagnoses were made on digital images. After the telepathology diagnoses, the glass slides of both the frozen sections and the definitive sections were sent to the remote pathologists for review. Four of 155 transmissions were considered inadequate by the remote pathologist. In the remaining 151 cases, the telepathology diagnosis agreed with the gold standard in 146 (96.7%). There was no significant divergence between the three pathologists in their sampling of the images. Each case comprised five images on average, acquired in four minutes. The overall time for transmission was about 19 minutes. The results suggest that in routine frozen section diagnosis an inexperienced pathologist can sample images sufficiently well to permit remote diagnosis. However, as expected, the internet is too unreliable for such a time dependent task. An improvement in the system would involve integrated real time features, so that there could be interaction between the two pathologists.

Gas hydrate hunting in China seas

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

A pressure core ultrasonic test system for on-board analysis of gas hydrate-bearing sediments under in situ pressures.

PubMed

Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng

2018-05-01

The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.

A pressure core ultrasonic test system for on-board analysis of gas hydrate-bearing sediments under in situ pressures

NASA Astrophysics Data System (ADS)

Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng

2018-05-01

The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.

Theoretical performance of some rocket propellants containing hydrogen, nitrogen, and oxygen

NASA Technical Reports Server (NTRS)

Miller, Riley O; Ordin, Paul M

1948-01-01

Theoretical performance data including nozzle-exit temperature, specific impulse, volume specific impulse and composition, temperature, and mean molecular weight of reaction products based on frozen equilibrium and isentropic expansion are presented for 13 propellant combinations at reaction pressure of 300 pounds per square inch absolute and expansion ratio of 20.4. On basis of maximum specific impulse alone, five fuels had the following order for any given oxidant: liquid hydrogen, hydrazine, liquid ammonia, and either hydrazine hydrate or hydroxylamine. Three oxidants with a given fuel had the following order: liquid ozone, liquid oxygen, and 100-percent hydrogen peroxide.

Anti-contamination device for cryogenic soft X-ray diffraction microscopy

DOE PAGES

Huang, Xiaojing; Miao, Huijie; Nelson, Johanna; ...

2011-05-01

Cryogenic microscopy allows one to view frozen hydrated biological and soft matter specimens with good structural preservation and a high degree of stability against radiation damage. We describe a liquid nitrogen-cooled anti-contamination device for cryogenic X-ray diffraction microscopy. The anti-contaminator greatly reduces the buildup of ice layers on the specimen due to condensation of residual water vapor in the experimental vacuum chamber. We show by coherent X-ray diffraction measurements that this leads to fivefold reduction of background scattering, which is important for far-field X-ray diffraction microscopy of biological specimens.

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

Artificial insemination of cranes with frozen semen

USGS Publications Warehouse

Gee, G.F.; Sexton, T.J.; Lewis, J.C.

1979-01-01

For the first time (1978) artificial insemination (AI) with frozen greater sandhill crane (Grus canadensis tabida) semen resulted in fertile eggs and chicks. During the 2 year (1977-78) study, 6 of 27 eggs produced were fertile. Three chicks hatched. Semen samples used for insemination were frozen and stored in liquid nitrogen for two months or less. Recent improvements in the laboratory indicated that a more effective sample can be prepared and greater fertility rates should be expected.

Investigation of the usefulness of fluorescein sodium fluorescence in stereotactic brain biopsy.

PubMed

Thien, Ady; Han, Julian Xinguang; Kumar, Krishan; Ng, Yew Poh; Rao, Jai Prashanth; Ng, Wai Hoe; King, Nicolas Kon Kam

2018-02-01

Intraoperative frozen section assessment, to confirm acquisition of pathological tissues, is used in stereotactic brain biopsy to minimise sampling errors. Limitations include the dependence on dedicated neuro-oncology pathologists and an increase in operative duration. We investigated the use of intraoperative fluorescein sodium, and compared it to frozen section assessment, for confirming pathological tissue samples in the stereotactic biopsy of gadolinium-contrast-enhancing brain lesions. This prospective observational study consisted of 18 consecutive patients (12 men; median age, 63 years) who underwent stereotactic biopsy of gadolinium-contrast-enhancing brain lesions with intravenous fluorescein sodium administration. Twenty-three specimens were obtained and examined for the presence of fluorescence using a microscope with fluorescence visualisation capability. Positive and negative predictive values were calculated based on the fluorescence status of the biopsy samples with its corresponding intraoperative frozen section and definitive histopathological diagnosis. Nineteen specimens (83%) were fluorescent and four (17%) were non-fluorescent. All 19 fluorescent specimens were confirmed to be lesional on intraoperative frozen section assessment and were suitable for histopathological diagnosis. Three of the non-fluorescent specimens were confirmed to be lesional on intraoperative frozen section assessment. One non-fluorescent specimen was non-diagnostic on frozen section and histological assessments. The positive predictive value was 100% and the negative predictive value was 25%. Fluorescein sodium fluorescence is as accurate as frozen section assessment in confirming sampling of pathological tissue in the stereotactic biopsy of gadolinium-contrast-enhancing brain lesions. Fluorescein sodium fluorescence-guided stereotactic biopsy is a useful addition to the neurosurgical armamentarium.

Freezing of homogenized sputum samples for intermittent storage.

PubMed

Holz, O; Mücke, M; Zarza, P; Loppow, D; Jörres, R A; Magnussen, H

2001-08-01

Among the reasons that restrict the application of sputum induction in outpatient settings is the need for processing of samples within 2 h after induction. The aim of our study was to assess whether freezing is suitable for intermediate storage of sputum samples before processing. We compared differential cell counts between two sputum aliquots derived from the same sample. One aliquot was processed within 2 h after production and one, after it had been frozen under addition of dimethyl-sulfoxid (DMSO) and stored up to 10 days at -20 degrees C. Thirty-five samples were frozen immediately prior to preparation of cytospins, and 10 samples were frozen at an even earlier stage, directly after homogenization. In both sets of experiments we observed a significant relationship between frozen and native samples regarding macrophages, neutrophils and eosinophils, as indicated by respective intraclass correlation coefficients of 0.96, 0.96, and 0.93 in the first, and of 0.92, 0.96 and 0.77 in the second experiments. Our results indicate that the freezing of sputum samples at different stages of processing does not alter sputum morphology to an extent that affects the results of differential cell counts.

Is Obsidian Hydration Dating Affected by Relative Humidity?

USGS Publications Warehouse

Friedman, I.; Trembour, F.W.; Smith, G.I.; Smith, F.L.

1994-01-01

Experiments carried out under temperatures and relative humidities that approximate ambient conditions show that the rate of hydration of obsidian is a function of the relative humidity, as well as of previously established variables of temperature and obsidian chemical composition. Measurements of the relative humidity of soil at 25 sites and at depths of between 0.01 and 2 m below ground show that in most soil environments, at depths below about 0.25 m, the relative humidity is constant at 100%. We have found that the thickness of the hydrated layer developed on obsidian outcrops exposed to the sun and to relative humidities of 30-90% is similar to that formed on other portions of the outcrop that were shielded from the sun and exposed to a relative humidity of approximately 100%. Surface samples of obsidian exposed to solar heating should hydrate more rapidly than samples buried in the ground. However, the effect of the lower mean relative humidity experiences by surface samples tends to compensate for the elevated temperature, which may explain why obsidian hydration ages of surface samples usually approximate those derived from buried samples.

Sensory descriptive quantitative analysis of unpasteurized and pasteurized juçara pulp (Euterpe edulis) during long-term storage

PubMed Central

da Silva, Paula Porrelli Moreira; Casemiro, Renata Cristina; Zillo, Rafaela Rebessi; de Camargo, Adriano Costa; Prospero, Evanilda Teresinha Perissinotto; Spoto, Marta Helena Fillet

2014-01-01

This study evaluated the effect of pasteurization followed by storage under different conditions on the sensory attributes of frozen juçara pulp using quantitative descriptive analysis (QDA). Pasteurization of packed frozen pulp was performed by its immersion in stainless steel tank containing water (80°C) for 5 min, followed by storage under refrigerated and frozen conditions. A trained sensory panel evaluated the samples (6°C) on day 1, 15, 30, 45, 60, 75, and 90. Sensory attributes were separated as follows: appearance (foamy, heterogeneous, purple, brown, oily, and creamy), aroma (sweet and fermented), taste (astringent, bitter, and sweet), and texture (oily and consistent), and compared to a reference material. In general, unpasteurized frozen pulp showed the highest score for foamy appearance, and pasteurized samples showed highest scores to creamy appearance. Pasteurized samples remained stable regarding brown color development while unpasteurized counterparts presented increase. Color is an important attribute related to the product identity. All attributes related to taste and texture remained constant during storage for all samples. Pasteurization followed by storage under frozen conditions has shown to be the best conservation method as samples submitted to such process received the best sensory evaluation, described as foamy, slightly heterogeneous, slightly bitter, and slightly astringent. PMID:25473489

Sensory descriptive quantitative analysis of unpasteurized and pasteurized juçara pulp (Euterpe edulis) during long-term storage.

PubMed

da Silva, Paula Porrelli Moreira; Casemiro, Renata Cristina; Zillo, Rafaela Rebessi; de Camargo, Adriano Costa; Prospero, Evanilda Teresinha Perissinotto; Spoto, Marta Helena Fillet

2014-07-01

This study evaluated the effect of pasteurization followed by storage under different conditions on the sensory attributes of frozen juçara pulp using quantitative descriptive analysis (QDA). Pasteurization of packed frozen pulp was performed by its immersion in stainless steel tank containing water (80°C) for 5 min, followed by storage under refrigerated and frozen conditions. A trained sensory panel evaluated the samples (6°C) on day 1, 15, 30, 45, 60, 75, and 90. Sensory attributes were separated as follows: appearance (foamy, heterogeneous, purple, brown, oily, and creamy), aroma (sweet and fermented), taste (astringent, bitter, and sweet), and texture (oily and consistent), and compared to a reference material. In general, unpasteurized frozen pulp showed the highest score for foamy appearance, and pasteurized samples showed highest scores to creamy appearance. Pasteurized samples remained stable regarding brown color development while unpasteurized counterparts presented increase. Color is an important attribute related to the product identity. All attributes related to taste and texture remained constant during storage for all samples. Pasteurization followed by storage under frozen conditions has shown to be the best conservation method as samples submitted to such process received the best sensory evaluation, described as foamy, slightly heterogeneous, slightly bitter, and slightly astringent.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Effect of freezing on electrical properties and quality of thawed chicken breast meat

PubMed Central

Wei, Ran; Wang, Peng; Han, Minyi; Chen, Tianhao; Xu, Xinglian; Zhou, Guanghong

2017-01-01

Objective The objective of this research was to study the electrical properties and quality of frozen-thawed chicken breast meat and to investigate the relationship between these parameters at different times of frozen storage. Methods Thawed samples of chicken breast muscles were evaluated after being kept in frozen storage at −18°C for different periods of time (1, 2, 3, 4, 5, 6, 7, and 8 months). Results The results showed that water-holding capacity (WHC) and protein solubility decreased while thiobarbituric acid-reactive substances content increased with increasing storage time. The impedance module of samples decreased during 8-month frozen storage. Pearson correlation coefficients showed that the impedance change ratio (Q value) was significantly (p<0.05) related to pH, color, WHC, lipid oxidation and protein solubility, indicating a good relationship between the electrical properties and qualities of frozen-thawed chicken breast meat. Conclusion Impedance measurement has a potential to assess the quality of frozen chicken meat combining with quality indices. PMID:27554358

Blood oxygen saturation of frozen tissue determined by hyper spectral imaging

NASA Astrophysics Data System (ADS)

Braaf, Boy; Nadort, Annemarie; Faber, Dirk; ter Wee, Rene; van Leeuwen, Ton; Aalders, Maurice

2008-02-01

A method is proposed for determining blood oxygen saturation in frozen tissue. The method is based on a spectral camera system equipped with an Acoustic-Optical-Tuneable-Filter. The HSI-setup is validated by measuring series of unfrozen and frozen samples of a hemoglobin-solution, a hemoglobin-intralipid mixture and whole blood with varying oxygen saturation. The theoretically predicted linear relation between oxygen saturation and absorbance was observed in both the frozen sample series and the unfrozen series. In a final proof of principal, frozen myocardial tissue was measured. Higher saturation values were recorded for ventricle and atria tissue compared to the septum and connective tissue. These results are not validated by measurements with another method. The formation of methemoglobin during freezing and the presence of myoglobin in the tissue turned out to be possible sources of error.

Investigation of the effect of hydration on dermal collagen in ex vivo human skin tissue using second harmonic generation microscopy

NASA Astrophysics Data System (ADS)

Samatham, Ravikant; Wang, Nicholas K.; Jacques, Steven L.

2016-02-01

Effect of hydration on the dermal collagen structure in human skin was investigated using second harmonic generation microscopy. Dog ears from the Mohs micrographic surgery department were procured for the study. Skin samples with subject aged between 58-90 years old were used in the study. Three dimensional Multiphoton (Two-photon and backward SHG) control data was acquired from the skin samples. After the control measurement, the skin tissue was either soaked in deionized water for 2 hours (Hydration) or kept at room temperature for 2 hours (Desiccation), and SHG data was acquired. The data was normalized for changes in laser power and detector gain. The collagen signal per unit volume from the dermis was calculated. The desiccated skin tissue gave higher backward SHG compared to respective control tissue, while hydration sample gave a lower backward SHG. The collagen signal decreased with increase in hydration of the dermal collagen. Hydration affected the packing of the collagen fibrils causing a change in the backward SHG signal. In this study, the use of multiphoton microscopy to study the effect of hydration on dermal structure was demonstrated in ex vivo tissue.

Measurements of gas hydrate formation probability distributions on a quasi-free water droplet

NASA Astrophysics Data System (ADS)

Maeda, Nobuo

2014-06-01

A High Pressure Automated Lag Time Apparatus (HP-ALTA) can measure gas hydrate formation probability distributions from water in a glass sample cell. In an HP-ALTA gas hydrate formation originates near the edges of the sample cell and gas hydrate films subsequently grow across the water-guest gas interface. It would ideally be desirable to be able to measure gas hydrate formation probability distributions of a single water droplet or mist that is freely levitating in a guest gas, but this is technically challenging. The next best option is to let a water droplet sit on top of a denser, immiscible, inert, and wall-wetting hydrophobic liquid to avoid contact of a water droplet with the solid walls. Here we report the development of a second generation HP-ALTA which can measure gas hydrate formation probability distributions of a water droplet which sits on a perfluorocarbon oil in a container that is coated with 1H,1H,2H,2H-Perfluorodecyltriethoxysilane. It was found that the gas hydrate formation probability distributions of such a quasi-free water droplet were significantly lower than those of water in a glass sample cell.

The case study of drillbit and borehole frozen water of the subglacial Lake Vostok, East Antarctica for microbial content

NASA Astrophysics Data System (ADS)

Bulat, Sergey; Doronin, Maxim; Dominique, Marie; Lipenkov, Vladimir; Lukin, Valery; Karlov, Denis; Demchenko, Leonid; Khilchenko, Margarita

The objective was to estimate microbial content and diversity in the subglacial Lake Vostok (buried beneath 4-km thick East Antarctic ice sheet) by studying the uppermost water layer which entered the borehole upon lake entry (February 5, 2012) and then shortly frozen within. The samples of so-called drillbit water frozen on a drill bit upon lake enter (RAE57) along with re-drilled so-called borehole-frozen water (RAE58) were provided for the study with the ultimate goal to discover the life in this extreme icy environment. The comprehensive analyses (constrained by Ancient DNA research criteria) of the first lake water samples - drillbit- (one sample) and borehole-frozen (3 different depths 5G-2N-3425, 3429 et 3450m), are nearly got finished. If the drillbit water sample was heavily polluted with drill fluid (at ratio 1:1), re-drilled borehole-frozen samples were proved to be rather clean but still strongly smelling kerosene and containing numerous micro-droplets of drill fluid making the ice non-transparent. The cell concentrations measured by flow cytofluorometry showed 167 cells per ml in the drillbit water sample while in borehole-frozen samples ranged from 5.5 (full-cylinder 3429m deep frozen water ice core) to 38 cells per ml (freeze-centre of 3450m deep moon-shape ice core). DNA analyses came up with total 44 bacterial phylotypes discovered by sequencing of different regions (v3-v5, v4-v8, v4-v6 et full-gene) of 16S rRNA genes. Amongst them all but two were considered to be contaminants (were present in our contaminant library, including drill fluid findings). The 1st remaining phylotype successfully passing all contamination criteria proved to be hitherto-unknown type of bacterium (group of clones, 3 allelic variants) showing less than 86% similarity with known taxa. Its phylogenetic assignment to bacterial divisions or lineages was also unsuccessful despite of the RDP has classified it belonging to OD1 uncultured Candidate Division. The 2nd phylotype was less remarkable and still dubious in terms of contamination. It was presented by just one clone and showed 93% similarity with Janthinobacterium sp of Oxalobacteraceae (Beta-Proteobacteria) - well-known ‘water-loving’ bacteria. No archaea were detected in lake water frozen samples. Thus, the unidentified and unclassified bacterial w123-10 phylotype for the first time discovered in the uppermost water layer in subglacial Lake Vostok might represent ingenious cell populations in the lake, making the life in the lake less elusive. The proof may come (as well as novel phylotype discoveries) with farther analyses (e.g., sample screening with w123-10-specific primers, 16S rRNA v4 region amplicon sequencing) of existing and newly requested moon-shape samples of borehole-frozen water which are on a way to laboratories. We are deeply grateful to Jean Robert Petit and Jean Martins, UJF-CNRS, Grenoble (France) for assistance in conducting some analyses.

A petroleum system model for gas hydrate deposits in northern Alaska

USGS Publications Warehouse

Lorenson, T.D.; Collett, Timothy S.; Wong, Florence L.

2011-01-01

Gas hydrate deposits are common on the North Slope of Alaska around Prudhoe Bay, however the extent of these deposits is unknown outside of this area. As part of a United States Geological Survey (USGS) and the Bureau of Land Management (BLM) gas hydrate research collaboration, well cutting and mud gas samples have been collected and analyzed from mainly industry-drilled wells on the Alaska North Slope for the purpose of prospecting for gas hydrate deposits. On the Alaska North Slope, gas hydrates are now recognized as an element within a petroleum systems approach or TPS (Total Petroleum System). Since 1979, 35 wells have been samples from as far west as Wainwright to Prudhoe Bay in the east. Geochemical studies of known gas hydrate occurrences on the North Slope have shown a link between gas hydrate and more deeply buried conventional oil and gas deposits. Hydrocarbon gases migrate from depth and charge the reservoir rock within the gas hydrate stability zone. It is likely gases migrated into conventional traps as free gas, and were later converted to gas hydrate in response to climate cooling concurrent with permafrost formation. Gas hydrate is known to occur in one of the sampled wells, likely present in 22 others based gas geochemistry and inferred by equivocal gas geochemistry in 11 wells, and absent in one well. Gas migration routes are common in the North Slope and include faults and widespread, continuous, shallowly dipping permeable sand sections that are potentially in communication with deeper oil and gas sources. The application of this model with the geochemical evidence suggests that gas hydrate deposits may be widespread across the North Slope of Alaska.

Microbiological quality of five potato products obtained at retail markets.

PubMed Central

Duran, A P; Swartzentruber, A; Lanier, J M; Wentz, B A; Schwab, A H; Barnard, R J; Read, R B

1982-01-01

The microbiological quality of frozen hash brown potatoes, dried hash brown potatoes with onions, frozen french fried potatoes, dried instant mashed potatoes, and potato salad was determined by a national sampling at the retail level. A wide range of results was obtained, with most sampling units of each products having excellent microbiological quality. Geometric mean aerobic plate counts were as follows: dried hash brown potatoes, 270/g; frozen hash brown potatoes with onions, 580/g; frozen french fried potatoes 78/g; dried instant mashed potatoes, 1.1 x 10(3)/g; and potato salad, 3.6 x 10(3)/g. Mean values of coliforms, Escherichia coli, and Staphylococcus aureus were less than 10/g. PMID:6758695

Characterization of Gas Hydrate Samples from IODP 311 using High Resolution Raman Spectroscopy, X-ray Diffraction and Differential Scanning Calorimetry

NASA Astrophysics Data System (ADS)

Schicks, J. M.; Ziemann, M. A.; Naumann, R.; Erzinger, J.

2006-12-01

Investigations on hydrate bearing sediments taken from different locations (Gulf of Mexico, Sea of Okhotsk, etc.) lead to the conclusion that the coexistence of gas hydrates with different structures and compositions in nature is possible (Sassen et al. 2000, Takeya et al 2006). The aim of this study is to get more information about the variation in local composition of gas hydrates in samples from IODP Leg 311 (Hole 1328) using Raman spectroscopy. Therefore, in addition to investigations performed at the same samples by Lu et al., experiments in this study have been carried out with a confocal Raman microprobe in high lateral and spectral resolution mode. The samples have been analysed at 153 K and at atmospheric pressure (single spots, line scans, area mapping). The specified structure I hydrates contain methane and H2S. The Raman bands at 2569 cm-1 and 2593 cm-1 indicate H2S in large and small cages, respectively. Further information is provided about the variation of the CH4-H2S- composition and the cage occupancy of the sample. The samples have also been investigated with X-ray diffraction and differential scanning calorimetry (DSC). DSC measurements hint at the coexistence of two different gas hydrates with significantly different decomposition temperatures at atmospheric pressure (206 K and 247 K). This could be caused by variable amounts of H2S incorporated in the hydrate lattice. The results from the investigation on the IODP Leg 311 samples are compared and discussed with results of similar investigations on samples of structure I hydrate from Mallik 5L-38 drill hole in the permafrost of NW Canada. References: R. Sassen, S.T. Sweet, D.A. DeFreitas, A.V. Milkov, 2000. Organic Geochemistry, 31, 1257-1262. S. Takeya, M. Kida, H. Minami, H. Sakagami, A. Hachikubo, N. Takahashi, H. Shoji, V. Soloviev, K. Wallmann, N. Biebow, A. Obzhirov, A Salomatin, J. Poort, 2006. Chemical Engineering Science, 61, 2670- 2674.

Evaporation process in histological tissue sections for neutron autoradiography.

PubMed

Espector, Natalia M; Portu, Agustina; Santa Cruz, Gustavo A; Saint Martin, Gisela

2018-05-01

The analysis of the distribution and density of nuclear tracks forming an autoradiography in a nuclear track detector (NTD) allows the determination of 10 B atoms concentration and location in tissue samples from Boron Neutron Capture Therapy (BNCT) protocols. This knowledge is of great importance for BNCT dosimetry and treatment planning. Tissue sections studied with this technique are obtained by cryosectioning frozen tissue specimens. After the slicing procedure, the tissue section is put on the NTD and the sample starts drying. The thickness varies from its original value allowing more particles to reach the detector and, as the mass of the sample decreases, the boron concentration in the sample increases. So in order to determine the concentration present in the hydrated tissue, the application of corrective coefficients is required. Evaporation mechanisms as well as various factors that could affect the process of mass variation are outlined in this work. Mass evolution for tissue samples coming from BDIX rats was registered with a semimicro analytical scale and measurements were analyzed with software developed to that end. Ambient conditions were simultaneously recorded, obtaining reproducible evaporation curves. Mathematical models found in the literature were applied for the first time to this type of samples and the best fit of the experimental data was determined. The correlation coefficients and the variability of the parameters were evaluated, pointing to Page's model as the one that best represented the evaporation curves. These studies will contribute to a more precise assessment of boron concentration in tissue samples by the Neutron Autoradiography technique.

Influence of the freezing method on the changes that occur in grape samples after frozen storage.

PubMed

Santesteban, Luis G; Miranda, Carlos; Royo, José B

2013-09-01

Sample freezing is frequently used in oenological laboratories as a compromise solution to increase the number of samples that can be analysed, despite the fact that some grape characteristics are known to change after frozen storage. However, freezing is usually performed using standard freezers, which provide a slow freezing. The aim of this work was to evaluate whether blast freezing would decrease the impact of standard freezing on grape composition. Grape quality parameters were assessed in fresh and in frozen stored samples that had been frozen using three different procedures: standard freezing and blast freezing using either a blast freezer or an ultra-freezer. The implications of frozen storage in grape samples reported in earlier research were observed for the three freezing methods evaluated. Although blast freezing improved repeatability for the most problematic parameters (tartaric acidity, TarA; total phenolics, TP), the improvement was not important from a practical point of view. However, TarA and TP were relatively repeatable among the three freezing procedures, which suggests that freezing had an effect on these parameters independently of the method used . According to our results, the salification potential of the must is probably implied in the changes observed for TarA, whereas for TP the precipitation of protoanthocyanins after association with cell wall material is hypothesized to cause the lack of repeatability between fresh and frozen grapes. Blast freezing would not imply a great improvement if implemented in oenological laboratories, at least for the parameters included in this study. © 2013 Society of Chemical Industry.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

In-Situ Sampling and Characterization of Naturally Occurring Marine Methane Hydrate Using the D/V JOIDES Resolution

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

Rack, Frank; Storms, Michael; Schroeder, Derryl

The primary accomplishments of the JOI Cooperative Agreement with DOE/NETL in this quarter were (1) the preliminary postcruise evaluation of the tools and measurement systems that were used during ODP Leg 204 to study hydrate deposits on Hydrate Ridge, offshore Oregon from July through September 2002; and (2) the preliminary study of the hydrate-bearing core samples preserved in pressure vessels and in liquid nitrogen cryofreezers, which are now stored at the ODP Gulf Coast Repository in College Station, TX. During ODP Leg 204, several newly modified downhole tools were deployed to better characterize the subsurface lithologies and environments hosting microbialmore » populations and gas hydrates. A preliminary review of the use of these tools is provided herein. The DVTP, DVTP-P, APC-methane, and APC-Temperature tools (ODP memory tools) were used extensively and successfully during ODP Leg 204 aboard the D/V JOIDES Resolution. These systems provided a strong operational capability for characterizing the in situ properties of methane hydrates in subsurface environments on Hydrate Ridge during ODP Leg 204. Pressure was also measured during a trial run of the Fugro piezoprobe, which operates on similar principles as the DVTP-P. The final report describing the deployments of the Fugro Piezoprobe is provided in Appendix A of this report. A preliminary analysis and comparison between the piezoprobe and DVTP-P tools is provided in Appendix B of this report. Finally, a series of additional holes were cored at the crest of Hydrate Ridge (Site 1249) specifically geared toward the rapid recovery and preservation of hydrate samples as part of a hydrate geriatric study partially funded by the Department of Energy (DOE). In addition, the preliminary results from gamma density non-invasive imaging of the cores preserved in pressure vessels are provided in Appendix C of this report. An initial visual inspection of the samples stored in liquid nitrogen is provided in Appendix D of this report.« less

Urine phenobarbital drug screening: potential use for compliance assessment in neonates.

PubMed

Guillet, Ronnie; Kwon, Jennifer M; Chen, Sixaio; McDermott, Michael P

2012-02-01

This study was done to determine if urine phenobarbital measurements provide a reliable indicator of presence of the drug in neonates. Urine was collected from neonates treated with phenobarbital for clinical indications within 4 to 6 hours of clinically indicated collection of serum phenobarbital levels. Urine samples were also collected from control neonates not treated with phenobarbital. One aliquot was assayed fresh, another frozen at -30°C and assayed 1 to 3 months later. Phenobarbital was assayed using the ONLINE TDM Roche/Hitachi automated clinical chemistry analyzer. Serum and urine concentrations were compared as were fresh and frozen urine measurements. Serum phenobarbital ranged from 5.6 to 52.7 μg/mL. Matched urine samples were 56.6 ± 12.5% of the serum level. Frozen samples were 98.3 ± 8.0% of the fresh samples. Urine phenobarbital concentrations, either fresh or frozen, can be used in neonates as a noninvasive estimate of drug levels.

Physical properties of northern Gulf of Mexico sediment and laboratory samples containing natural and synthetic methane gas hydrate

NASA Astrophysics Data System (ADS)

Winters, W. J.; Waite, W. F.; Mason, D. H.; Lorenson, T. L.; Paull, C. K.; Novosel, I.; Boldina, O. M.; Dallimore, S. R.; Collett, T. S.; Page 127 Shipboard Sc. Party

2003-04-01

The U.S. Geological Survey (USGS) has been involved in oceanographic and Arctic field programs and laboratory studies to better understand the relationship between natural gas hydrate and physical properties of surrounding sediment. Recently, the Institut Polaire Francais, Paul-Emile Victor (IPEV) and the USGS jointly conducted a cruise aboard the Marion Dufresne to collect giant piston cores to determine the distribution of gas hydrate in the northern Gulf of Mexico. Hydrates recovered during the cruise did not appear to be lithologically controlled (unlike Canadian Arctic cores) and were either disseminated or were massive layers. Sediment water content typically decreases rapidly to a subbottom depth of about 8 to 9 m, but then decreases at a lower rate. At-sea help was provided by the IMAGES (International Marine Past Global Changes Study) and PAGE (Paleoceanography of the Atlantic and Geochemistry) programs, and funding was provided by the U.S. Dept. of Energy. We have used the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) to analyze sediment containing natural gas hydrate and to examine hydrate formed within (a) initially water-saturated and (b) partly-water saturated sieved Ottawa sand specimens at a pore pressure of 12 MPa and 250 kPa confining stress. Hydrate is formed when methane gas is slowly percolated into a 70-mm diameter by 140-mm long cylindrical specimen and subsequently the temperature is lowered to about 6 degrees C. We have found that acoustic velocity, shear strength, and permeability of samples containing different initial water contents are significantly affected by (a) the amount of hydrate present, (b) its distribution, (c) its position within pores, and (d) concentration at key locations. Acoustic P-wave velocities can increase from 1.7 km/s to 4.0 km/s using different hydrate and synthetic sample formation techniques. Although acoustic properties are significantly affected by hydrate at grain boundaries, the mere presence of hydrate in pores (but not necessarily at grain contacts) causes strength to significantly increase because dilation during undrained shear results in greater negative pore pressures. Recently determined strengths of three Ottawa sand samples are exponentially related to the degree of water saturation, bulk density, and hydrate content.

A novel method for single sample multi-axial nanoindentation of hydrated heterogeneous tissues based on testing great white shark jaws.

PubMed

Ferrara, Toni L; Boughton, Philip; Slavich, Eve; Wroe, Stephen

2013-01-01

Nanomechanical testing methods that are suitable for a range of hydrated tissues are crucial for understanding biological systems. Nanoindentation of tissues can provide valuable insights into biology, tissue engineering and biomimetic design. However, testing hydrated biological samples still remains a significant challenge. Shark jaw cartilage is an ideal substrate for developing a method to test hydrated tissues because it is a unique heterogeneous composite of both mineralized (hard) and non-mineralized (soft) layers and possesses a jaw geometry that is challenging to test mechanically. The aim of this study is to develop a novel method for obtaining multidirectional nanomechanical properties for both layers of jaw cartilage from a single sample, taken from the great white shark (Carcharodon carcharias). A method for obtaining multidirectional data from a single sample is necessary for examining tissue mechanics in this shark because it is a protected species and hence samples may be difficult to obtain. Results show that this method maintains hydration of samples that would otherwise rapidly dehydrate. Our study is the first analysis of nanomechanical properties of great white shark jaw cartilage. Variation in nanomechanical properties were detected in different orthogonal directions for both layers of jaw cartilage in this species. The data further suggest that the mineralized layer of shark jaw cartilage is less stiff than previously posited. Our method allows multidirectional nanomechanical properties to be obtained from a single, small, hydrated heterogeneous sample. Our technique is therefore suitable for use when specimens are rare, valuable or limited in quantity, such as samples obtained from endangered species or pathological tissues. We also outline a method for tip-to-optic calibration that facilitates nanoindentation of soft biological tissues. Our technique may help address the critical need for a nanomechanical testing method that is applicable to a variety of hydrated biological materials whether soft or hard.

Frozen tissue preparation for high-resolution multiplex histological analyses of human brain specimens.

PubMed

Shao, Fangjie; Jiang, Wenhong; Gao, Qingqing; Li, Baizhou; Sun, Chongran; Wang, Qiyuan; Chen, Qin; Sun, Bing; Shen, Hong; Zhu, Keqing; Zhang, Jianmin; Liu, Chong

2017-10-01

The availability of a comprehensive tissue library is essential for elucidating the function and pathology of human brains. Considering the irreplaceable status of the formalin-fixation-paraffin-embedding (FFPE) preparation in routine pathology and the advantage of ultra-low temperature to preserve nucleic acids and proteins for multi-omics studies, these methods have become major modalities for the construction of brain tissue libraries. Nevertheless, the use of FFPE and snap-frozen samples is limited in high-resolution histological analyses because the preparation destroys tissue integrity and/or many important cellular markers. To overcome these limitations, we detailed a protocol to prepare and analyze frozen human brain samples that is particularly suitable for high-resolution multiplex immunohistological studies. As an alternative, we offered an optimized procedure to rescue snap-frozen tissues for the same purpose. Importantly, we provided a guideline to construct libraries of frozen tissue with minimal effort, cost and space. Taking advantage of this new tissue preparation modality to nicely preserve the cellular information that was otherwise damaged using conventional methods and to effectively remove tissue autofluorescence, we described the high-resolution landscape of the cellular composition in both lower-grade gliomas and glioblastoma multiforme samples. Our work showcases the great value of fixed frozen tissue in understanding the cellular mechanisms of CNS functions and abnormalities.

Gas content and composition of gas hydrate from sediments of the southeastern North American continental margin

USGS Publications Warehouse

Lorenson, T.D.; Collett, T.S.

2000-01-01

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from ??13C of -62.5??? to -70.7??? and ??D of -175??? to -200??? and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from ??13C of -5.7 to -6.9, about 15??? lighter than CO2 derived from nearby sediment.

Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization

USGS Publications Warehouse

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

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X– ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization

USGS Publications Warehouse

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

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X-ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma

DOE PAGES

Jacobs, Anne C.; Fair, Jeanne Marie

2015-10-09

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. Here, we tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throatedmore » flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. Finally, we caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis.« less

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma.

PubMed

Jacobs, Anne C; Fair, Jeanne M

2016-01-01

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. We tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throated flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. We caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis. Copyright © 2015 Elsevier Inc. All rights reserved.

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma

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

Jacobs, Anne C.; Fair, Jeanne Marie

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. Here, we tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throatedmore » flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. Finally, we caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis.« less

Magnetic properties of Japan Sea sediments in areas which host shallow gas hydrates and in relation to the the amount of gas hydrate

NASA Astrophysics Data System (ADS)

Shimono, T.; Matsumoto, R.

2016-12-01

Shallow gas hydrate is known to occur as massive nodular aggregates in subsurface and/or shallow marine sediments (e.g. Matsumoto et al. 2009). We conducted a rock magnetic study of marine core sediments to clarify the relationship between shallow gas hydrate and the surrounding sediments. The core samples were taken from around Oki area and offshore Joetsu, the eastern margin of Japan Sea, during PS15 cruise in 2015. We mainly report magnetic susceptibility measurement of whole-round core samples. From the onboard measurements, the magnetic susceptibilities of gas hydrates indicated diamagnetic mineral like water or ice ( -0.9 x 10-5 vol. SI). Moreover, we introduce a method to assess the amount of gas hydrate present within marine sediments using magnetic susceptibility and rock magnetic analyses. This study was conducted under the commission from AIST as a part of the methane hydrate research project of METI (the Ministry of Economy, Trade and Industry, Japan).

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

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

Seol, Yongkoo; Myshakin, Evgeniy

2011-01-01

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

Freezing-thawing and sub-sampling influence the marination performance of chicken breast meat.

PubMed

Bowker, B; Zhuang, H

2017-09-01

Vacuum-tumbling marination is often used to improve the yield and quality of whole or portioned broiler breast fillets. The relationship between the marination performance of whole Pectoralis major muscles and breast fillet sub-samples is not well understood. The objective was to determine the effects of sub-sampling and freezing-thawing on the marination performance and cook loss of broiler breast meat. Paired right and left breast fillets were marinated as whole fillets or sub-samples (cranial and mid-caudal portions). Samples were marinated at 48 h postmortem (fresh) or stored at -20°C and then thawed prior to marination (frozen-thawed). Samples were vacuum-tumbled in 20% wt/wt brine (5% NaCl, 3% STP) and weighed pre-marination, during marination (15, 30, and 45 min), and 24 h post-marination. Samples were then cooked to 75°C for determination of cook loss. Marinade uptake was greater in caudal sub-samples than intact fillets and cranial sub-samples after 15 min of marination (P < 0.0001). After 30 min, marinade uptake was greater in caudal sub-samples and intact fillets than cranial sub-samples (P < 0.05). After 45 min, marinade uptake for fresh samples was greatest in intact fillets and lowest in cranial sub-samples. For frozen-thawed samples, marinade uptake at 45 min was greater in caudal sub-samples and intact fillets than cranial sub-samples (P < 0.0001). Marinade uptake in sub-samples at 30 min was greater in frozen-thawed versus fresh fillets (P < 0.05). Differences in marinade retention were not observed. Cook loss was similar between fresh and frozen-thawed samples but was greater in sub-samples compared to intact fillets (P < 0.0001). Correlations between marinade uptake in intact fillets and cranial sub-samples were greater in fresh (r = 0.64 to 0.78) than frozen-thawed samples (r = 0.39 to 0.59). Correlations between marinade uptake in intact fillets and caudal sub-samples were greater in frozen-thawed (r = 0.79 to 0.82) than fresh samples (r = 0.46 to 0.63). Data suggest that the relationships between marination performance of whole breast fillets and fillet sub-samples are dependent upon prior sample handling and intra-fillet sampling location. Published by Oxford University Press on behalf of Poultry Science Association 2017.

Frozen yogurt with added inulin and isomalt.

PubMed

Isik, U; Boyacioglu, D; Capanoglu, E; Erdil, D Nilufer

2011-04-01

The objective of this study was to produce a frozen yogurt containing low fat and no added sugar. Samples containing 5% polydextrose, 0.065% aspartame and acesulfame-K mixture, and different levels of inulin and isomalt (5.0, 6.5, and 8.0%) were produced at pilot scale and analyzed for their physical and chemical properties including proximate composition, viscosity, acidity, overrun, melting rate, heat shock stability, as well as sensory characteristics, and viability of lactic acid bacteria. With the addition of inulin and isomalt, viscosity increased by 19 to 52% compared with that of sample B (reduced-fat control). The average calorie values of samples substituted with sweeteners were about 43% lower than that of original sample. Low-calorie frozen yogurt samples melted about 33 to 48% slower than the reduced-fat control sample at 45 min. Based on quantitative descriptive profile test results, statistically significant differences among products were observed for hardness, iciness, foamy melting, whey separation, and sweetness characteristics. The results of principal component analysis showed that the sensory properties of the sample containing 6.5% inulin and 6.5% isomalt were similar to those of control. Lactic acid bacteria counts of frozen yogurt were found to be between 8.12 and 8.49 log values, 3 mo after the production. The overall results showed that it is possible to produce an attractive frozen yogurt product with the incorporation of inulin and isomalt with no added sugar and reduced fat. Copyright © 2011 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

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.

Simulations of single-particle imaging of hydrated proteins with x-ray free-electron lasers

NASA Astrophysics Data System (ADS)

Fortmann-Grote, C.; Bielecki, J.; Jurek, Z.; Santra, R.; Ziaja-Motyka, B.; Mancuso, A. P.

2017-08-01

We employ start-to-end simulations to model coherent diffractive imaging of single biomolecules using x-ray free electron lasers. This technique is expected to yield new structural information about biologically relevant macromolecules thanks to the ability to study the isolated sample in its natural environment as opposed to crystallized or cryogenic samples. The effect of the solvent on the diffraction pattern and interpretability of the data is an open question. We present first results of calculations where the solvent is taken into account explicitly. They were performed with a molecular dynamics scheme for a sample consisting of a protein and a hydration layer of varying thickness. Through R-factor analysis of the simulated diffraction patterns from hydrated samples, we show that the scattering background from realistic hydration layers of up to 3 Å thickness presents no obstacle for the resolution of molecular structures at the sub-nm level.

Relative merits and limiting factors for x-ray and electron microscopy of thick, hydrated organic materials

DOE PAGES

Du, Ming; Jacobsen, Chris

2017-10-07

Electron and x-ray microscopes allow one to image the entire, unlabeled structure of hydrated materials at a resolution well beyond what visible light microscopes can achieve. However, both approaches involve ionizing radiation, so that radiation damage must be considered as one of the limits to imaging. Drawing upon earlier work, we describe here a unified approach to estimating the image contrast (and thus the required exposure and corresponding radiation dose) in both x-ray and electron microscopy. This approach accounts for factors such as plural and inelastic scattering, and (in electron microscopy) the use of energy filters to obtain so-called "zeromore » loss" images. As expected, it shows that electron microscopy offers lower dose for specimens thinner than about 1 mu m (such as for studies of macromolecules, viruses, bacteria and archaebacteria, and thin sectioned material), while x-ray microscopy offers superior characteristics for imaging thicker specimen such as whole eukaryotic cells, thick-sectioned tissues, and organs. The required radiation dose scales strongly as a function of the desired spatial resolution, allowing one to understand the limits of live and frozen hydrated specimen imaging. Lastly, we consider the factors limiting x-ray microscopy of thicker materials, suggesting that specimens as thick as a whole mouse brain can be imaged with x-ray microscopes without significant image degradation should appropriate image reconstruction methods be identified.« less

Coupling between the Dynamics of Water and Surfactants in Lyotropic Liquid Crystals.

PubMed

McDaniel, Jesse G; Yethiraj, Arun

2017-05-18

Bilayers composed of lipid or surfactant molecules are central to biological membranes and lamellar lyotropic liquid crystalline (LLC) phases. Common to these systems are phases that exhibit either ordered or disordered packing of the hydrophobic tails. In this work, we study the impact of surfactant ordering, i.e., disordered L α and ordered L β LLC phases, on the dynamics of water and sodium ions in the lamellar phases of dicarboxylate gemini surfactants. We study the different phases at identical hydration levels by changing the length of the hydrophobic tails; surfactants with shorter tails form L α phases and those with longer tails form L β phases. We find that the L α phases exhibit lower density and greater compressibility than the L β phases, with a hydration-dependent headgroup surface area. These structural differences significantly affect the relative dynamic properties of the phases, primarily the mobility of the surfactant molecules tangential to the bilayer surface, as well as the rates of water and ion diffusion. We find ∼20-50% faster water diffusion in the L α phases compared to the L β phases, with the differences most pronounced at low hydration. This coupling between water dynamics and surfactant mobility is verified using additional simulations in which the surfactant tails are frozen. Our study indicates that gemini surfactant LLCs provide an important prototypical system for characterizing properties shared with more complex biological lipid membranes.

Relative merits and limiting factors for x-ray and electron microscopy of thick, hydrated organic materials

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

Du, Ming; Jacobsen, Chris

Electron and x-ray microscopes allow one to image the entire, unlabeled structure of hydrated materials at a resolution well beyond what visible light microscopes can achieve. However, both approaches involve ionizing radiation, so that radiation damage must be considered as one of the limits to imaging. Drawing upon earlier work, we describe here a unified approach to estimating the image contrast (and thus the required exposure and corresponding radiation dose) in both x-ray and electron microscopy. This approach accounts for factors such as plural and inelastic scattering, and (in electron microscopy) the use of energy filters to obtain so-called "zeromore » loss" images. As expected, it shows that electron microscopy offers lower dose for specimens thinner than about 1 mu m (such as for studies of macromolecules, viruses, bacteria and archaebacteria, and thin sectioned material), while x-ray microscopy offers superior characteristics for imaging thicker specimen such as whole eukaryotic cells, thick-sectioned tissues, and organs. The required radiation dose scales strongly as a function of the desired spatial resolution, allowing one to understand the limits of live and frozen hydrated specimen imaging. Lastly, we consider the factors limiting x-ray microscopy of thicker materials, suggesting that specimens as thick as a whole mouse brain can be imaged with x-ray microscopes without significant image degradation should appropriate image reconstruction methods be identified.« less

Gas hydrate prospecting using well cuttings and mud-gas geochemistry from 35 wells, North Slope, Alaska

USGS Publications Warehouse

Lorenson, T.D.; Collett, Timothy S.

2011-01-01

Gas hydrate deposits are common on the North Slope of Alaska around Prudhoe Bay; however, the extent of these deposits is unknown outside of this area. As part of a U.S. Geological Survey (USGS) and Bureau of Land Management gas hydrate research collaboration, well-cutting and mud-gas samples have been collected and analyzed from mainly industry-drilled wells on the North Slope for the purpose of prospecting for gas hydrate deposits. On the Alaska North Slope, gas hydrates are now recognized as an element within a petroleum systems approach or "total petroleum system." Since 1979, 35 wells have been sampled from as far west as Wainwright to Prudhoe Bay in the east. Regionally, the USGS has assessed the gas hydrate resources of the North Slope and determined that there is about 85.4 trillion cubic feet of technically recoverable hydrate-bound gas within three assessment units. The assessment units are defined mainly by three separate stratigraphic sections and constrained by the physical temperatures and pressures where gas hydrate can form. Geochemical studies of known gas hydrate occurrences on the North Slope have shown a link between gas hydrate and more deeply buried conventional oil and gas deposits. The link is established when hydrocarbon gases migrate from depth and charge the reservoir rock within the gas hydrate stability zone. It is likely gases migrated into conventional traps as free gas and were later converted to gas hydrate in response to climate cooling concurrent with permafrost formation. Results from this study indicate that some thermogenic gas is present in 31 of the wells, with limited evidence of thermogenic gas in four other wells and only one well with no thermogenic gas. Gas hydrate is known to occur in one of the sampled wells, likely present in 22 others on the basis of gas geochemistry, and inferred by equivocal gas geochemistry in 11 wells, and one well was without gas hydrate. Gas migration routes are common in the North Slope and include faults and widespread, continuous shallowly dipping permeable sand sections that are potentially in communication with deeper oil and gas sources. The application of the petroleum system model with the geochemical evidence suggests that gas hydrate deposits may be widespread across the North Slope of Alaska.

Characterization of methane-hydrate formation inferred from insitu Vp-density relationship for hydrate-bearing sediment cores obtained off the eastern coast of India

NASA Astrophysics Data System (ADS)

Kinoshita, M.; Hamada, Y.; Hirose, T.; Yamada, Y.

2017-12-01

In 2015, the Indian National Gas Hydrate Program (NGHP) Drilling Expedition 02 was carried out off the eastern margin of the Indian Peninsula in order to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. One of the target areas (area B) is located on the axial and flank of an anticline, where the BSR is identified 100 m beneath the summit of anticline. 3 sites were drilled in the crest. The lower potential hydrate zone II was suggested by downhole logging (LWD) at 270-290 m below seafloor across the top of anticline. Core samples from this interval is characterized by a higher natural gamma radiation, gamma-ray-based higher bulk density and lower porosity, and higher electrical resistivity. All these features are in good agreement with LWD results. During this expedition, numerous special core sampling operations (PCAT) were carried out, keeping its insitu pressure in a pressure-tight vessel. They enabled acquiring insitu P-wave velocity and gamma-ray attenuation density measurements. In-situ X-CT images exhibit very clear hydrate distribution as lower density patches. Hydrate-bearing sediments exhibit a Vp-density trend that is clearly different from the ordinary formation. Vp values are significantly higher than 2 km/s whereas the density remains constant at 2-2.2 g/cm3 in hydrate zones. At some hydrate-bearing sediments, we noticed that Vp is negatively correlated to the density in the deeper portion (235-285 mbsf). On the other hand, in the shallower portion they are positively correlated. From lithostratigraphy the shallower portion consists of sand, whereas deeper portion are silty-clay dominant. We infer that the sand-dominant, shallower hydrate is a pore-filling type, and Vp is correlated positively to density. On the other hand, the clay-dominant, deeper hydrate is filled in vertical veins, and Vp is negatively correlated to density. Negative correlation may be explained by a (partial) replacement of pore water with hydrate because the density of hydrate is lower than the water.

Volatile generation in bell peppers during frozen storage and thawing using selected ion flow tube mass spectrometry (SIFT-MS).

PubMed

Wampler, Brendan; Barringer, Sheryl A

2012-06-01

To determine volatile formation during storage and thawing, whole, pureed, blanched, and raw green and red bell peppers (Capsicum annuum) were frozen quickly or slowly then stored at -18 °C for up to 7 mo, with and without SnCl(2) addition during thawing. Headspace analysis was performed by a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). After blanching, (Z)-3-hexenal had a large significant decrease in concentration since it is a heat labile compound while most other volatiles did not change in concentration. The freezing process increased volatile levels in the puree only. Slow freeze peppers had higher levels of some LOX generated volatiles during storage than quick freeze. During frozen storage of blanched samples (E)-2-hexenal, (Z and E)-hexen-1-ol, and (E)-2-pentenal increased likely because of nonenzymatic autoxidation of fatty acids while other volatiles remained constant. In Raw Whole peppers, (Z)-3-hexenal, hexanal, and 2-pentylfuran were generated during storage likely because the LOX enzyme is still active during frozen storage. However, blanched samples had higher concentrations of (E)-2-hexenal, (Z and E)-hexen-1-ol, 1-penten-3-one, and (E)-2-heptenal because of enzymatic destruction of these volatiles in the raw samples. The levels of many of the volatiles in the raw samples, including (Z)-3-hexenal, (E)-2-hexenal, (Z and E)-hexen-1-ol, hexanal, (E)-2-pentenal, and 2-pentylfuran, appeared to peak around 34 d after freezing. Pureed samples had significantly higher levels of volatiles than the whole samples, and volatiles peaked earlier. Green bell pepper volatile levels were always higher than red bell pepper. Significantly higher volatile formation occurred during thawing than it did during frozen storage. Studying and monitoring the headspace volatiles with a SIFT-MS can give information that will help manufacturers better understand how the volatiles in bell peppers change during frozen storage. This will give valuable information to processors on how to minimize volatile changes during storage of frozen peppers. © 2012 Institute of Food Technologists®

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

Assessment of frozen storage duration effect on quality characteristics of various horse muscles.

PubMed

Seong, Pil Nam; Seo, Hyun Woo; Kim, Jin-Hyoung; Kang, Geun Ho; Cho, Soo-Hyun; Chae, Hyun Seok; Park, Beom Young; Van Ba, Hoa

2017-12-01

The study aimed at assessing the effects of frozen storage duration on quality characteristics, lipid oxidation and sensory quality of various horse muscles. Five representative muscles: longissimus dorsi (LD), gluteus medius (GM), semimembranosus (SM), biceps femoris (BF), and triceps brachii (TB) at 24 h post-mortem obtained from 28-mo-old Jeju female breed horses (n = 8) were used in the present investigation. The muscles were vacuum-packaged and frozen at -20°C for 120, 240, and 360 days. All the samples were analyzed for thawing and cooking losses, pH, Warner-Bratzler shear forces (WBSF), color traits, total volatile basic nitrogen (TVBN), thiobarbituric acid reactive substances (TBARS) and sensory traits. The muscle samples analyzed on day 0 of frozen storage (fresh, non-frozen) were used for comparison. Results revealed that thawing and cooking losses significantly (p<0.05) increased in all the muscles after 120 days and then remained unchanged up to 360 days of frozen storage. The TBARS and TVBN contents significantly increased as increasing frozen storage time up to 360 days (p<0.05). While, significant decreases in WBSF values were observed for all the muscles with increased frozen storage time (p<0.05). Frozen storage variously affected the color traits of the muscles for instance; the redness of LD, GM, and BF muscles showed a decreasing tendency during frozen storage while it was not changed in TB and SM muscles. Furthermore, the frozen storage did not produce detrimental effects on sensory quality as it did not cause flavor and juiciness defects whereas it partially improved the tenderness of all the muscles studied. Based on the results obtained from our work, it is concluded that frozen storage could be applied to increase the long-term shelf life of horsemeat while still retaining its sensory quality.

Inadequate Hydration, BMI, and Obesity Among US Adults: NHANES 2009-2012.

PubMed

Chang, Tammy; Ravi, Nithin; Plegue, Melissa A; Sonneville, Kendrin R; Davis, Matthew M

2016-07-01

Improving hydration is a strategy commonly used by clinicians to prevent overeating with the goal of promoting a healthy weight among patients. The relationship between weight status and hydration, however, is unclear. Our objective was to assess the relationship between inadequate hydration and BMI and inadequate hydration and obesity among adults in the United States. Our study used a nationally representative sample from the National Health and Nutrition Examination Survey (NHANES) 2009 to 2012, and included adults aged 18 to 64 years. The primary outcome of interest was body mass index (BMI), measured in continuous values and also categorized as obese (BMI ≥30) or not (BMI <30). Individuals with urine osmolality values of 800 mOsm/kg or greater were considered to be inadequately hydrated. Linear and logistic regressions were performed with continuous BMI and obesity status as the outcomes, respectively. Models were adjusted for known confounders including age, race/ethnicity, sex, and income-to-poverty ratio. In this nationally representative sample (n = 9,528; weighted n = 193.7 million), 50.8% were women, 64.5% were non-Hispanic white, and the mean age was 41 years. Mean urine osmolality was 631.4 mOsm/kg (SD = 236.2 mOsm/kg); 32.6% of the sample was inadequately hydrated. In adjusted models, adults who were inadequately hydrated had higher BMIs (1.32 kg/m(2); 95% CI, 0.85-1.79; P <.001) and higher odds of being obese (OR = 1.59; 95% CI, 1.35-1.88; P <.001) compared with hydrated adults. We found a significant association between inadequate hydration and elevated BMI and inadequate hydration and obesity, even after controlling for confounders. This relationship has not previously been shown on a population level and suggests that water, an essential nutrient, may deserve greater focus in weight management research and clinical strategies. © 2016 Annals of Family Medicine, Inc.

Quantitative Method for Analysis of Hydrocodone, Hydromorphone and Norhydrocodone in Human Plasma by Liquid Chromatography-tandem Mass Spectrometry

DTIC Science & Technology

2013-03-01

ratio ranges obtained for the six standards. Twelve samples were analyzed to demonstrate the efficiency of the extraction procedure. Drug and internal...frozen (−70 ◦C). Refrigerated samples were tested after 2 months of storage ; frozen samples were tested for up to 1 year from stor- age date. The...freeze–thaw stability was evaluated by analyzing three subject samples with known drug concentrations and two quality control samples at concentrations

Simultaneous measurement for thermal conductivity, diffusivity, and specific heat of methane hydrate bearing sediments recovered from Nankai-Trough wells

NASA Astrophysics Data System (ADS)

Muraoka, M.; Ohtake, M.; Susuki, N.; Yamamoto, Y.; Suzuki, K.; Tsuji, T.

2014-12-01

This study presents the results of the measurements of the thermal constants of natural methane-hydrate-bearing sediments samples recovered from the Tokai-oki test wells (Nankai-Trough, Japan) in 2004. The thermal conductivity, thermal diffusivity, and specific heat of the samples were simultaneously determined using the hot-disk transient method. The thermal conductivity of natural hydrate-bearing sediments decreases slightly with increasing porosity. In addition, the thermal diffusivity of hydrate-bearing sediment decrease as porosity increases. We also used simple models to calculate the thermal conductivity and thermal diffusivity. The results of the distribution model (geometric-mean model) are relatively consistent with the measurement results. In addition, the measurement results are consistent with the thermal diffusivity, which is estimated by dividing the thermal conductivity obtained from the distribution model by the specific heat obtained from the arithmetic mean. In addition, we discuss the relation between the thermal conductivity and mineral composition of core samples in conference. Acknowledgments. This work was financially supported by MH21 Research Consortium for Methane Hydrate Resources in Japan on the National Methane Hydrate Exploitation Program planned by the Ministry of Economy, Trade and Industry.

The characteristics of gas hydrates occurring in natural environment

NASA Astrophysics Data System (ADS)

Lu, H.; Moudrakovski, I.; Udachin, K.; Enright, G.; Ratcliffe, C.; Ripmeester, J.

2009-12-01

In the past few years, extensive analyses have been carried out for characterizing the natural gas hydrate samples from Cascadia, offshore Vancouver Island; Mallik, Mackenzie Delta; Mount Elbert, Alaska North Slope; Nankai Trough, offshore Japan; Japan Sea and offshore India. With the results obtained, it is possible to give a general picture of the characteristics of gas hydrates occurring in natural environment. Gas hydrate can occur in sediments of various types, from sands to clay, although it is preferentially enriched in sediments of certain types, for example coarse sands and fine volcanic ash. Most of the gas hydrates in sediments are invisible, occurring in the pores of the sediments, while some hydrates are visible, appearing as massive, nodular, planar, vein-like forms and occurring around the seafloor, in the fractures related to fault systems, or any other large spaces available in sediments. Although methane is the main component of most of the natural gas hydrates, C2 to C7 hydrocarbons have been recognized in hydrates, sometimes even in significant amounts. Shallow marine gas hydrates have been found generally to contain minor amounts of hydrogen sulfide. Gas hydrate samples with complex gas compositions have been found to have heterogeneous distributions in composition, which might reflect changes in the composition of the available gas in the surrounding environment. Depending on the gas compositions, the structure type of a natural gas hydrate can be structure I, II or H. For structure I methane hydrate, the large cages are almost fully occupied by methane molecules, while the small cages are only partly occupied. Methane hydrates occurring in different environments have been identified with almost the same crystallographic parameters.

Comparative atomic-scale hydration of the ceramide and phosphocholine headgroup in solution and bilayer environments

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

Gillams, Richard J.; McLain, Sylvia E., E-mail: sylvia.mclain@bioch.ox.ac.uk; Lorenz, Christian D., E-mail: chris.lorenz@kcl.ac.uk

2016-06-14

Previous studies have used neutron diffraction to elucidate the hydration of the ceramide and the phosphatidylcholine headgroup in solution. These solution studies provide bond-length resolution information on the system, but are limited to liquid samples. The work presented here investigates how the hydration of ceramide and phosphatidylcholine headgroups in a solution compares with that found in a lipid bilayer. This work shows that the hydration patterns seen in the solution samples provide valuable insight into the preferential location of hydrating water molecules in the bilayer. There are certain subtle differences in the distribution, which result from a combination of themore » lipid conformation and the lipid-lipid interactions within the bilayer environment. The lipid-lipid interactions in the bilayer will be dependent on the composition of the bilayer, whereas the restricted exploration of conformational space is likely to be applicable in all membrane environments. The generalized description of hydration gathered from the neutron diffraction studies thus provides good initial estimation for the hydration pattern, but this can be further refined for specific systems.« less

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.

Oxidative status of human milk and its variations during cold storage.

PubMed

Miranda, María; Muriach, María; Almansa, Inmaculada; Jareño, Enrique; Bosch-Morell, Francisco; Romero, Francisco J; Silvestre, Dolores

2004-01-01

Breastfeeding and human milk are widely accepted as optimal for human infants' nutrition. Nowadays lifestyle often makes it difficult to maintain or even initiate human lactation. This situation is mostly related to the workload of women away from home. New approaches are needed to enable maternal lactation under these circumstances. Human breastmilk storage for differed use is one possibility. The aim of this study was to assess changes in glutathione peroxidase (GPx) activity and in the concentration of the lipid peroxidation marker, malondialdehyde (MDA), when human milk was kept refrigerated or frozen. Thirty-two human milk samples were assayed for GPx activity and MDA concentration. Samples were divided in three aliquot portions, the first to be immediately analysed, the second to be refrigerated at 4 degrees C and analysed 24 h thereafter, and the third to be frozen at -20 degrees C and assayed after 10 days. GPx activity was significantly decreased in refrigerated and in frozen milk, when compared to their control samples. MDA was increased only in refrigerated milk but not in frozen samples. Thus, freezing seems better than refrigeration in order to prevent lipid peroxidation in stored human milk samples.

Oxidative stability of red palm oils blended chicken nuggets during frozen storage

NASA Astrophysics Data System (ADS)

Kamaruzaman, Nurkhuzaiah; Babji, Abdul Salam

2014-09-01

The effects of red palm oils known as Naturally Vitamin Rich Oil (NVRO) on the lipid stability of chicken nuggets were determined. Lipid oxidation was analyzed during frozen storage (-18 °C) for up to 4 months. Thiobarbituric acid (TBA) values and peroxide value (PV) for all samples chicken nuggets increased throughout 3 months of frozen storage and then start to decrease thereafter. Chicken nuggets formulated with NVRO, NVRO-100 and NVRO-50 showed lower TBA values and PV compared to the samples prepared with chicken fat. However, among NVRO, there were not significantly different for most of the months. It was concluded that the utilization of red palm oils in chicken nuggets significantly reduced the oxidation of lipid, which was indicated by the PV throughout 4 months of frozen storage.

System for maintaining materials at freezer temperatures for shipping

DOEpatents

Schabron, John F [Laramie, WY; Sorini-Wong, Susan S [Laramie, WY

2007-08-28

At least one embodiment of the inventive technology relates to a frozen environmental sample temperature control system that comprises a frozen formulation having water in an amount from substantially 87% to 78% by weight of the formulation, and salt in an amount from substantially 13% to 22% by weight of the formulation, the system further including at least one container containing the frozen formulation; and a cooler having insulating material disposed between an outer wall and an inner surface that defines an inner chamber into which the at least one container and the at least one frozen environmental sample may be placed for storage and/or transport. Various embodiments may incorporate specific types of insulating material and/or adaptations to an inner surface of the cooler to enhance the insulation effected thereby.

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

PubMed Central

Sparrow, Katy J.; Kessler, John D.; Southon, John R.; Garcia-Tigreros, Fenix; Schreiner, Kathryn M.; Ruppel, Carolyn D.; Miller, John B.; Lehman, Scott J.; Xu, Xiaomei

2018-01-01

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon–sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere. PMID:29349299

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

USGS Publications Warehouse

Sparrow, Katy J.; Kessler, John D.; Southon, John R.; Garcia-Tigreros, Fenix; Schreiner, Kathryn M.; Ruppel, Carolyn D.; Miller, John B.; Lehman, Scott J.; Xu, Xiaomei

2018-01-01

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon–sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere.

Indication and method of frozen section in vaginal radical trachelectomy.

PubMed

Chênevert, Jacinthe; Têtu, Bernard; Plante, Marie; Roy, Michel; Renaud, Marie-Claude; Grégoire, Jean; Grondin, Katherine; Dubé, Valérie

2009-09-01

Vaginal radical trachelectomy (VRT) is a fertility-sparing surgical technique used as an alternative to radical hysterectomy in early stage cervical carcinoma. With the advent of VRT, preoperative evaluation of the surgical margin has become imperative, because if the tumor is found within 5 mm of the endocervical margin, additional surgical resection is required. In a study published earlier from our center, we came to the conclusion that a frozen section should be conducted only when a cancerous lesion is grossly visible, and that it could be omitted in normal-looking specimens or VRT with nonspecific lesions. Since then, 53 VRT have been performed in our center, and frozen sections were conducted according to these recommendations. Fifteen VRT were grossly normal, 24 had a nonspecific lesion and 14 showed a grossly visible lesion. Final margins were satisfactory on all 15 grossly normal specimens. Of the 24 VRT with nonspecific lesions, 2 cases for which no frozen section was performed had unsatisfactory final margins (<5 mm). Of the 14 VRT with grossly visible lesions, 3 cases were inadequately evaluated by frozen section due to sampling errors, which led to unsatisfactory final margin assessment. These results confirm that a frozen section can be omitted on normal looking VRT specimens, but contrary to results published earlier, we recommend that a frozen section be performed on all VRT with nonspecific lesions. As for VRT with a grossly visible lesion, frozen section evaluation is still warranted, and we recommend increasing the sampling to improve the adequacy of frozen sections.

Comparative performance of isolation methods using Preston broth, Bolton broth and their modifications for the detection of Campylobacter spp. from naturally contaminated fresh and frozen raw poultry meat.

PubMed

Seliwiorstow, T; De Zutter, L; Houf, K; Botteldoorn, N; Baré, J; Van Damme, I

2016-10-03

The performance of different isolation methods was evaluated for the detection of Campylobacter from naturally contaminated raw poultry meat. Therefore, fresh and frozen poultry meat samples were analysed using the standard procedure (ISO 10272-1:2006), enrichment in Preston broth, and enrichment in modified Bolton broth (supplemented with (i) potassium clavulanate (C-BB), (ii) triclosan (T-BB), (iii) polymyxin B (P-BB)). The enrichment cultures were streaked onto both modified charcoal cefoperazone deoxycholate agar (mCCDA) and RAPID'Campylobacter agar (RCA). Moreover, direct plating on mCCDA and RCA was performed to quantify Campylobacter. In total, 33 out of 59 fresh retail meat samples (55.9%) were Campylobacter positive. For both fresh and frozen poultry meat samples, enrichment in Bolton broth (ISO 10272-1:2006) resulted in a higher number of positive samples than enrichment in Preston broth. Supplementation of Bolton broth with potassium clavulanate (C-BB) and triclosan (T-BB) enhanced the Campylobacter recovery from fresh poultry meat compared to non-supplemented Bolton broth, although the use of C-BB was less applicable than T-BB for Campylobacter recovery from frozen samples. Additionally, the use of RCA resulted in a higher isolation rate compared to mCCDA. The present study demonstrates the impact of culture medium on the recovery of Campylobacter from fresh and frozen naturally contaminated poultry meat samples and can support laboratories in choosing the most appropriate culturing method to detect Campylobacter. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydrated Minerals and Evaporites as Key Targets for a Mars Sample Return Mission

NASA Astrophysics Data System (ADS)

Adeli, S.; Hauber, E.; Jaumann, R.

2018-04-01

Here we focus on hydrated minerals and evaporites as paleo-environment indicators with preservation capacity. Thus, samples from these materials would increase our knowledge about the past aqueous activities of Mars and its habitability potentials.

A Study of Moisture Sorption and Dielectric Processes of Starch and Sodium Starch Glycolate : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Hiew, Tze Ning; Huang, Rongying; Popov, Ivan; Feldman, Yuri; Heng, Paul Wan Sia

2017-12-01

This study explored the potential of combining the use of moisture sorption isotherms and dielectric relaxation profiles of starch and sodium starch glycolate (SSG) to probe the location of moisture in dried and hydrated samples. Starch and SSG samples, dried and hydrated, were prepared. For hydrated samples, their moisture contents were determined. The samples were probed by dielectric spectroscopy using a frequency band of 0.1 Hz to 1 MHz to investigate their moisture-related relaxation profiles. The moisture sorption and desorption isotherms of starch and SSG were generated using a vapor sorption analyzer, and modeled using the Guggenheim-Anderson-de Boer equation. A clear high frequency relaxation process was detected in both dried and hydrated starches, while for dried starch, an additional slower low frequency process was also detected. The high frequency relaxation processes in hydrated and dried starches were assigned to the coupled starch-hydrated water relaxation. The low frequency relaxation in dried starch was attributed to the local chain motions of the starch backbone. No relaxation process associated with water was detected in both hydrated and dried SSG within the frequency and temperature range used in this study. The moisture sorption isotherms of SSG suggest the presence of high energy free water, which could have masked the relaxation process of the bound water during dielectric measurements. The combined study of moisture sorption isotherms and dielectric spectroscopy was shown to be beneficial and complementary in probing the effects of moisture on the relaxation processes of starch and SSG.

Colloid centrifugation of fresh stallion semen before cryopreservation decreased microorganism load of frozen-thawed semen without affecting seminal kinetics.

PubMed

Guimarães, T; Lopes, G; Pinto, M; Silva, E; Miranda, C; Correia, M J; Damásio, L; Thompson, G; Rocha, A

2015-01-15

Freezability of equine semen may be influenced by microorganism population of semen. The objective of this study was to verify the effect of single-layer density gradient centrifugation (SLC) of fresh semen before cryopreservation on semen's microbial load (ML) and sperm cells kinetics after freezing-thawing. For that, one ejaculate was collected from 20 healthy stallions and split into control (C) samples (cryopreserved without previous SLC) and SLC samples (subjected to SLC). Semen cryopreservation was performed according to the same protocol in both groups. Microbial load of each microorganism species and total microbial load (TML) expressed in colony-forming units (CFU/mL) as well as frozen-thawed sperm kinetics were assessed in both groups. Additional analysis of the TML was performed, subdividing the frozen-thawed samples in "suitable" (total motility ≥ 30%) and "unsuitable" (total motility < 30%) semen for freezing programs, and comparing the C and SLC groups within these subpopulations. After thawing, SLC samples had less (P < 0.05) TML (88.65 × 10(2) ± 83.8 × 10(2) CFU/mL) than C samples (155.69 × 10(2) ± 48.85 × 10(2) CFU/mL), mainly due to a reduction of Enterococcus spp. and Bacillus spp. A relationship between post-thaw motility and SLC effect on ML was noted, as only in samples with more than 30% total motility was ML reduced (P < 0.05) by SLC (from 51.33 × 10(2) ± 33.26 × 10(2) CFU/mL to 26.68 × 10(2) ± 12.39 × 10(2) CFU/mL in "suitable" frozen-thawed semen vs. 240.90 × 10(2) ± 498.20 × 10(2) to 139.30 × 10(2) ± 290.30 × 10(2) CFU/mL in "unsuitable" frozen-thawed semen). The effect of SLC on kinetics of frozen-thawed sperm cells was negligible. Copyright © 2015 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Global Assessment of Methane Gas Hydrates: Outreach for the public and policy makers

NASA Astrophysics Data System (ADS)

Beaudoin, Yannick

2010-05-01

The United Nations Environment Programme (UNEP), via its official collaborating center in Norway, GRID-Arendal, is in the process of implementing a Global Assessment of Methane Gas Hydrates. Global reservoirs of methane gas have long been the topic of scientific discussion both in the realm of environmental issues such as natural forces of climate change and as a potential energy resource for economic development. Of particular interest are the volumes of methane locked away in frozen molecules known as clathrates or hydrates. Our rapidly evolving scientific knowledge and technological development related to methane hydrates makes these formations increasingly prospective to economic development. In addition, global demand for energy continues, and will continue to outpace supply for the foreseeable future, resulting in pressure to expand development activities, with associated concerns about environmental and social impacts. Understanding the intricate links between methane hydrates and 1) natural and anthropogenic contributions to climate change, 2) their role in the carbon cycle (e.g. ocean chemistry) and 3) the environmental and socio-economic impacts of extraction, are key factors in making good decisions that promote sustainable development. As policy makers, environmental organizations and private sector interests seek to forward their respective agendas which tend to be weighted towards applied research, there is a clear and imminent need for a an authoritative source of accessible information on various topics related to methane gas hydrates. The 2008 United Nations Environment Programme Annual Report highlighted methane from the Arctic as an emerging challenge with respect to climate change and other environmental issues. Building upon this foundation, UNEP/GRID-Arendal, in conjunction with experts from national hydrates research groups from Canada, the US, Japan, Germany, Norway, India and Korea, aims to provide a multi-thematic overview of the key aspects of the current methane hydrate debate for both the land-based Arctic deposits and those in the marine environment. The Global Assessment of Methane Gas Hydrates will consist in: 1. An electronic publication (e-book) which would have the advantages over a printed publication of broad exposure and ease of distribution, as well as being easier to update. This medium allows for dynamic graphics, interactive figures and multimedia content. An example e-book produced by UNEP/GRID-Arendal can be viewed at www.grida.no/publications/vg/kick/ebook.aspx . 2. A limited printing of a hardcopy version is also proposed, for distribution to policy makers and to targeted stakeholders. 3. A dedicated hydrates web portal containing the latest scientific research results in a format accessible to decision makers, the general public and the media. Versatile web applications, interactive, dynamic visualization tools and dedicated evolving indicators are all tools proposed to be included in the portal. This tool is planned to allow for research scientists to update outputs with new data and is meant as a long term repository of scientific knowledge of global methane gas hydrates.

Hydration reactivity of crystalline and vitrified diopside under hydrothermal conditions

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

Grzeszczyk, S.; Szuba, J.

1990-07-01

Hydration reactivity of diopside in both the crystalline and amorphous (glassy) phase was studied under hydrothermal conditions. Samples were treated in an autoclave at 200{degrees}C in saturated vapor for 24 and 72 h. The progress of hydration was determined by X-ray powder diffractometry and IR spectroscopy. Results indicate that crystalline diopside possessed poor hydraulic activity. However, once vitrified it proved to be much more reactive. The principal hydration products found for the glassy diopside after 24 and 72 h of treatment were calcium silicate hydrate (xonotlite) and magnesium silicate hydrates (chrysotile and tremolite).

The use of microgravity to study phototropism-the TROPI experiments on the ISS

NASA Astrophysics Data System (ADS)

Kiss, John Z.; Kumar, Prem; Correll, Melanie; Edelmann, Richard

On Earth, it is very difficult to study the interacting effects of gravity and other stimuli such as light on plant growth. However, a project termed TROPI (for tropisms) was performed to examine these interactions in seedlings of Arabidopsis thaliana that were grown on the International Space Station (ISS). A major goal of these experiments was to gain insights into the cellular and molecular mechanisms of phototropism, the directed growth of plants in response to light. TROPI utilized the EMCS (European Modular Cultivation System) which has an incubator, lighting, high-resolution video and two centrifuge platforms so that experiments were conducted at µg, 1g (control), and fractional g-levels during ISS Increment 14 from October to December 2006. Dry seeds of the wild type (Landsberg strain) along with the phytochrome mutants phyA, phyB, and phyAB were used in these studies. The experiments were started by the automated hydration of seeds using hardware specially designed for these experiments. The time line consisted of a growth phase and a stimulation phase in which seedlings received unilateral red or blue illumination. At the end of the experiments, an astronaut placed the seedlings in an on-orbit -80° C degree freezer. The data obtained from TROPI consisted of video observations of seedlings and frozen specimens which are being used in microarray studies to monitor gene expression changes in the different light and gravity treatments. Video tapes and frozen samples were returned on three space shuttle missions in 2007, and we are in the process of analyzing the data from both types of experiments. This paper will focus on growth and phototropism of seedlings in response to blue and red light.

The Lithological Constraint To Gas Hydrate Formation: Evidence OF Grain Size Of Sediments From IODP 311 On CASCADIA Margin

NASA Astrophysics Data System (ADS)

Wang, J.

2006-12-01

A total of 614 sediment samples at intervals of about 1.5 m from all 5 sites of the Integrated Ocean Drilling Program (IODP) Expedition 311 on Cascadia Margin were analyzed using a Beckman Coulter LS-230 Particle Analyzer. The grain-size data were then plotted in depth and compared with other proxies of gas hydrate- occurrence such as soupy/mousse-like structures in sediments, gas hydrate concentration (Sh) derived from LWD data using Archie's relation, IR core images (infrared image) and the recovered samples of gas hydrate¨Cbearing sediments. A good relationship between the distribution of coarse grains in size of 31-63¦Ìm and 63-125¦Ìm sediments and the potential occurrence of gas hydrate was found across the entire gas hydrate stability zone. The depth distribution of grain size from the Site U1326 shows clear excursions at depths of 5-8, 21-26, 50- 123, 132-140, 167-180, 195-206 and 220-240 mbsf, which coincide with the potential occurrence of gas hydrate suggested by soupy/mousse-like structures, logging-derived gas hydrate concentrations (Sh) and the recovered samples of the gas hydrate¨Cbearing sand layers. The lithology of sediments significantly affects the formation of gas hydrate. Gas hydrate forms preferentially within relatively coarse grain-size sediments above 31 ¦Ìm. Key words: grain size of sediments, constraint, occurrence of gas hydrate, IODP 311 IODP Expedition 311 Scientists: Michael Riedel (Co-chief Scientist), Timothy S. Collett (Co-chief Scientist), Mitchell Malone (Expedition Project Manager/Staff Scientist), Gilles Gu¨¨rin, Fumio Akiba, Marie-Madeleine Blanc-Valleron, Michelle Ellis, Yoshitaka Hashimoto, Verena Heuer, Yosuke Higashi, Melanie Holland, Peter D. Jackson, Masanori Kaneko, Miriam Kastner, Ji-Hoon Kim, Hiroko Kitajima, Philip E. Long, Alberto Malinverno, Greg Myers, Leena D. Palekar, John Pohlman, Peter Schultheiss, Barbara Teichert, Marta E. Torres, Anne M. Tr¨¦hu, Jiasheng Wang, Ulrich G. Wortmann, Hideyoshi Yoshioka. Acknowledgement: This study was supported by the IODP/JOI Alliance, IODP-China 863 Project (grant 2004AA615030) and NSFC Project (grant 40472063).

TL and ESR based identification of gamma-irradiated frozen fish using different hydrolysis techniques

NASA Astrophysics Data System (ADS)

Ahn, Jae-Jun; Akram, Kashif; Shahbaz, Hafiz Muhammad; Kwon, Joong-Ho

2014-12-01

Frozen fish fillets (walleye Pollack and Japanese Spanish mackerel) were selected as samples for irradiation (0-10 kGy) detection trials using different hydrolysis methods. Photostimulated luminescence (PSL)-based screening analysis for gamma-irradiated frozen fillets showed low sensitivity due to limited silicate mineral contents on the samples. Same limitations were found in the thermoluminescence (TL) analysis on mineral samples isolated by density separation method. However, acid (HCl) and alkali (KOH) hydrolysis methods were effective in getting enough minerals to carry out TL analysis, which was reconfirmed through the normalization step by calculating the TL ratios (TL1/TL2). For improved electron spin resonance (ESR) analysis, alkali and enzyme (alcalase) hydrolysis methods were compared in separating minute-bone fractions. The enzymatic method provided more clear radiation-specific hydroxyapatite radicals than that of the alkaline method. Different hydrolysis methods could extend the application of TL and ESR techniques in identifying the irradiation history of frozen fish fillets.

Electrical conductivity of lab-formed methane hydrate + sand mixtures; technical developments and new results

NASA Astrophysics Data System (ADS)

Stern, L.; Du Frane, W. L.; Weitemeyer, K. A.; Constable, S.; Roberts, J. J.

2012-12-01

Electromagnetic (EM) measurement techniques used in permafrost and marine wells show that electrical conductivity (σ) of gas-hydrate-bearing zones is typically lower than that of surrounding sediments. However, while σ has been measured on analogue materials, it has seldom been studied on methane hydrate, the most common gas hydrate in the shallow geosphere. Additional petrophysical information - such as mixing relations and/or compositions of individual components - is also needed to more accurately relate σ to quantitative estimates of gas hydrate in EM-surveyed regions. To help address these needs, we first quantified the electrical properties of lab-formed methane hydrate at geologically relevant temperatures and pressures (Du Frane et al. GRL, 2011; also AGU 2011). A high-pressure cell was constructed to form hydrate from melting granular ice (made from distilled-deionized water) in the presence of pressurized CH4 gas, while measuring frequency-dependent impedance (Z) and σ. Final samples were pure, polycrystalline methane hydrate with excess CH4 gas but no excess H2O. The hydrate was then either quenched for grain-scale assessment by cryogenic SEM imaging, or dissociated in situ for further Z and σ measurement. Du Frane et al. [GRL, 2011] reported σ of methane hydrate to range from 10-5 to 10-4 S/m between -15 and 15°C, with activation energy (Ea) of 30.6 kJ/mol. In comparison, σ of the dissociated ice byproduct was ~400% higher with ~50% higher Ea. Measurements were then performed on methane hydrate mixed with known amounts of a standard quartz sand (Oklahoma #1, ~125 μm grain size) or similarly-sized silica glass beads in proportions ranging 10 to 90 vol. % relative to the hydrate phase. Several samples were dissociated at temperatures below -3°C for Z and σ measurement of the resulting ice/sand mixtures, and all samples were imaged for phase distribution. Adding sand complicated Z spectra for frequencies < 1 kHz and > 1MHz. However, the impedance at the frequency associated with the highest phase angle (typically 100 kHz) could be used to effectively isolate the electrical response of the sample from system contributions, enabling determination of σ. Surprisingly, the addition of sand, a nominal insulator, served to increase the overall σ of mixtures with sand fractions up through ~50 vol. % (i.e. those samples with well-connected methane hydrate), while Ea significantly decreased relative to single-phase methane hydrate. The reduced Ea suggests that a separate conduction mechanism operates when sand is present. One possible explanation is that ionic impurities from sand surfaces chemically diffuse into the hydrate grains, increasing their concentration of mobile charge-carrying defects. The fact that the addition of glass beads did not produce the same results supports this hypothesis. Geometrical mixing laws alone may therefore not sufficiently describe complicated mixing relationships between gas hydrate and sediment. Further tests are needed to resolve the competing effects, particularly if results are to be applied to systems that are not dominated by the presence of seawater. Work was performed under the auspices of U.S. DOE contracts DE-NT0005668 and DE-AC52-07NA27344, and DOE/USGS Interagency Agreement DE-NT0006147.

Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation

NASA Astrophysics Data System (ADS)

Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J.; Kusalik, Peter G.; Ciccotti, Giovanni

2015-06-01

For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ˜80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs.

Challenges, uncertainties, and issues facing gas production from gas-hydrate deposits

USGS Publications Warehouse

Moridis, G.J.; Collett, T.S.; Pooladi-Darvish, M.; Hancock, S.; Santamarina, C.; Boswel, R.; Kneafsey, T.; Rutqvist, J.; Kowalsky, M.B.; Reagan, M.T.; Sloan, E.D.; Sum, A.K.; Koh, C.A.

2011-01-01

The current paper complements the Moridis et al. (2009) review of the status of the effort toward commercial gas production from hydrates. We aim to describe the concept of the gas-hydrate (GH) petroleum system; to discuss advances, requirements, and suggested practices in GH prospecting and GH deposit characterization; and to review the associated technical, economic, and environmental challenges and uncertainties, which include the following: accurate assessment of producible fractions of the GH resource; development of methods for identifying suitable production targets; sampling of hydrate-bearing sediments (HBS) and sample analysis; analysis and interpretation of geophysical surveys of GH reservoirs; well-testing methods; interpretation of well-testing results; geomechanical and reservoir/well stability concerns; well design, operation, and installation; field operations and extending production beyond sand-dominated GH reservoirs; monitoring production and geomechanical stability; laboratory investigations; fundamental knowledge of hydrate behavior; the economics of commercial gas production from hydrates; and associated environmental concerns. ?? 2011 Society of Petroleum Engineers.

Comparison of techniques for stabilizing hemoglobins of rainbow trout (Salmo gairdneri) during frozen storage

USGS Publications Warehouse

Reinitz, G.L.

1976-01-01

1. The stability of hemoglobin of rainbow trout under frozen conditions in oxyform, carboxyform, and cyanometform was examined.2. Carboxyhemoglobin retained its original electrophoretic banding pattern after 14 days of frozen storage, whereas oxyform and cyanometform hemoglobins did not.3. Banding patterns changed in some samples in all treatment groups after 21 days of storage.

Prevalence of Listeria spp and Listeria monocytogenes in meat and fermented fish in Malaysia.

PubMed

Hassan, Z; Purwati, E; Radu, S; Rahim, R A; Rusul, G

2001-06-01

Fermented fish and meat samples were purchased from supermarket and wet market for microbiological analysis of Listeria species and Listeria monocytogenes contamination. Listeria species were isolated from 17 (73.9%) of 23 samples of imported frozen beef, 10 (43.5%) of the 23 samples of local beef and 14 (56%) of the 25 samples of fermented fish from wet market. Listeria monocytogenes occurred in 15 (75%) of the frozen beef samples, 6 (30.4%) of the 23 samples of local meat and 3 (12%) of the 25 samples from fermented fish. Listeria species was not isolated from any of the 23 samples of imported frozen beef from supermarket and from the 5 samples of buffalo meat examined. This highlights the possibility of Listeria spp or L. monocytogenes to persist in meat and fermented fish in wet market and raises the problem of illness due to the handling and consumption of Listeria-contaminated meat or fermented fish are likely as evidence by the high contamination rates of samples sold at the wet market.

Effect of ELISA kit manufacturing process and incubation time on progesterone concentration measured in dog serum for ovulation diagnosis - Short communication.

PubMed

Thuróczy, Julianna; Reiczigel, Jenő; Balogh, Lajos

2016-09-01

Twenty-two serum samples of healthy bitches were tested with the frozen and lyophilised version of the same ELISA kit (Quanticheck, Faculty of Veterinary Science, Budapest, Hungary). Samples were chosen on the basis of their progesterone (P4) concentrations, which were between 1.00 and 20.00 ng/mL. As it is well known, this range has the highest clinical relevance in ovulation diagnosis. Both types of microplates were read at 15-min intervals from the 15th until the 90th minute (min) of incubation, and the results were compared with those of frozen plates at 60 min of incubation as 100 percent. Lyophilised microplates gave on average 18 percent higher results than the frozen version at equal incubation times. The highest difference between lyophilised and frozen samples was observed at 45 and 60 min of incubation. Ninety-four percent of the reaction in the frozen microplate occurred in the first 15 min, and during the subsequent 30 min the reaction seemingly stopped. After the 45th min of incubation, this 94 percent increased to 108 percent in the subsequent 30 min, which remained the final approximate result at the end of the 90 min of incubation. In contrast to the frozen microplate, the measured concentration increased continuously in the lyophilised version and reached the highest level at the 60th min. The results of the lyophilised microplate reached the same level at 30 min of incubation as those of the frozen version at 60 min. In conclusion, a mechanical increase or decrease of the incubation time does not generate a linear change in the test results. This study demonstrated that the results of a series of samples collected from the same bitch cannot be compared if they are measured with different laboratory methods or different ELISA kits.

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

USGS Publications Warehouse

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

1998-01-01

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

Molecular and isotopic analyses of the hydrocarbon gases within gas hydrate-bearing rock units of the Prudhoe Bay-Kuparuk River area in northern Alaska

USGS Publications Warehouse

Valin, Zenon C.; Collett, Timothy S.

1992-01-01

Gas hydrates, which are crystalline substances of water molecules that encase gas molecules, have the potential for being a significant source of natural gas. World-wide estimates for the amount of gas contained in hydrates range from 1.1 x 105 to 2.7 x 108 trillion cubic feet. Gas hydrates exist in many Arctic regions, including the North Slope of Alaska. The two primary objectives of the U.S. Geological Survey Gas Hydrate Research Project are (1) to map the distribution of in-situ gas hydrates on the North Slope of Alaska, and (2) to evaluate the geologic parameters that control the distribution of these gas hydrates. To aid in this study, British Petroleum Exploration, ARCO Alaska, Exxon Company USA, and the Continental Oil Company allowed the U.S. Geological Survey to collect geochemical samples from drilling North Slope production wells. Molecular analysis of gaseous drill cutting and free-flowing gas samples from 10 production wells drilled in the Prudhoe Bay, Kuparuk River, and Milne Point oil fields indicates that methane is the primary hydrocarbon gas in the gas hydrate-bearing stratigraphic units. Isotopic data for several of these rock units indicate that the methane within the inferred gas hydrate occurences originated from both microbial and thermogenic processes.

Freeze chromatography method and apparatus

DOEpatents

Scott, C.D.

1987-04-16

A freeze chromatography method and apparatus are provided which enable separation of the solutes contained in a sample. The apparatus includes an annular column construction comprising cylindrical inner and outer surfaces defining an annular passage therebetween. One of the surfaces is heated and the other cooled while passing an eluent through the annular passageway so that the eluent in contact with the cooled surface freezes and forms a frozen eluent layer thereon. A mixture of solutes dissolved in eluent is passed through the annular passageway in contact with the frozen layer so that the sample solutes in the mixture will tend to migrate either toward or away the frozen layer. The rate at which the mixture flows through the annular passageway is controlled so that the distribution of the sample solutes approaches that at equilibrium and thus a separation between the sample solutes occurs. 3 figs.

[Adaptability of sweet corn ears to a frozen process].

PubMed

Ramírez Matheus, Alejandra O; Martínez, Norelkys Maribel; de Bertorelli, Ligia O; De Venanzi, Frank

2004-12-01

The effects of frozen condition on the quality of three sweet corn ears (2038, 2010, 2004) and the pattern (Bonanza), were evaluated. Biometrics characteristics like ear size, ear diameter, row and kernel deep were measured as well as chemical and physical measurement in fresh and frozen states. The corn ears were frozen at -95 degrees C by 7 minutes. The yield and stability of the frozen ears were evaluated at 45 and 90 days of frozen storage (-18 degrees C). The average commercial yield as frozen corn ear for all the hybrids was 54.2%. The industry has a similar value range of 48% to 54%. The ear size average was 21.57 cm, row number was 15, ear diameter 45.54 mm and the kernel corn deep was 8.57 mm. All these measurements were found not different from commercial values found for the industry. All corn samples evaluated showed good stability despites the frozen processing and storage. Hybrid 2038 ranked higher in quality.

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

PubMed

Ellis, P R; Morris, E R

1991-05-01

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

UT-GOM2-1: Prospecting, Drilling and Sampling a Coarse-Grained Hydrate Reservoir in Green Canyon 955, the Deepwater Gulf of Mexico

NASA Astrophysics Data System (ADS)

Flemings, P. B.; Phillips, S. C.

2017-12-01

In May 2017, a science team led by the University of Texas-Austin conducted drilling and coring operations from the Helix Q4000 targeting gas hydrates in sand-rich reservoirs in the Green Canyon 955 block in the northern Gulf of Mexico. The UT-GOM2-1 expedition goals were to 1) test two configurations of pressure coring devices to assess relative performance with respect to recovery and quality of samples and 2) gather sufficient samples to allow laboratories throughout the US to investigate a range of outstanding science questions related to the origin and nature of gas hydrate-bearing sands. In the first well (UT-GOM2-1-H002), 1 of the 8 cores were recovered under pressure with 34% recovery. In the second well (UT-GOM2-1-H005), 12 of 13 cores were recovered under pressure with 77% recovery. The pressure cores were imaged and logged under pressure. Samples were degassed both shipboard and dockside to interpret hydrate concentration and gas composition. Samples for microbiological and porewater analysis were taken from the depressurized samples. 21 3 ft pressure cores were returned to the University of Texas for storage, distribution, and further analysis. Preliminary analyses document that the hydrate-bearing interval is composed of two interbedded (cm to m thickness) facies. Lithofacies II is composed of sandy silt and has trough cross bedding whereas Lithofacies III is composed of clayey silt and no bedforms are observed. Lithofacies II has low density (1.7 to 1.9 g/cc) and high velocity (3000-3250 m/s) beds whereas Lithofacies 3 has high density ( 1.9-2.1g/cc) and low velocity ( 1700 m/s). Quantitative degassing was used to determine that Lithofacies II contains high hydrate saturation (66-87%) and Lithofacies III contains moderate saturation ( 18-30%). Gas samples were analyzed periodically in each experiment and were composed of primarily methane with an average of 94 ppm ethane and detectable, but not quantifiable, propane. The core data will provide a foundation for scientific exploration by the greater hydrate research community.

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

NASA Astrophysics Data System (ADS)

Holtzman, R.; Juanes, R.

2009-12-01

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

Frozen and fresh ovarian tissue require different culture media to promote in vitro development of bovine preantral follicles.

PubMed

Castro, Simone Vieira; Carvalho, Adeline Andrade; Silva, Cleidson Manoel Gomes; Santos, Francielli Weber; Campello, Cláudio Cabral; de Figueiredo, José Ricardo; Rodrigues, Ana Paula Ribeiro

2014-10-01

The aim of this study was to evaluate the efficiency of different media in the in vitro culture of bovine preantral follicles that were used either fresh or following slow freezing treatment. Frozen and fresh noncultured or cultured ovarian fragments were processed for histological, viability, and cell proliferation analyses. For cryopreservation, a solution containing 1.5 M ethylene glycol was frozen in a programmable biological freezer. After thawing, a portion of the samples was destined for frozen controls. The remainder were cultured in vitro for 5 days in three media: α-MEM, McCoy, or M199. Samples from these culture media were collected on days 1 and 5 for quantification of reactive oxygen species (ROS) and for hormonal assays. In fresh-cultured tissues, the percentage of morphologically normal follicles was significantly higher when cultured in M199 compared to that in the other media. In frozen-cultured tissues, McCoy medium was significantly superior to the other media, and was the only treatment that helped in maintaining the viability similar to fresh and frozen controls. Upon quantification of the nucleolus organizer region, we observed greater proliferation of granulosa cells in the frozen-cultured tissues with McCoy medium, and lesser proliferation in fresh-cultured tissues only with α-MEM. In frozen-cultured tissues, ROS levels were highest at day 1 and progressively reduced during culture, independent of the media used. In conclusion, under the conditions used in this study, the M199 and McCoy media are recommended for the culture of follicles derived from fresh and frozen ovarian tissues, respectively.

Effect of freezing, irradiation, and frozen storage on survival of Salmonella in concentrated orange juice.

PubMed

Niemira, Brendan A; Sommers, Christopher H; Boyd, Glenn

2003-10-01

Six strains of Salmonella (Anatum F4317, Dublin 15480, Enteritidis 13076, Enteritidis WY15159, Stanley H0588, and Typhimurium 14028) were individually inoculated into orange juice concentrate (OJC) and frozen to -20 degrees C. The frozen samples were treated with 0 (nonirradiated), 0.5, 1.0, or 2.0 kGy of gamma radiation and held frozen for 1 h, and the surviving bacterial population was assessed. The strains showed significant variability in their response to freezing and to freezing in combination with irradiation. The response was dose dependent. Relative to the nonfrozen, nonirradiated control, the reduction following the highest dose (2.0 kGy) ranged from 1.29 log CFU/ml (Salmonella Typhimurium) to 2.17 log CFU/ml (Salmonella Stanley). Samples of OJC inoculated with Salmonella Enteritidis WY15159 and irradiated were stored at -20 degrees C for 1, 2, 7, or 14 days, and the surviving population was determined. Relative to the nonfrozen, nonirradiated control, after 14 days, the population was reduced by 1.2 log CFU/ml in the nonirradiated samples and by 3.3 log CFU/ml following treatment with 2.0 kGy. The combination of frozen storage plus irradiation resulted in greater overall reductions than either process alone.

Binary effect of fly ash and palm oil fuel ash on heat of hydration aerated concrete.

PubMed

Mehmannavaz, Taha; Ismail, Mohammad; Radin Sumadi, Salihuddin; Rafique Bhutta, Muhammad Aamer; Samadi, Mostafa; Sajjadi, Seyed Mahdi

2014-01-01

The binary effect of pulverized fuel ash (PFA) and palm oil fuel ash (POFA) on heat of hydration of aerated concrete was studied. Three aerated concrete mixes were prepared, namely, concrete containing 100% ordinary Portland cement (control sample or Type I), binary concrete made from 50% POFA (Type II), and ternary concrete containing 30% POFA and 20% PFA (Type III). It is found that the temperature increases due to heat of hydration through all the concrete specimens especially in the control sample. However, the total temperature rises caused by the heat of hydration through both of the new binary and ternary concrete were significantly lower than the control sample. The obtained results reveal that the replacement of Portland cement with binary and ternary materials is beneficial, particularly for mass concrete where thermal cracking due to extreme heat rise is of great concern.

Binary Effect of Fly Ash and Palm Oil Fuel Ash on Heat of Hydration Aerated Concrete

PubMed Central

Mehmannavaz, Taha; Ismail, Mohammad; Radin Sumadi, Salihuddin; Rafique Bhutta, Muhammad Aamer; Samadi, Mostafa

2014-01-01

The binary effect of pulverized fuel ash (PFA) and palm oil fuel ash (POFA) on heat of hydration of aerated concrete was studied. Three aerated concrete mixes were prepared, namely, concrete containing 100% ordinary Portland cement (control sample or Type I), binary concrete made from 50% POFA (Type II), and ternary concrete containing 30% POFA and 20% PFA (Type III). It is found that the temperature increases due to heat of hydration through all the concrete specimens especially in the control sample. However, the total temperature rises caused by the heat of hydration through both of the new binary and ternary concrete were significantly lower than the control sample. The obtained results reveal that the replacement of Portland cement with binary and ternary materials is beneficial, particularly for mass concrete where thermal cracking due to extreme heat rise is of great concern. PMID:24696646

Photochemical Production of Singlet Oxygen from Dissolved Organic Matter in Ice.

PubMed

Fede, Alexis; Grannas, Amanda M

2015-11-03

Dissolved natural organic matter (DOM) is a ubiquitous component of natural waters and an important photosensitizer. A variety of reactive oxygen species (ROS) are known to be produced from DOM photochemistry, including singlet oxygen, 1O2. Recently, it has been determined that humic-like substances and unknown organic chromophores are significant contributors to sunlight absorption in snowpack; however, DOM photochemistry in snow/ice has received little attention in the literature. We recently showed that DOM plays an important role in indirect photolysis processes in ice, producing ROS and leading to the efficient photodegradation of a probe hydrophobic organic pollutant, aldrin.1 ROS scavenger experiments indicated that 1O2 played a significant role in the indirect photodegradation of aldrin. Here we quantitatively examine 1O2 photochemically produced from DOM in frozen and liquid aqueous solutions. Steady-state 1O2 production is enhanced up to nearly 1000 times in frozen DOM samples compared to liquid samples. 1O2 production is dependent on the concentration of DOM, but the nature of the DOM source (terrestrial vs microbial) does not have a significant effect on 1O2 production in liquid or frozen samples, with different source types producing similar steady-state concentrations of 1O2. The temperature of frozen samples also has a significant effect on steady-state 1O2 production in the range of 228-262 K, with colder samples producing more steady-state 1O2. The large enhancement in 1O2 in frozen samples suggests that it may play a significant role in the photochemical processes that occur in snow and ice, and DOM could be a significant, but to date poorly understood, oxidant source in snow and ice.

Gas adsorption on commercial magnesium stearate: Effects of degassing conditions on nitrogen BET surface area and isotherm characteristics.

PubMed

Lapham, Darren P; Lapham, Julie L

2017-09-15

Commercial grades of magnesium stearate have been analysed by nitrogen adsorption having been pre-treated at temperatures between 30°C and 110°C and in the as-received state. Characteristics of nitrogen adsorption/desorption isotherms are assessed through the linearity of low relative pressure isotherm data and the BET transform plot together with the extent of isotherm hysteresis. Comparison is made between thermal gravimetric analysis and mass loss on drying. Features of gas adsorption isotherms considered atypical are identified and possible causes presented. It is shown that atypical isotherm features and issues of applying BET theory to the calculation of S BET are linked to the presence of hydrated water and that these depend on the hydration state: being more pronounced for the di-hydrate than the mono-hydrate. Dehydration reduces the extent of atypical features. S BET of a mono-hydrate sample is 5.6m 2 g -1 and 3.2m 2 g -1 at 40°C and 100°C degassing respectively but 23.9m 2 g 1 and 5.9m 2 g -1 for di-hydrate containing samples under comparable degassing. Di-hydrated samples also show S BET >15m 2 g 1 , BET C-values <7 and BET correlation coefficients <0.98 before dehydration. Possible mechanisms for atypical isotherms are critically discussed together with the suitability of applying BET theory to nitrogen adsorption data. Copyright © 2017 Elsevier B.V. All rights reserved.

Fast X-Ray Fluorescence Microtomography of Hydrated Biological Samples

PubMed Central

Lombi, Enzo; de Jonge, Martin D.; Donner, Erica; Kopittke, Peter M.; Howard, Daryl L.; Kirkham, Robin; Ryan, Chris G.; Paterson, David

2011-01-01

Metals and metalloids play a key role in plant and other biological systems as some of them are essential to living organisms and all can be toxic at high concentrations. It is therefore important to understand how they are accumulated, complexed and transported within plants. In situ imaging of metal distribution at physiological relevant concentrations in highly hydrated biological systems is technically challenging. In the case of roots, this is mainly due to the possibility of artifacts arising during sample preparation such as cross sectioning. Synchrotron x-ray fluorescence microtomography has been used to obtain virtual cross sections of elemental distributions. However, traditionally this technique requires long data acquisition times. This has prohibited its application to highly hydrated biological samples which suffer both radiation damage and dehydration during extended analysis. However, recent advances in fast detectors coupled with powerful data acquisition approaches and suitable sample preparation methods can circumvent this problem. We demonstrate the heightened potential of this technique by imaging the distribution of nickel and zinc in hydrated plant roots. Although 3D tomography was still impeded by radiation damage, we successfully collected 2D tomograms of hydrated plant roots exposed to environmentally relevant metal concentrations for short periods of time. To our knowledge, this is the first published example of the possibilities offered by a new generation of fast fluorescence detectors to investigate metal and metalloid distribution in radiation-sensitive, biological samples. PMID:21674049

Dissociation of Laboratory-Synthesized Methane Hydrate in Coarse-Grained Sediments by Slow Depressurization

NASA Astrophysics Data System (ADS)

Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.

2016-12-01

We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.

Comparison of human papillomavirus detection between freshly frozen tissue and paraffin embedded tissue of invasive cervical cancer

PubMed Central

2010-01-01

Background Human Papillomavirus (HPV) detection results comparing paraffin embedded cervical tissue and other cervical specimens have been done with varying degrees of agreement. However, studies comparing freshly frozen specimens and paraffin embedded specimens of invasive cervical carcinomas are lacking. The aim of the study was to compare HPV detection using SPF10 broad-spectrum primers PCR followed by DEIA and genotyping by LiPA25 (version 1) between freshly frozen cervical tissue samples and paraffin embedded blocks of cervical tissue from the same patient. There were 171 pairs of paraffin embedded and freshly frozen samples analyzed from cervical carcinoma cases from Kampala, Uganda. Results 88.9% (95% CI: 83.2%-93.2%) of paraffin embedded samples were HPV positive compared with 90.1% (95% CI: 84.6%-94.1%) of freshly frozen samples, giving an overall agreement in HPV detection between fresh tissue and paraffin embedded tissue at 86.0% (95% CI: 79.8%-90.8%). Although the proportion of HPV positive cases in freshly frozen tissue was higher than those in paraffin blocks, the difference was not statistically significant (p > 0.05). In both types of tissues, single HPV infections were predominant, with HPV16 accounting for 47% of positive cases. Comparison in the overall agreement, taking into accounts not only positivity in general, but also HPV types, showed a 65% agreement (complete agreement of 59.7%, partial agreement of 5.3%) and complete disagreement of 35.0%. HPV detection in squamous cell carcinomas (SCC) and adenocarcinomas (ADC) was similar in fresh tissue or paraffin blocks (p ≥ 0.05). p16 immunostaining in samples that had at least one HPV negative results showed that 24 out of 25 cases had an over-expressed pattern. Conclusions HPV DNA detection was lower among ADC as compared to SCC. However, such differences were minimized when additional p16 testing was added, suggesting that the technical issues may largely explain the HPV negative cases. PMID:20846370

Geochemistry of a naturally occurring massive marine gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.; Threlkeld, C.N.; Dendy, Sloan E.

1984-01-01

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4??C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ???0.2% ethane, and ???0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 permil(( 0 00), relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift. ?? 1984.

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

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

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

Effect of inulin on the physicochemical properties, flow behavior and probiotic survival of frozen yogurt.

PubMed

Rezaei, Rahil; Khomeiri, Morteza; Aalami, Mehran; Kashaninejad, Mahdi

2014-10-01

This study investigated the effect of inulin (0, 1 and 2 %), on some physicochemical properties of frozen yogurt, as well as its effect on flow behavior and probiotic survival. The results showed that the addition of inulin improved overrun, viscosity and melting properties significantly (p < 0.05); when added at 2 % level, it also had significant effect on pH. Total acceptability of samples revealed that frozen yogurt with 2 % inulin had the most appealing sensory characteristics. The flow behavior of all samples showed their pseudoplastic nature; power law was the best model to predict their flow behavior. In terms of probiotic survival, the sample with 2 % inulin significantly improved the viability of Lactobacillus acidophilus and Bifidobacterium lactis.

Effect of Hydration State of Martian Perchlorate Salts on their Decomposition Temperatures during Thermal Extraction

NASA Astrophysics Data System (ADS)

Royle, S. H.; Montgomery, W.; Kounaves, S. P.; Sephton, M. A.

2017-12-01

A number of missions to Mars have analyzed the composition of surface samples using thermal extraction techniques. The temperatures of decomposition have been used as diagnostic information for the materials present. One material of great current interest is perchlorate, a relatively recently discovered component of Mars surface geochemistry that leads to deleterious effects on organic matter during thermal extraction. Knowledge of the thermal decomposition behavior of perchlorate salts is essential for mineral identification and possible avoidance of confounding interactions with organic matter. We have performed a series of stepped pyrolysis experiments on samples of magnesium perchlorate hydrate which were dehydrated to various extents - as confirmed by XRD and FTIR analysis. Our data reveal that the hydration state of magnesium perchlorate has a significant effect on decomposition temperature, with differing temperature releases of oxygen corresponding to different perchlorate hydration states. We find that the peak temperature of oxygen release increases from 500 to 600°C as the proportion of the tetrahydrate form in the sample increases and the hexahydrate form decreases. It was known previously that cation chemistry can affect the temperature of oxygen release and now our work shows that the hydration state of these salts can lead to similar variations. Consequently, incorrect identification of perchlorate species may occur if hydration state is not taken into account and a mixture of metastable hydration states (of one type of perchlorate) may be mistaken for a mixture of perchlorate salts. Our findings are important for Mars as the hydration state of salts in the regolith may change throughout the Martian year due to large variations in humidity and temperature.

Logistics and quality control for DNA sampling in large multicenter studies.

PubMed

Nederhand, R J; Droog, S; Kluft, C; Simoons, M L; de Maat, M P M

2003-05-01

To study associations between genetic variation and disease, large bio-banks need to be created in multicenter studies. Therefore, we studied the effects of storage time and temperature on DNA quality and quantity in a simulation experiment with storage up to 28 days frozen, at 4 degrees C and at room temperature. In the simulation experiment, the conditions did not influence the amount or quality of DNA to an unsatisfactory level. However, the amount of extracted DNA was decreased in frozen samples and in samples that were stored for > 7 days at room temperature. In a sample of patients from 24 countries of the EUROPA trial obtained by mail with transport times up to 1 month DNA yield and quality were adequate. From these results we conclude that transport of non-frozen blood by ordinary mail is usable and practical for DNA isolation for polymerase chain reaction in clinical and epidemiological studies.

DNA methylation profiling of genomic DNA isolated from urine in diabetic chronic kidney disease: A pilot study

PubMed Central

Sexton-Oates, Alexandra; Carmody, Jake; Ekinci, Elif I.; Dwyer, Karen M.; Saffery, Richard

2018-01-01

Aim To characterise the genomic DNA (gDNA) yield from urine and quality of derived methylation data generated from the widely used Illuminia Infinium MethylationEPIC (HM850K) platform and compare this with buffy coat samples. Background DNA methylation is the most widely studied epigenetic mark and variations in DNA methylation profile have been implicated in diabetes which affects approximately 415 million people worldwide. Methods QIAamp Viral RNA Mini Kit and QIAamp DNA micro kit were used to extract DNA from frozen and fresh urine samples as well as increasing volumes of fresh urine. Matched buffy coats to the frozen urine were also obtained and DNA was extracted from the buffy coats using the QIAamp DNA Mini Kit. Genomic DNA of greater concentration than 20μg/ml were used for methylation analysis using the HM850K array. Results Irrespective of extraction technique or the use of fresh versus frozen urine samples, limited genomic DNA was obtained using a starting sample volume of 5ml (0–0.86μg/mL). In order to optimize the yield, we increased starting volumes to 50ml fresh urine, which yielded only 0–9.66μg/mL A different kit, QIAamp DNA Micro Kit, was trialled in six fresh urine samples and ten frozen urine samples with inadequate DNA yields from 0–17.7μg/mL and 0–1.6μg/mL respectively. Sufficient genomic DNA was obtained from only 4 of the initial 41 frozen urine samples (10%) for DNA methylation profiling. In comparison, all four buffy coat samples (100%) provided sufficient genomic DNA. Conclusion High quality data can be obtained provided a sufficient yield of genomic DNA is isolated. Despite optimizing various extraction methodologies, the modest amount of genomic DNA derived from urine, may limit the generalisability of this approach for the identification of DNA methylation biomarkers of chronic diabetic kidney disease. PMID:29462136

DNA methylation profiling of genomic DNA isolated from urine in diabetic chronic kidney disease: A pilot study.

PubMed

Lecamwasam, Ashani; Sexton-Oates, Alexandra; Carmody, Jake; Ekinci, Elif I; Dwyer, Karen M; Saffery, Richard

2018-01-01

To characterise the genomic DNA (gDNA) yield from urine and quality of derived methylation data generated from the widely used Illuminia Infinium MethylationEPIC (HM850K) platform and compare this with buffy coat samples. DNA methylation is the most widely studied epigenetic mark and variations in DNA methylation profile have been implicated in diabetes which affects approximately 415 million people worldwide. QIAamp Viral RNA Mini Kit and QIAamp DNA micro kit were used to extract DNA from frozen and fresh urine samples as well as increasing volumes of fresh urine. Matched buffy coats to the frozen urine were also obtained and DNA was extracted from the buffy coats using the QIAamp DNA Mini Kit. Genomic DNA of greater concentration than 20μg/ml were used for methylation analysis using the HM850K array. Irrespective of extraction technique or the use of fresh versus frozen urine samples, limited genomic DNA was obtained using a starting sample volume of 5ml (0-0.86μg/mL). In order to optimize the yield, we increased starting volumes to 50ml fresh urine, which yielded only 0-9.66μg/mL A different kit, QIAamp DNA Micro Kit, was trialled in six fresh urine samples and ten frozen urine samples with inadequate DNA yields from 0-17.7μg/mL and 0-1.6μg/mL respectively. Sufficient genomic DNA was obtained from only 4 of the initial 41 frozen urine samples (10%) for DNA methylation profiling. In comparison, all four buffy coat samples (100%) provided sufficient genomic DNA. High quality data can be obtained provided a sufficient yield of genomic DNA is isolated. Despite optimizing various extraction methodologies, the modest amount of genomic DNA derived from urine, may limit the generalisability of this approach for the identification of DNA methylation biomarkers of chronic diabetic kidney disease.

Measured temperature and pressure dependence of Vp and Vs in compacted, polycrystalline sI methane and sII methane-ethane hydrate

USGS Publications Warehouse

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

2003-01-01

We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17??C in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15??C and 0 to 105 MPa applied piston pressure.

Coupling between the Dynamics of Water and Surfactants in Lyotropic Liquid Crystals

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2017-04-26

Bilayers composed of lipid or surfactant molecules are central to biological membranes and lamellar lyotropic liquid crystalline (LLC) phases. Common to these systems are phases that exhibit either ordered or disordered packing of the hydrophobic tails. In this work, we study the impact of surfactant ordering, i.e., disordered L α and ordered L β LLC phases, on the dynamics of water and sodium ions in the lamellar phases of dicarboxylate gemini surfactants. We study the different phases at identical hydration levels by changing the length of the hydrophobic tails; surfactants with shorter tails form L α phases and those withmore » longer tails form L β phases. We find that the L α phases exhibit lower density and greater compressibility than the L β phases, with a hydration-dependent headgroup surface area. These structural differences significantly affect the relative dynamic properties of the phases, primarily the mobility of the surfactant molecules tangential to the bilayer surface, as well as the rates of water and ion diffusion. We find ~20–50% faster water diffusion in the L α phases compared to the L β phases, with the differences most pronounced at low hydration. This coupling between water dynamics and surfactant mobility is verified using additional simulations in which the surfactant tails are frozen. Our study indicates that gemini surfactant LLCs provide an important prototypical system for characterizing properties shared with more complex biological lipid membranes.« less

Relative merits and limiting factors for x-ray and electron microscopy of thick, hydrated organic materials.

PubMed

Du, Ming; Jacobsen, Chris

2018-01-01

Electron and x-ray microscopes allow one to image the entire, unlabeled structure of hydrated materials at a resolution well beyond what visible light microscopes can achieve. However, both approaches involve ionizing radiation, so that radiation damage must be considered as one of the limits to imaging. Drawing upon earlier work, we describe here a unified approach to estimating the image contrast (and thus the required exposure and corresponding radiation dose) in both x-ray and electron microscopy. This approach accounts for factors such as plural and inelastic scattering, and (in electron microscopy) the use of energy filters to obtain so-called "zero loss" images. As expected, it shows that electron microscopy offers lower dose for specimens thinner than about 1 µm (such as for studies of macromolecules, viruses, bacteria and archaebacteria, and thin sectioned material), while x-ray microscopy offers superior characteristics for imaging thicker specimen such as whole eukaryotic cells, thick-sectioned tissues, and organs. The required radiation dose scales strongly as a function of the desired spatial resolution, allowing one to understand the limits of live and frozen hydrated specimen imaging. Finally, we consider the factors limiting x-ray microscopy of thicker materials, suggesting that specimens as thick as a whole mouse brain can be imaged with x-ray microscopes without significant image degradation should appropriate image reconstruction methods be identified. Copyright © 2017 Elsevier B.V. All rights reserved.

The influence of porosity and structural parameters on different kinds of gas hydrate dissociation

PubMed Central

Misyura, S. Y.

2016-01-01

Methane hydrate dissociation at negative temperatures was studied experimentally for different artificial and natural samples, differing by macro- and micro-structural parameters. Four characteristic dissociation types are discussed in the paper. The internal kinetics of artificial granule gas hydrates and clathrate hydrates in coal is dependent on the porosity, defectiveness and gas filtration rate. The density of pores distribution in the crust of formed ice decreases by the several orders of magnitude and this change significantly the rate of decay. Existing models for describing dissociation at negative temperatures do not take into account the structural parameters of samples. The dissociation is regulated by internal physical processes that must be considered in the simulation. Non-isothermal dissociation with constant external heat flux was simulated numerically. The dissociation is simulated with consideration of heat and mass transfer, kinetics of phase transformation and gas filtering through a porous medium of granules for the negative temperatures. It is shown that the gas hydrate dissociation in the presence of mainly microporous structures is fundamentally different from the disintegration of gas hydrates containing meso and macropores. PMID:27445113

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

PubMed

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

2016-07-12

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

Effect of Frozen Human Epidermis Storage Duration and Cryoprotectant on Barrier Function using Two Model Compounds

PubMed Central

Barbero, Ana M.; Frasch, H. Frederick

2015-01-01

Skin is commonly stored frozen and then thawed prior to use for in-vitro permeation experiments. Does frozen storage of skin alter its barrier property? Numerous studies have found contradictory answers to this question. In this study, the steady state flux and lag time of diethyl phthalate (DEP) were measured for fresh human skin and skin frozen at −85 °C for 1, 2, 3, 6, 9, 12, and 18 months, with 10% glycerol as cryoprotective agent. No significant differences in steady state flux were found between fresh and previously frozen samples (P = 0.6). For lag time, a significant (P = 0.002) difference was found among all groups but comparisons with fresh skin were not significant. Does glycerol have a cryoprotective effect? The steady state flux and lag time of DEP and caffeine were measured through human skin stored at −85 °C for up to 12 months with and without 10 % glycerol. No significant differences in steady state flux or lag time were found between samples stored with or without glycerol for either DEP or caffeine (P ≥ 0.17). These findings support the use of frozen skin to measure the passive permeation of chemicals in studies unconcerned with viability and metabolism. PMID:26606593

Physiochemical Characterization of Iodine (V) Oxide: Hydration Rates

DTIC Science & Technology

2014-12-15

decomposition .21 2 Distribution A Scheme 1. Iodine (V) Oxide‐Water System Hydration : 3I2O5(s) + H2O(g) → 2HI3O8(s) + 2H2O(g) → 6HIO3(s...dehydration steps and decomposition step for each sample. The corresponding percent compositions of the three hydration forms of the oxide have been...135 Physiochemical Characterization of Iodine (V) Oxide: Hydration Rates Distribution A: Approved for public release; distribution unlimited

Hydrates of nat­ural gas in continental margins

USGS Publications Warehouse

Kvenvolden, K.A.; Barnard, L.A.

1982-01-01

Natural gas hydrates in continental margin sediment can be inferred from the widespread occurrence of an anomalous seismic reflector which coincides with the predicted transition boundary at the base of the gas hydrate zone. Direct evidence of gas hydrates is provided by visual observations of sediments from the landward wall of the Mid-America Trench off Mexico and Guatemala, from the Blake Outer Ridge off the southeastern United States, and from the Black Sea in the U.S.S.R. Where solid gas hydrates have been sampled, the gas is composed mainly of methane accompanied by CO2 and low concentrations of ethane and hydrocarbons of higher molecular weight. The molecular and isotopic composition of hydrocarbons indicates that most of the methane is of biolog cal origin. The gas was probably produced by the bacterial alteration of organic matter buried in the sediment. Organic carbon contents of the sediment containing sampled gas hydrates are higher than the average organic carbon content of marine sediments. The main economic importance of gas hydrates may reside in their ability to serve as a cap under which free gas can collect. To be producible, however, such trapped gas must occur in porous and permeable reservoirs. Although gas hydrates are common along continental margins, the degree to which they are associated with significant reservoirs remains to be investigated.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Differentiation of fresh and frozen-thawed fish samples using Raman spectroscopy coupled with chemometric analysis.

PubMed

Velioğlu, Hasan Murat; Temiz, Havva Tümay; Boyaci, Ismail Hakki

2015-04-01

The potential of Raman spectroscopy was investigated in terms of its capability to discriminate the species of the fish samples and determine their freshness according to the number of freezing/thawing cycles they exposed. Species discrimination analysis was carried out on sixty-four fish samples from six different species, namely horse mackerel (Trachurus trachurus), European anchovy (Engraulis encrasicolus), red mullet (Mullus surmuletus), Bluefish (Pomatamus saltatrix), Atlantic salmon (Salmo salar) and flying gurnard (Trigla lucerna). Afterwards, fish samples were exposed to different numbers of freezing/thawing cycles and separated into three batches, namely (i) fresh, (ii) once frozen-thawed (OF) and (iii) twice frozen-thawed (TF) samples, in order to perform the freshness analysis. Raman data collected were used as inputs for chemometric analysis, which enabled us to develop two main PCA models to successfully terminate the studies for both species discrimination and freshness determination analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Histology as a Valid Tool To Differentiate Fresh from Frozen-Thawed Marinated Fish.

PubMed

Meistro, Serena; Pezzolato, Marzia; Muscolino, Daniele; Giarratana, Filippo; Baioni, Elisa; Panebianco, Antonio; Bozzetta, Elena

2016-08-01

European Commission Regulation (EU) 1276/2011 requires that fishery products intended for raw consumption be frozen at -20°C for not less than 24 h or at -35°C for at least 15 h in order to kill viable parasites other than trematodes. But because marinating processes are not always effective in destroying nematode larvae, raw marinated fish preparations should be frozen before consumption. This study evaluated the performance of a standardized histological method to distinguish between fresh and frozen-thawed raw marinated fish. Sixty anchovy (Engraulis encrasicolus) fillets were sampled: 30 were marinated at +4°C for 24 h, and 30 were frozen at -20°C for 24 h before being marinated for 24 h. All 60 samples were fixed in formalin, processed for paraffin embedding, cut, and stained with hematoxylin and eosin. The slide preparations were examined microscopically by three independent histopathologists and classified as frozen-thawed or negative according to standard operating procedure criteria in use at our laboratory. Performance evaluation of the method showed 100% sensitivity (95% confidence interval [CI], 88.4 to 100%) and 100% specificity (95% CI, 88.4 to 100%), and the interrater agreement (Cohen's kappa) was 1 (95% CI, 0.85 to 1). Histology proved a valid and reliable tool to distinguish fresh from frozen-thawed marinated fish. It can be applied to deliver safe raw fishery products to consumers in order to minimize the risk of anisakidosis.

The impact of hydration changes in fresh bio-tissue on THz spectroscopic measurements.

PubMed

Png, G M; Choi, J W; Ng, B W-H; Mickan, S P; Abbott, D; Zhang, X-C

2008-07-07

We present a study of how residual hydration in fresh rat tissue samples can vastly alter their extracted terahertz (THz) optical properties and influence their health assessment. Fresh (as opposed to preserved) tissue most closely mimics in vivo conditions, but high water content creates many challenges for tissue handling and THz measurement. Our THz measurements of fresh tissue over time highlight the effect of tissue hydration on tissue texture and dimension, the latter directly influencing the accuracy of calculated optical properties. We then introduce lyophilization (freeze drying) as a viable solution for overcoming hydration and freshness problems. Lyophilization removes large amounts of water while retaining sample freshness. In addition, lyophilized tissue samples are easy to handle and their textures and dimensions do not vary over time, allowing for consistent and stable THz measurements. A comparison of lyophilized and fresh tissue shows for the first time that freeze drying may be one way of overcoming tissue hydration issues while preserving tissue cellular structure. Finally, we compare THz measurements from fresh tissue against necrotic tissue to verify freshness over time. Indeed, THz measurements from fresh and necrotic tissues show marked differences.

The effect of protein oxidation on hydration and water-binding in pork packaged in an oxygen-enriched atmosphere.

PubMed

Delles, Rebecca M; Xiong, Youling L

2014-06-01

This study investigated the in situ oxidative process of myofibrillar proteins in boneless pork loin chops (Longissimus lumborum) packaged in an oxygen-enriched atmosphere (HiOx: 80% O2/20% CO2), an air-permeable polyvinylchloride (PVC) overwrap, or a partial vacuum (VP) throughout display at 2°C for up to 14, 7, and 21days, respectively. Samples stored in HiOx were susceptible to lipid (TBARS) and protein (carbonyls, sulfhydryls, and aggregation) oxidation, while samples in PVC and VP showed lesser oxidative changes. Water-holding capacity of raw muscle decreased (P<0.05) when stored in HiOx but not in PVC and VP. Upon salt and phosphate brine marination, HiOx and PVC muscle samples had improved hydration capacity during display compared with non-stored control, but display generally decreased hydration of VP samples. The result was in agreement with myofibril structural changes. Despite the enhanced hydration, HiOx muscle was least capable of withholding moisture upon cooking. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Filter paper-assisted cell transfer (FaCT) technique: A novel cell-sampling technique for intraoperative diagnosis of central nervous system tumors.

PubMed

Kawamura, Jumpei; Kamoshida, Shingo; Shimakata, Takaaki; Hayashi, Yurie; Sakamaki, Kuniko; Denda, Tamami; Kawai, Kenji; Kuwao, Sadahito

2017-04-01

Intraoperative diagnosis of central nervous system (CNS) tumors provides critical guidance to surgeons in the determination of surgical resection margins and treatment. The techniques and preparations used for the intraoperative diagnosis of CNS tumors include frozen sectioning and cytologic methods (squash smear and touch imprint). Cytologic specimens, which do not have freezing artifacts, are important as an adjuvant tool to frozen sections. However, if the amount of submitted tissue samples is limited, then it is difficult to prepare both frozen sections and squash smears or touch imprint specimens from a single sample at the same time. Therefore, the objective of this study was to derive cells directly from filter paper on which tumor samples are placed. The authors established the filter paper-assisted cell transfer (FaCT) smear technique, in which tumor cells are transferred onto a glass slide directly from the filter paper sample spot after the biopsy is removed. Cell yields and diagnostic accuracy of the FaCT smears were assessed in 40 CNS tumors. FaCT smears had ample cell numbers and well preserved cell morphology sufficient for cytologic diagnosis, even if the submitted tissues were minimal. The overall diagnostic concordance rates between frozen sections and FaCT smears were 90% and 87.5%, respectively (no significant differences). When combining FaCT smears with frozen sections, the diagnostic concordance rate rose to 92.5%. The current results suggest that the FaCT smear technique is a simple and effective processing method that has significant value for intraoperative diagnosis of CNS tumors. Cancer Cytopathol 2017;125:277-282. © 2016 American Cancer Society. © 2017 American Cancer Society.

Origin Of Methane Gas And Migration Through The Gas Hydrate Stability Zone Beneath The Permafrost Zone

NASA Astrophysics Data System (ADS)

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

2005-12-01

In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data as well as visible gas hydrates have confirmed pore-space hydrate as intergranular pore filling within sandy layers whose saturations are up to 80% in pore volume, but muddy sediments scarcely contain. Plenty of gas hydrate-bearing sand core samples have been obtained from the Mallik wells. According to grain size distributions pore-space hydrate is dominant in medium- to very fine-grained sandy strata. Methane gas accumulation and original pore space large enough to occur within host sediments may be required for forming highly saturated gas hydrate in pore system. The distribution of a porous and coarser-grained host rock should be one of the important factors to control the occurrence of gas hydrate, as well as physicochemical conditions. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sandy core samples also revealed important geologic and sedimentological controls on the formation and concentration of natural gas hydrate. This appears to be a similar mode for conventional oil and gas accumulations. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. The isotopic data of methane show that hydrocarbon gas contained in gas hydrate is generated by thermogenic decomposition of kerogen in deep mature sediments. Based on geochemical and geological data, methane is inferred to migrate upward closely associated with pore water hundreds of meters into and through the hydrate stability zone partly up to the permafrost zone and the surface along faults and permeable sandy pathways. It should be remarked that there are many similar features in appearance and characteristics between the terrestrial and deep marine areas such as Nankai Trough with observations of well-interconnected and highly saturated pore-space hydrate.

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Cryopreserved and frozen hyaline cartilage imaged by environmental scanning electron microscope. An experimental and prospective study.

PubMed

Sastre, Sergi; Suso, Santiago; Segur, Josep-Maria; Bori, Guillem; Carbonell, José-Antonio; Agustí, Elba; Nuñez, Montse

2008-08-01

To obtain images of the articular surface of osteochondral grafts (fresh, frozen, and cryopreserved in RPMI) using an environmental scanning electron microscope (ESEM). To evaluate and compare the main morphological aspects of the chondral surface of the fresh, frozen, and cryopreserved grafts as visualized via ESEM. The study was based on osteochondral fragments from the internal condyle of the knee joint of New Zealand rabbits, corresponding to the chondral surface from fresh, frozen, and cryopreserved samples. One hundred ESEM images were obtained from each group and then classified according to a validated system. The kappa index and the corresponding concordance index were calculated, and the groups were compared by Pearson's chi-squared test (p < 0.05). The articular surface of cryopreserved osteochondral grafts had fewer even surfaces and filled lacunae and a higher number of empty lacunae as compared to fresh samples; these differences correspond to images of cell membrane lesions that lead to destruction of the chondrocyte. Frozen grafts showed more hillocky and knobby surfaces than did fresh grafts; they also had a greater number of empty chondrocyte lacunae. ESEM is useful for obtaining images of the surface of osteochondral grafts. When compared to fresh samples, cryopreservation in RPMI medium produces changes in the surface of hyaline cartilage, but to a lesser extent than those produced by freezing.

Validation of freezing tissues and cells for analysis of DNA strand break levels by comet assay

PubMed Central

Jackson, Petra

2013-01-01

The comet analysis of DNA strand break levels in tissues and cells has become a common method of screening for genotoxicity. The large majority of published studies have used fresh tissues and cells processed immediately after collection. However, we have used frozen tissues and cells for more than 10 years, and we believe that freezing samples improve efficiency of the method. We compared DNA strand break levels measured in fresh and frozen bronchoalveolar cells, and lung and liver tissues from mice exposed to the known mutagen methyl methanesulphonate (0, 25, 75, 112.5mg/kg). We used a high-throughput comet protocol with fully automated scoring of DNA strand break levels. The overall results from fresh and frozen samples were in agreement [R 2 = 0.93 for %DNA in tail (%TDNA) and R 2 = 0.78 for tail length (TL)]. A slightly increased %TDNA was observed in lung and liver tissue from vehicle controls; and TL was slightly reduced in bronchoalveolar lavage cells from the high-dose group. In our comet protocol, a small block of tissue designated for comet analysis is frozen immediately at tissue collection and kept deep frozen until rapidly homogenised and embedded in agarose. To demonstrate the feasibility of long-term freezing of samples, we analysed the day-to-day variation of our internal historical negative and positive comet assay controls collected over a 10-year period (1128 observations, 11 batches of frozen untreated and H2O2-treated A549 lung epithelial cells). The H2O2 treatment explained most of the variation 57–77% and the day-to-day variation was only 2–12%. The presented protocol allows analysis of samples collected over longer time span, at different locations, with reduced variation by reducing number of electrophoreses and is suitable for both toxicological and epidemiological studies. The use of frozen tissues; however, requires great care during preparation before analysis, with handling as a major risk factor. PMID:24136994

Joint Measurements Of Acoustic And Mechanical Properties For Methane Hydrate-Bearing Unconsolidated Sediments Synthesized In Laboratory

NASA Astrophysics Data System (ADS)

Yang, Z.; He, T.

2017-12-01

To more accurately explain geophysical exploration data of natural gas hydrate reservoir and to better assess the formation stability for geological or engineering hazards, it is important to comprehensively understand the geophysical and mechanical properties of hydrate-bearing unconsolidated marine sediments, which are significantly different from sea-water saturated ones. Compared to hard-to-control in-situ measurement, laboratory methods are important and feasible to investigate the parameter effects. With the new designed experimental apparatus, we measured ultrasonic velocity, resistivity and stress-strain relation of methane hydrate-bearing unconsolidated sediments. The experimental mineral mixture is prepared as the composition of sample HY-3 of core SH-7 from Shenhu area, South China Sea. It composed of 0.4 wt. % kaolinite, 23.5 wt. % silt (4 - 63 μm), 32.1 wt. % fine sand (63 - 250 μm), 29.2 wt. % medium sand (250 - 500 μm) and 14.8 wt. % coarse sand (500 - 2000 μm). The pure methane enters into the brine (NaCl salinity of 3.5%) saturated sample all around to synthesis methane hydrate. The methane hydrate saturation was calculated by methane consumption amount, which was in turn calculated by gas state equation using the measured methane pressure drop in high pressure reactor. The ultrasonic velocities and resistivity were measured frequently during methane hydrate saturation increasing to examine the velocity varying pattern, especially for S-wave velocities, which may reflect different hydrate occurrence states in sediment pores: load-bearing or not. The stress - strain curves of methane hydrate - bearing sediments showed typical elastic - plastic characteristics and were used to obtain Young's modulus, Poisson's ratio, failure strength and other mechanical parameters. With these results, we can know better about the hydrate reservoir at Shenhu area.

Blind Biobanking of the Prostatectomy Specimen: Critical Evaluation of the Existing Techniques and Development of the New 4-Level Tissue Extraction Model With High Sampling Efficacy.

PubMed

Tolkach, Yuri; Eminaga, Okyaz; Wötzel, Fabian; Huss, Sebastian; Bettendorf, Olaf; Eltze, Elke; Abbas, Mahmoud; Imkamp, Florian; Semjonow, Axel

2017-03-01

Fresh tissue is mandatory to perform high-quality translation studies. Several models for tissue extraction from prostatectomy specimens without guidance by frozen sections are already introduced. However, little is known about the sampling efficacy of these models, which should provide representative tissue in adequate volumes, account for multifocality and heterogeneity of tumor, not violate the routine final pathological examination, and perform quickly without frozen section-based histological control. The aim of the study was to evaluate the sampling efficacy of the existing tissue extraction models without guidance by frozen sections ("blind") and to develop an optimized model for tissue extraction. Five hundred thirty-three electronic maps of the tumor distribution in prostates from a single-center cohort of the patients subjected to radical prostatectomy were used for analysis. Six available models were evaluated in silico for their sampling efficacy. Additionally, a novel model achieving the best sampling efficacy was developed. The available models showed high efficacies for sampling "any part" from the tumor (up to 100%), but were uniformly low in efficacy to sample all tumor foci from the specimens (with the best technique sampling only 51.6% of the all tumor foci). The novel 4-level extraction model achieved a sampling efficacy of 93.1% for all tumor foci. The existing "blind" tissue extraction models from prostatectomy specimens without frozen sections control are suitable to target tumor tissues but these tissues do not represent the whole tumor. The novel 4-level model provides the highest sampling efficacy and a promising potential for integration into routine. Prostate 77: 396-405, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Effect of surface modification on hydration kinetics of carbamazepine anhydrate using isothermal microcalorimetry.

PubMed

Otsuka, Makoto; Ishii, Mika; Matsuda, Yoshihisa

2003-01-01

The purpose of this research was to improve the stability of carbamazepine (CBZ) bulk powder under high humidity by surface modification. The surface-modified anhydrates of CBZ were obtained in a specially designed surface modification apparatus at 60 degrees C via the adsorption of n-butanol, and powder x-ray diffraction, Fourier-Transformed Infrared spectra, and differential scanning calorimetry were used to determine the crystalline characteristics of the samples. The hydration process of intact and surface-modified CBZ anhydrate at 97% relative humidity (RH) and 40 +/-C 1 degrees C was automatically monitored by using isothermal microcalorimetry (IMC). The dissolution test for surface-modified samples (20 mg) was performed in 900 mL of distilled water at 37 +/-C 0.5 degrees C with stirring by a paddle at 100 rpm as in the Japanese Pharmacopoeia XIII. The heat flow profiles of hydration of intact and surface-modified CBZ anhydrates at 97% RH by using IMC profiles showed a maximum peak at around 10 hours and 45 hours after 0 and 10 hours of induction, respectively. The result indicated that hydration of CBZ anhydrate was completely inhibited at the initial stage by surface modification of n-butanol and thereafter transformed into dihydrate. The hydration of surface-modified samples followed a 2-dimensional phase boundary process with an induction period (IP). The IP of intact and surface-modified samples decreased with increase of the reaction temperature, and the hydration rate constant (k) increased with increase of the temperature. The crystal growth rate constants of nuclei of the intact sample were significantly larger than the surface-modified sample's at each temperature. The activation energy (E) of nuclei formation and crystal growth process for hydration of surface-modified CBZ anhydrate were evaluated to be 20.1 and 32.5 kJ/mol, respectively, from Arrhenius plots, but the Es of intact anhydrate were 56.3 and 26.8 kJ/mol, respectively. The dissolution profiles showed that the surface-modified sample dissolved faster than the intact sample at the initial stage. The dissolution kinetics were analyzed based on the Hixon-Crowell equation, and the dissolution rate constants for intact and surface-modified anhydrates were found to be 0.0102 +/-C 0.008 mg(1/3) x min(-1) and 0.1442 +/-C 0.0482 mg(1/3) x min(-1). The surface-modified anhydrate powders were more stable than the nonmodified samples under high humidity and showed resistance against moisture. However, surface modification induced rapid dissolution in water compared to the control.

Disparities in Intratumoral Steroidogenesis

DTIC Science & Technology

2013-07-01

Tuesday shipment only) by overnight express for next day delivery on dry ice. Frozen specimens will be shipped on dry ice to the following address...Samples will be labeled with the study subject number and date of surgery. Frozen samples will be batch shipped (Monday and Tuesday shipment only) by... Morris MJ, de Bono JS, Ryan CJ, Denmeade SR, Smith MR, et al. Phase II multicenter study of abiraterone acetate plus prednisone therapy in patients

A rapid and efficient DNA extraction protocol from fresh and frozen human blood samples.

PubMed

Guha, Pokhraj; Das, Avishek; Dutta, Somit; Chaudhuri, Tapas Kumar

2018-01-01

Different methods available for extraction of human genomic DNA suffer from one or more drawbacks including low yield, compromised quality, cost, time consumption, use of toxic organic solvents, and many more. Herein, we aimed to develop a method to extract DNA from 500 μL of fresh or frozen human blood. Five hundred microliters of fresh and frozen human blood samples were used for standardization of the extraction procedure. Absorbance at 260 and 280 nm, respectively, (A 260 /A 280 ) were estimated to check the quality and quantity of the extracted DNA sample. Qualitative assessment of the extracted DNA was checked by Polymerase Chain reaction and double digestion of the DNA sample. Our protocol resulted in average yield of 22±2.97 μg and 20.5±3.97 μg from 500 μL of fresh and frozen blood, respectively, which were comparable to many reference protocols and kits. Besides yielding bulk amount of DNA, our protocol is rapid, economical, and avoids toxic organic solvents such as Phenol. Due to unaffected quality, the DNA is suitable for downstream applications. The protocol may also be useful for pursuing basic molecular researches in laboratories having limited funds. © 2017 Wiley Periodicals, Inc.

Sea Spray Aerosol Structure and Composition Using Cryogenic Transmission Electron Microscopy

PubMed Central

2016-01-01

The composition and surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface and internal structure often undergo physicochemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of cryogenic transmission electron microscopy where laboratory generated sea spray aerosol particles are flash frozen in their native state with iterative and controlled thermal and/or pressure exposures and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including whole hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets—all of which will have distinct biological, chemical, and physical processes. We anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere. PMID:26878061

Characterization of internal structure of hydrated agar and gelatin matrices by cryo-SEM.

PubMed

Rahbani, Janane; Behzad, Ali R; Khashab, Niveen M; Al-Ghoul, Mazen

2013-02-01

There has been a considerable interest in recent years in developing polymer gel matrices for many important applications such as 2DE for quantization and separation of a variety of proteins and drug delivery system to control the release of active agents. However, a well-defined knowledge of the ultrastructures of the gels has been elusive. In this study, we report the characterization of two different polymers used in 2DE: Gelatin, a naturally occurring polymer derived from collagen (protein) and agar, a polymer of polysaccharide (sugar) origin. Low-temperature SEM is used to examine the internal structure of these gels in their frozen natural hydrated states. Results of this study show that both polymers have an array of hollow cells that resembles honeycomb structures. While agar pores are almost circular, the corresponding Gaussian curve is very broad exhibiting a range of radii from nearly 370 to 700 nm. Gelatin pores are smaller and more homogeneous reflecting a narrower distribution from nearly 320 to 650 nm. Overall, these ultrastructural findings could be used to correlate with functions of the polymers. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of cryopreservation on goat semen characteristics related to sperm freezability.

PubMed

Dorado, J; Muñoz-Serrano, A; Hidalgo, M

2010-08-01

Seminal quality parameters were used to evaluate the effect of freeze-thawing procedure on goat sperm characteristics, and to relate possible changes in sperm parameters to cryopreservation success. Semen samples (n=110) were frozen with TRIS and milk-based extenders and thawed. Sperm quality parameters (motility, morphology and acrosome) were compared between fresh and frozen-thawed samples. Sperm freezability was judged by classifying the semen samples as "suitable" or "not suitable" according to the sperm quality parameters assessed before and after thawing. Fertility data was obtained after cervical insemination with frozen semen doses. The ejaculates were grouped into two categories according to their fertility results. In experiment 1, significant differences were found between semen extenders (P<0.001), bucks (P<0.05) and ejaculates within the same male (P<0.05) in terms of sperm quality. There was no seasonal effect (P>0.05) on the majority of the sperm parameters assessed after thawing. Moreover, significant differences (P<0.001) in semen parameters assessed in fresh semen and frozen-thawed samples were found between groups. The effect of the freeze-thawing procedure on sperm quality parameters was also different (P<0.05) between extenders within the same group. The number of sperm quality parameters that had changed after cryopreservation was lower in "suitable" semen samples before and after thawing. In experiment 2, no differences (P>0.05) in semen parameters assessed in fresh semen and frozen-thawed samples were found between groups. The effect of freezing and thawing on sperm quality parameters were different (P<0.05) between extenders within the same group. Only mean beat cross frequency (BCF) values were significantly higher (P<0.05) in TRIS diluted samples that led to successful pregnancies after artificial insemination. In conclusion, CASA-derived motility parameters, together with traditional semen assessment methods, give valuable information on sperm quality before and after freezing. Therefore, the identification of ejaculates as "good" or "bad" based on fresh and post-thaw semen parameters studied in the present experiment were good indicators of goat semen freezability, although the fertilizing capacity of frozen-thawed goat spermatozoa are not revealed by this quality study. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

USGS Publications Warehouse

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

1998-01-01

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25-30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140-200 K, Pc = 50-100 MPa, and ?? = 10-4 10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

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

Sundaramurthi, Prakash; Patapoff, Thomas W.; Suryanarayanan, Raj

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozenmore » solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.« less

The effect of Arabic gum on frozen dough properties and the sensory assessments of the bread produced.

PubMed

Tavakoli, Hamid Reza; Jonaidi Jafari, Nematollah; Hamedi, Hassan

2017-04-01

The use of hydrocolloids in frozen dough has become frequent as bread improvers due to their anti-staling effect. Nevertheless, the impact of both different frozen storage and Arabic gum level in non-prefermented flat dough with following thawing procedure have not been studied. This work intended to study the effect of three different ratio of Arabic gum on rheological properties of 1, 7, and 30 days of frozen storage and the quality of the bread made from. In order to gain the least detrimental effects on gluten network, we used rapid rate freezing and microwave heating in thawing stage. Rheological results showed that the unfrozen samples to which Arabic gum had been added rendered the highest resistance to extension. The resistance of gum fortified samples were less than fresh dough, however the decline was not significant in 3.0% Arabic gum dough kept in a month storage (p > .05). The similar findings were obtained for extensibility and adhesiveness; in which the maximum incorporation of Arabic gum lessen the destructive impact of long freezing storage. Addition of 3% gum could be able to retard staling through an increment in hydrophilic bonds between water molecules and amylose during thawing (p < .05). The overall rating of Arabic gum enriched samples was similar with bread made from non-frozen dough, even after 30 days of storage as indicated by the sensory evaluation of breads. Producing a chapatti-like fermented bread without long fermentation period. Formulation a frozen dough without using chemical additives. Introducing a proper use of a new defrosting method with the aim of achieving a better texture. Improvement in retarding staling by the use of Gum Arabic after 7 days. © 2016 Wiley Periodicals, Inc.

Effect of different concentrations of egg yolk and virgin coconut oil in Tris-based extenders on chilled and frozen-thawed bull semen.

PubMed

Tarig, A A; Wahid, H; Rosnina, Y; Yimer, N; Goh, Y M; Baiee, F H; Khumran, A M; Salman, H; Ebrahimi, M

2017-07-01

The aim of this study was to evaluate the effects of 8% virgin coconut oil (VCO) combined with different percentages of egg yolk in Tris extender on the quality of chilled and frozen-thawed bull semen. A total of 24 ejaculates from four bulls were collected using an electroejaculator. Semen samples were diluted with 8% VCO in Tris extender which contained different concentrations 0% (control), 4%, 8%, 12%, 16% and 20% egg yolk. The diluted semen samples were divided into two fractions: one was chilled and stored at 4°C until evaluation after 24, 72, and 144h; the second fraction was processed by chilling for 3h at 4°C to equilibrate, then packaged in 0.25ml straws and frozen and stored in liquid nitrogen at -196°C until evaluation after 7 and 14 days. Both chilled and frozen semen samples were then thawed at 37°C and assessed for general motility using computer-assisted semen analysis (CASA), viability, acrosome integrity, and morphology (eosin-nigrosin), membrane integrity (hypo-osmotic swelling test) and lipid peroxidation (thiobarbituric acid-reactive substances (TBARS)). The results indicate treatments with 8%, 12%, 16% and 20% egg yolk with 8% VCO had greater sperm quality (P<0.05) as compared with the control. The treatment with 20% egg yolk had the greatest sperm quality (P<0.05) among the treated groups for both chilled and frozen-thawed semen. In conclusion, the use of 8% VCO combined with 20% egg yolk in a Tris-based extender enhanced the values for chilled and frozen-thawed quality variables of bull sperm. Copyright © 2017 Elsevier B.V. All rights reserved.

Immunoreactive LH in long-term frozen human urine samples.

PubMed

Singh, Gurmeet Kaur Surindar; Jimenez, Mark; Newman, Ron; Handelsman, David J

2014-04-01

Urine provides a convenient non-invasive alternative to blood sampling for measurement of certain hormones. Urinary luteinizing hormone (LH) measurements have been used for endocrinology research and anti-doping testing. However, the commercially available LH immunoassays are developed and validated for human blood samples but not urine so that LH assays intended for use with urine samples need thorough validation. Therefore, the present study evaluated the measurement of urinary LH immunoreactivity using previously validated immunofluorometric (IF) and immunochemiluminometric (ICL) LH assays after prolonged frozen storage. LH was measured in serial urine samples following administration of a single injection of one of two doses of recombinant human chorionic hormone (rhCG) with assays run at the end of study (2008) and again after four years of frozen (-20 °C) storage where samples were stored without adding preservatives. The ICL assay showed quantitatively reproducible LH measurements after prolonged -20 °C storage. However, the IF immunoassay gave consistently lower LH levels relative to ICL (2008) with a further proportionate reduction after four years of sample storage (2012). Yet, both the assays displayed similar patterns of the time-course of urine LH measurement both before and after four years of frozen storage. In conclusion, we found that both immunoassays are suitable for urinary LH measurements with ICL assay being more robust for quantitative urinary LH measurement such as for anti-doping purposes, whereas the IF could be applicable for research studies where urine LH levels are compared within-study but not in absolute terms. Copyright © 2013 John Wiley & Sons, Ltd.

Site selection for DOE/JIP gas hydrate drilling in the northern Gulf of Mexico

USGS Publications Warehouse

Hutchinson, Deborah; Shelander, Dianna; Dai, J.; McConnell, D.; Shedd, William; Frye, Matthew; Ruppel, Carolyn D.; Boswell, R.; Jones, Emrys; Collett, Timothy S.; Rose, Kelly K.; Dugan, Brandon; Wood, Warren T.

2008-01-01

n 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 analyses

[Raman Characterization of Hydrate Crystal Structure Influenced by Mine Gas Concentration].

PubMed

Zhang, Bao-yong; Zhou, Hong-ji; Wu, Qiang; Gao, Xia

2016-01-01

CH4 /C2H6/N2 mixed hydrate formation experiments were performed at 2 degrees C and 5 MPa for three different mine gas concentrations (CH4/C2H6/N2, G1 = 54 : 36 : 10, G2 = 67.5 : 22.5 : 10, G3 = 81 : 9 : 10). Raman spectra for hydration products were obtained by using Microscopic Raman Spectrometer. Hydrate structure is determined by the Raman shift of symmetric C-C stretching vibration mode of C2H6 in the hydrate phase. This work is focused on the cage occupancies and hydration numbers, calculated by the fitting methods of Raman peaks. The results show that structure I (s I) hydrate forms in the G1 and G2 gas systems, while structure II (s II) hydrate forms in the G3 gas system, concentration variation of C2H6 in the gas samples leads to a change in hydrate structure from s I to s II; the percentages of CH4 and C2H6 in s I hydrate phase are less affected by the concentration of gas samples, the percentages of CH4 are respectively 34.4% and 35.7%, C2H6 are respectively 64.6% and 63.9% for gas systems of G1 and G2, the percentages of CH4 and 2 H6 are respectively 73.5% and 22.8% for gas systems of G3, the proportions of object molecules largely depend on the hydrate structure; CH4 and C2H6 molecules occupy 98%, 98% and 92% of the large cages and CH4 molecules occupy 80%, 60% and 84% of the small cages for gas systems of G1, G2 and G3, respectively; additionally, N2 molecules occupy less than 5% of the small cages is due to its weak adsorption ability and the lower partial pressure.

Is sperm cryopreservation at -150 degree C a feasible alternative?

PubMed

Medrano, A; Cabrera, F; González, F; Batista, M; Gracia, A

2002-01-01

A series of experiments was carried out to validate a -150 degree C ultra-low temperature freezer for its possible use to properly freeze and store semen. In the first part, crude sample handling was simulated to see whether temperature of stored samples was maintained within a safe range; also, the freezing point and latent heat of fusion plateau of a semen extender were monitored. In the second part, buck semen was (i) frozen in liquid nitrogen and stored in the ultra-low freezer, (ii) frozen and stored in the ultra-low freezer, and (iii) frozen and stored in liquid nitrogen, to compare sperm cryosurvival between freezing methods. Both, frequent removal of samples and long opening of the freezer door did not negatively affect stored sample temperature; latent heat of fusion plateau was 5 minutes long. Semen stored either at -150 degree C or at -196 degree C cryosurvived similarly after 2 days and after 2 months of cryopreservation.

Borehole Tool for the Comprehensive Characterization of Hydrate-bearing Sediments

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

Dai, Sheng; Santamarina, J. Carlos

Reservoir characterization and simulation require reliable parameters to anticipate hydrate deposits responses and production rates. The acquisition of the required fundamental properties currently relies on wireline logging, pressure core testing, and/or laboratory observations of synthesized specimens, which are challenged by testing capabilities and innate sampling disturbances. The project reviews hydrate-bearing sediments, properties, and inherent sampling effects, albeit lessen with the developments in pressure core technology, in order to develop robust correlations with index parameters. The resulting information is incorporated into a tool for optimal field characterization and parameter selection with uncertainty analyses. Ultimately, the project develops a borehole tool formore » the comprehensive characterization of hydrate-bearing sediments at in situ, with the design recognizing past developments and characterization experience and benefited from the inspiration of nature and sensor miniaturization.« less

A Molecular Framework for Understanding DCIS

DTIC Science & Technology

2016-10-01

frozen patient biopsies, these have been annotated by our pathologist and prepared to be taken on for sequencing. The tissue includes DCIS, IDC...stroma adjacent to DCIS/IDC and normal tissue . We have initiated the RNA sequencing from these samples and also the DNA sequencing 15. SUBJECT TERMS DCIS...before they reach 55. Utilizing a unique bank of frozen mammary biopsies, containing samples with DCIS alone, and a combination of DCIS and IDC, we aim

Consistency of signal intensity and T2* in frozen ex vivo heart muscle, kidney, and liver tissue.

PubMed

Kaye, Elena A; Josan, Sonal; Lu, Aiming; Rosenberg, Jarrett; Daniel, Bruce L; Pauly, Kim Butts

2010-03-01

To investigate tissue dependence of the MRI-based thermometry in frozen tissue by quantification and comparison of signal intensity and T2* of ex vivo frozen tissue of three different types: heart muscle, kidney, and liver. Tissue samples were frozen and imaged on a 0.5 Tesla MRI scanner with ultrashort echo time (UTE) sequence. Signal intensity and T2* were determined as the temperature of the tissue samples was decreased from room temperature to approximately -40 degrees C. Statistical analysis was performed for (-20 degrees C, -5 degrees C) temperature interval. The findings of this study demonstrate that signal intensity and T2* are consistent across three types of tissue for (-20 degrees C, -5 degrees C) temperature interval. Both parameters can be used to calculate a single temperature calibration curve for all three types of tissue and potentially in the future serve as a foundation for tissue-independent MRI-based thermometry.

Magnetic hysteresis parameters and Day plot analysis to characterize diagenetic alteration in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Enkin, Randolph J.; Baker, Judith; Nourgaliev, Danis; Iassonov, Pavel; Hamilton, Tark S.

2007-06-01

The J meter coercivity spectrometer is a machine capable of rapid and simple measurement of magnetic hysteresis, isothermal remanence acquisition and magnetic viscosity of rocks and sediments. The J meter was used to study a suite of samples collected from strata in the gas hydrate-bearing JAPEX/JNOC/GSC Mallik 5L-38 well (69.5°N, 134.6°W) in the Mackenzie Delta of the northwestern Canadian Arctic. The Day plot of magnetic hysteresis ratios for these samples is exotic in that the points do not plot along a hyperbola as is usually observed. Rather, they plot as a scatter which is shown to contour into vertical slices using coercivity field (HC) or saturation magnetization (JS), and horizontal slices using the relative quantity of superparamagnetism (JSPM/JS). Optical microscopy reveals that the magnetic minerals are detrital magnetite and authigenic greigite. Greigite is dominant in sands which in situ had >70% gas hydrate saturation and in silts in which gas hydrate growth was blocked by insufficient porosity. We infer that the silts were the accumulation sites for solutes which had been excluded from the pore waters in neighboring coarser-grained sediments during the course of gas hydrate formation. Consequently, we conclude that magnetic properties are related to gas hydrate-related processes, and as such, may have potential as a method of remote sensing for gas hydrate deposits.

The role of water in gas hydrate dissociation

USGS Publications Warehouse

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

2004-01-01

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

New hydrate formation methods in a liquid-gas medium

NASA Astrophysics Data System (ADS)

Chernov, A. A.; Pil'Nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

New hydrate formation methods in a liquid-gas medium.

PubMed

Chernov, A A; Pil'nik, A A; Elistratov, D S; Mezentsev, I V; Meleshkin, A V; Bartashevich, M V; Vlasenko, M G

2017-01-18

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

New hydrate formation methods in a liquid-gas medium

PubMed Central

Chernov, A. A.; Pil’nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated. PMID:28098194

PAHs distribution in sediments associated with gas hydrate and oil seepage from the Gulf of Mexico.

PubMed

Wang, Cuiping; Sun, Hongwen; Chang, Ying; Song, Zhiguang; Qin, Xuebo

2011-12-01

Six sediment samples collected from the Gulf of Mexico were analyzed. Total concentrations of the PAHs ranged from 52 to 403 ng g(-1) dry weight. The lowest PAH concentration without 5-6 rings PAHs appeared in S-1 sample associated with gas hydrate or gas venting. Moreover, S-1 sample had the lowest organic carbon content with 0.85% and highest reduced sulfur level with 1.21% relative to other samples. And, analysis of the sources of PAHs in S-1 sample indicated that both pyrogenic and petrogenic sources, converserly, while S-8, S-10 and S-11 sample suggested petrogenic origin. The distribution of dibenzothiophene, fluorine and dibenzofuran and the maturity parameters of triaromatic steranes suggested that organic matters in S-1 sample were different from that in S-8, S-10 and S-11 sample. This study suggested that organic geochemical data could help in distinguish the characteristic of sediment associated with gas hydrate or with oil seepage. Copyright © 2011 Elsevier Ltd. All rights reserved.

Zernike phase contrast cryo-electron tomography of whole bacterial cells

PubMed Central

Guerrero-Ferreira, Ricardo C.; Wright, Elizabeth R.

2014-01-01

Cryo-electron tomography (cryo-ET) provides three-dimensional (3D) structural information of bacteria preserved in a native, frozen-hydrated state. The typical low contrast of tilt-series images, a result of both the need for a low electron dose and the use of conventional defocus phase-contrast imaging, is a challenge for high-quality tomograms. We show that Zernike phase-contrast imaging allows the electron dose to be reduced. This limits movement of gold fiducials during the tilt series, which leads to better alignment and a higher-resolution reconstruction. Contrast is also enhanced, improving visibility of weak features. The reduced electron dose also means that more images at more tilt angles could be recorded, further increasing resolution. PMID:24075950

Three-dimensional structural analysis of eukaryotic flagella/cilia by electron cryo-tomography

PubMed Central

Bui, Khanh Huy; Pigino, Gaia; Ishikawa, Takashi

2011-01-01

Electron cryo-tomography is a potential approach to analyzing the three-dimensional conformation of frozen hydrated biological macromolecules using electron microscopy. Since projections of each individual object illuminated from different orientations are merged, electron tomography is capable of structural analysis of such heterogeneous environments as in vivo or with polymorphism, although radiation damage and the missing wedge are severe problems. Here, recent results on the structure of eukaryotic flagella, which is an ATP-driven bending organelle, from green algae Chlamydomonas are presented. Tomographic analysis reveals asymmetric molecular arrangements, especially that of the dynein motor proteins, in flagella, giving insight into the mechanism of planar asymmetric bending motion. Methodological challenges to obtaining higher-resolution structures from this technique are also discussed. PMID:21169680

Innovations in Sampling Pore Fluids From Deep-Sea Hydrate Sites

NASA Astrophysics Data System (ADS)

Lapham, L. L.; Chanton, J. P.; Martens, C. S.; Schaefer, H.; Chapman, N. R.; Pohlman, J. W.

2003-12-01

We have developed a sea-floor probe capable of collecting and returning undecompressed pore water samples at in situ pressures for determination of dissolved gas concentrations and isotopic values in deep-sea sediments. In the summer of 2003, we tested this instrument in sediments containing gas hydrates off Vancouver Island, Cascadia Margin from ROPOS (a remotely operated vehicle) and in the Gulf of Mexico from Johnson-Sea-Link I (a manned submersible). Sediment push cores were collected alongside the probe to compare methane concentrations and stable carbon isotope compositions in decompressed samples vs. in situ samples obtained by probe. When sufficient gas was available, ethane and propane concentrations and isotopes were also compared. Preliminary data show maximum concentrations of dissolved methane to be 5mM at the Cascadia Margin Fish Boat site (850m water depth) and 12mM in the Gulf of Mexico Bush Hill hydrate site (550m water depth). Methane concentrations were, on average, five times as high in probe samples as in the cores. Carbon isotopic values show a thermogenic input and oxidative effects approaching the sediment-water interface at both sites. This novel data set will provide information that is critical to the understanding of the in situ processes and environmental conditions controlling gas hydrate occurrences in sediments.

Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

USGS Publications Warehouse

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

1997-01-01

Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Reliability of a Cryoscopic Micro-Osmometer Using 15-µL Plasma Samples to Measure Hydration Status in Varied Environmental Conditions

ERIC Educational Resources Information Center

Scanlan, Aaron T.; Richter-Stretton, Gina L.; Madueno, Maria C.; Borges, Nattai R.; Fenning, Andrew S.

2017-01-01

Measurement of plasma osmolality (P[subscript osm]) remains popular for assessing hydration status in exercise science. However, a controlled reliability assessment of micro-osmometry using small sample volumes to measure Posm remains to be performed. This study aimed to examine the reliability of a cryoscopic micro-osmometer requiring 15-µL…

Effect of osmotic dehydration pretreatment and glassy state storage on the quality attributes of frozen mangoes under long-term storage.

PubMed

Zhao, Jin-Hong; Xiao, Hong-Wei; Ding, Yang; Nie, Ying; Zhang, Yu; Zhu, Zhen; Tang, Xuan-Ming

2017-05-01

Changes in the quality of frozen mango cuboids were investigated during long-term glassy state storage with and without osmotic dehydration pretreatment. The mango cuboids were dehydrated in mixed solutions (sucrose: glucose: fructose in a ratio of 3.6:1:3) of different concentrations (30, 40, and 50% (wt/wt)) prior to freezing and then stored at -55 °C (in the glassy state) for 6 months. The results revealed that compared with the untreated samples, osmotic pretreatment decreased total color difference (reduced by 15.6-62.3%), drip loss (reduced by 8.2-29.5%) and titration acidity (reduced by 1.3-9.4%), while increasing hardness (increased by 48.8-82.3%), vitamin C content (increased by 72.5-120.6%) and total soluble solids (increased by 21.8-53.7%) of frozen mangoes after 6 months. Dehydration with a sugar concentration of 40% was considered as the optimal pretreatment condition. In addition, a storage temperature of -55 °C provided better retention of quality than rubbery state storage at -18 °C. With prolonged storage time, the quality of frozen mangoes continued to change, even in the glassy state. However, the changes in quality of the osmotic-dehydrated samples were less than those of the untreated samples. The current work indicates that osmotic pretreatment and glassy state storage significantly improved the quality of frozen mangoes during long-term storage.

Observations of mass fractionation of noble gases in synthetic methane hydrate

USGS Publications Warehouse

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

2011-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2004-10-01

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

Environmental Factors Related to a Semiarid Climate Influence the Freezability of Sperm from Collared Peccaries (Pecari tajacu Linnaeus, 1758).

PubMed

Maia, Keilla M; Souza, Ana L P; Praxedes, Erica C G; Bezerra, Luana G P; Silva, Andreia M; Campos, Livia B; Moreira, Samara S J; Apolinário, Carlos A C; Souza, João B F; Silva, Alexandre R

2018-04-30

The influence of environmental factors in a semiarid climate on characteristics of fresh and frozen/thawed sperm collected from collared peccaries (Pecari tajacu) was assessed. Semen from 11 male collared peccaries was collected by electroejaculation during the peaks of the dry and rainy periods while rainfall indices, air temperatures, relative humidity levels, and wind speeds were measured. The number, motility, morphology, osmotic response, and membrane integrity of sperm in the collected ejaculates were assessed. Samples were then frozen in liquid nitrogen, thawed, and reassessed. The rainfall index of the rainy period (73.2 mm) was significantly higher than that of the dry period (13.6 mm) and the relative humidity was significantly higher during the rainy period (74.6%) than it was during the dry period (66.8%). Air temperature and wind speed did not differ between the two periods. Characteristics of sperm in the fresh samples were not affected by environmental parameters. In contrast, computerized analysis revealed that sperm in samples frozen during the rainy period exhibited better post-thaw membrane integrity (28.6 ± 6%), motility (29.5 ± 7.7%), and rapid sperm population (13.7 ± 6.2%) than did sperm in samples frozen during the dry period (23.4 ± 3% membrane integrity, 14.6 ± 4.1% motility, and 4.1 ± 1.2% rapid sperm; p < 0.05). Other characteristics of the frozen/thawed sperm did not differ depending on the period in which they were collected. We demonstrated that environmental parameters did not affect the quality of fresh sperm, but could influence the freezability of sperm collected from collared peccaries raised under a semiarid climate.

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

NASA Astrophysics Data System (ADS)

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

2011-10-01

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

An assessment of the resolution limitation due to radiation-damage in X-ray diffraction microscopy

DOE PAGES

Howells, M. R.; Beetz, T.; Chapman, H. N.; ...

2008-11-17

X-ray diffraction microscopy (XDM) is a new form of x-ray imaging that is being practiced at several third-generation synchrotron-radiation x-ray facilities. Nine years have elapsed since the technique was first introduced and it has made rapid progress in demonstrating high-resolution three-dimensional imaging and promises few-nm resolution with much larger samples than can be imaged in the transmission electron microscope. Both life- and materials-science applications of XDM are intended, and it is expected that the principal limitation to resolution will be radiation damage for life science and the coherent power of available x-ray sources for material science. In this paper wemore » address the question of the role of radiation damage. We use a statistical analysis based on the so-called "dose fractionation theorem" of Hegerl and Hoppe to calculate the dose needed to make an image of a single life-science sample by XDM with a given resolution. We find that for simply-shaped objects the needed dose scales with the inverse fourth power of the resolution and present experimental evidence to support this finding. To determine the maximum tolerable dose we have assembled a number of data taken from the literature plus some measurements of our own which cover ranges of resolution that are not well covered otherwise. The conclusion of this study is that, based on the natural contrast between protein and water and "Rose-criterion" image quality, one should be able to image a frozen-hydrated biological sample using XDM at a resolution of about 10 nm.« less

Conventional freezing plus high pressure-low temperature treatment: Physical properties, microbial quality and storage stability of beef meat.

PubMed

Fernández, Pedro P; Sanz, Pedro D; Molina-García, Antonio D; Otero, Laura; Guignon, Bérengère; Vaudagna, Sergio R

2007-12-01

Meat high-hydrostatic pressure treatment causes severe decolouration, preventing its commercialisation due to consumer rejection. Novel procedures involving product freezing plus low-temperature pressure processing are here investigated. Room temperature (20°C) pressurisation (650MPa/10min) and air blast freezing (-30°C) are compared to air blast freezing plus high pressure at subzero temperature (-35°C) in terms of drip loss, expressible moisture, shear force, colour, microbial quality and storage stability of fresh and salt-added beef samples (Longissimus dorsi muscle). The latter treatment induced solid water transitions among ice phases. Fresh beef high pressure treatment (650MPa/20°C/10min) increased significantly expressible moisture while it decreased in pressurised (650MPa/-35°C/10min) frozen beef. Salt addition reduced high pressure-induced water loss. Treatments studied did not change fresh or salt-added samples shear force. Frozen beef pressurised at low temperature showed L, a and b values after thawing close to fresh samples. However, these samples in frozen state, presented chromatic parameters similar to unfrozen beef pressurised at room temperature. Apparently, freezing protects meat against pressure colour deterioration, fresh colour being recovered after thawing. High pressure processing (20°C or -35°C) was very effective reducing aerobic total (2-log(10) cycles) and lactic acid bacteria counts (2.4-log(10) cycles), in fresh and salt-added samples. Frozen+pressurised beef stored at -18°C during 45 days recovered its original colour after thawing, similarly to just-treated samples while their counts remain below detection limits during storage.

Microgravity

NASA Image and Video Library

1996-03-24

Astronaut Michael Clifford places a liquid nitrogen Dewar containing frozen protein solutions aboard Russia's space station Mir during a visit by the Space Shuttle (STS-76). The protein samples were flash-frozen on Earth and will be allowed to thaw and crystallize in the microgravity environment on Mir Space Station. A later crew will return the Dewar to Earth for sample analysis. Dr. Alexander McPherson of the University of California at Riverside is the principal investigator. Photo credit: NASA/Johnson Space Center.

Microgravity

NASA Image and Video Library

1996-09-20

Astronaut Tom Akers places a liquid nitrogen Dewar containing frozen protein solutions aboard Russia's space Station Mir during a visit by the Space Shuttle (STS-79). The protein samples were flash-frozen on Earth and will be allowed to thaw and crystallize in the microgravity environment on Mir Space Station. A later crew will return the Dewar to Earth for sample analysis. Dr. Alexander McPherson of the University of California at Riverside is the principal investigator. Photo credit: NASA/Johnson Space Center.

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.

A cryopreservation method for Pasteurella multocida from wetland samples

USGS Publications Warehouse

Moore, Melody K.; Shadduck, D.J.; Goldberg, Diana R.; Samuel, M.D.

1998-01-01

A cryopreservation method and improved isolation techniques for detection of Pasteurella multocida from wetland samples were developed. Wetland water samples were collected in the field, diluted in dimethyl sulfoxide (DMSO, final concentration 10%), and frozen at -180 C in a liquid nitrogen vapor shipper. Frozen samples were transported to the laboratory where they were subsequently thawed and processed in Pasteurella multocida selective broth (PMSB) to isolate P. multocida. This method allowed for consistent isolation of 2 to 18 organisms/ml from water seeded with known concentrations of P. multocida. The method compared favorably with the standard mouse inoculation method and allowed for preservation of the samples until they could be processed in the laboratory.

Cryo-electron microscopy and cryo-electron tomography of nanoparticles.

PubMed

Stewart, Phoebe L

2017-03-01

Cryo-transmission electron microscopy (cryo-TEM or cryo-EM) and cryo-electron tomography (cryo-ET) offer robust and powerful ways to visualize nanoparticles. These techniques involve imaging of the sample in a frozen-hydrated state, allowing visualization of nanoparticles essentially as they exist in solution. Cryo-TEM grid preparation can be performed with the sample in aqueous solvents or in various organic and ionic solvents. Two-dimensional (2D) cryo-TEM provides a direct way to visualize the polydispersity within a nanoparticle preparation. Fourier transforms of cryo-TEM images can confirm the structural periodicity within a sample. While measurement of specimen parameters can be performed with 2D TEM images, determination of a three-dimensional (3D) structure often facilitates more spatially accurate quantization. 3D structures can be determined in one of two ways. If the nanoparticle has a homogeneous structure, then 2D projection images of different particles can be averaged using a computational process referred to as single particle reconstruction. Alternatively, if the nanoparticle has a heterogeneous structure, then a structure can be generated by cryo-ET. This involves collecting a tilt-series of 2D projection images for a defined region of the grid, which can be used to generate a 3D tomogram. Occasionally it is advantageous to calculate both a single particle reconstruction, to reveal the regular portions of a nanoparticle structure, and a cryo-electron tomogram, to reveal the irregular features. A sampling of 2D cryo-TEM images and 3D structures are presented for protein based, DNA based, lipid based, and polymer based nanoparticles. WIREs Nanomed Nanobiotechnol 2017, 9:e1417. doi: 10.1002/wnan.1417 For further resources related to this article, please visit the WIREs website. © 2016 Wiley Periodicals, Inc.

Effect of sample handling on thiamine and thiaminolytic activity in alewife

USGS Publications Warehouse

Wright, G.M.; Brown, S.B.; Brown, L.R.; Moore, K.; Villella, M.; Zajicek, J.L.; Tillitt, D.E.; Fitzsimons, J.D.; Honeyfield, D.C.

2005-01-01

Alewives Alosa pseudoharengus were collected to evaluate handling and processing conditions that may affect the measurement of their thiamine-thiaminase content. Fish were captured by otter trawl, and reference samples of live fish were quick-frozen on dry ice immediately following capture. Other samples were placed on wet ice (4??C) or held in ambient lake water (21.5??C) for periods of up to 5 h before freezing. Total thiamine levels for reference samples averaged 26 nmol/g and consisted of 66, 15, and 19% thiamine pyrophosphate (TPP), thiamine monophosphate (TMP), and unphosphorylated thiamine (Th), respectively. After 120 min at either 4??C or 21.5??C, total thiamine concentrations were lower. At 21.5??C, the TPP proportion had decreased by 30 min and the proportion as Th increased after 60 min. In the groups sampled after 5 h, total thiamine concentrations were not altered but the proportion of TPP was lower and that of Th was higher than in reference samples. The stability of thiamine in thawed muscle samples from previously frozen alewives was poor (40% loss by 1 h at 22??C and 30% loss by 2 h at 4??C). Thiaminase activity averaged 5,975 pmol??g wet weight -1??min-1 in reference samples. In fresh-caught alewives, thiaminase activities were remarkably consistent throughout the sampling period. At 4??C, thiaminase activity in muscle tissue from previously frozen alewives was stable for the entire investigation period. At 25??C, the activity initially increased by 40% after 60 min but then decreased to 50% of initial value after 5 h. We conclude that sampling times greater than 25 min could cause some changes in the various thiamine forms and net loss in total thiamine. The thiamine content in previously frozen alewife samples is highly labile, requiring low temperatures during processing for analysis. ?? Copyright by the American Fisheries Society 2005.

Hydrogen speciation in hydrated layers on nuclear waste glass

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

Aines, R.D.; Weed, H.C.; Bates, J.K.

1987-12-31

The hydration of an outer layer on nuclear waste glasses in known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. In addition, molecular watermore » was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. The hydrated layer on the nuclear waste glasses appears to be of relatively low water content (4 to 7% by weight) and is not substantially hydroxylated. Thus, these layers do not have many of the properties associated with gel layers.« less

The influence of silanized nano-SiO{sub 2} on the hydration of cement paste: NMR investigations

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

Bede, A., E-mail: Andrea.Bede@phys.utcluj.ro; Pop, A.; Ardelean, I.

2015-12-23

It is known that by adding a small amount of nanoparticles to the cement-based materials a strong influence on the workability, strength and durability is obtained. These characteristics of the material are fundamentally determined by the hydration process taking place after mixing the cement grains with water. In the present study the influence introduced by the addition of nano-silica with silanized surfaces on the hydration process was investigated using low-field nuclear magnetic resonance (NMR) relaxometry. The cement samples were prepared using gray cement at a water-to-cement ratio of 0.4 and a 5% addition of nanosilica. The surface of the nanoparticlesmore » was modified using a coating of Silane A174. The cement pastes were monitored during their standard curing time of 28 days. It was established that, by using unmodified nanosilica particles, an acceleration of the hydration process takes place as compared with the pure cement paste. On the other side, by adding silanized nanoparticles, the dormancy stage significantly extends and the hydration process is slower. This slowing down process could enhance the mechanical strength of cement based materials as a result of a better compaction of the hydrated samples.« less

Evaluation of motility, membrane status and DNA integrity of frozen-thawed bottlenose dolphin (Tursiops truncatus) spermatozoa after sex-sorting and recryopreservation.

PubMed

Montano, G A; Kraemer, D C; Love, C C; Robeck, T R; O'Brien, J K

2012-06-01

Artificial insemination (AI) with sex-sorted frozen-thawed spermatozoa has led to enhanced management of ex situ bottlenose dolphin populations. Extended distance of animals from the sorting facility can be overcome by the use of frozen-thawed, sorted and recryopreserved spermatozoa. Although one bottlenose dolphin calf had been born using sexed frozen-thawed spermatozoa derived from frozen semen, a critical evaluation of in vitro sperm quality is needed to justify the routine use of such samples in AI programs. Sperm motility parameters and plasma membrane integrity were influenced by stage of the sex-sorting process, sperm type (non-sorted and sorted) and freezing method (straw and directional) (P<0.05). After recryopreservation, sorted spermatozoa frozen with the directional freezing method maintained higher (P<0.05) motility parameters over a 24-h incubation period compared to spermatozoa frozen using straws. Quality of sperm DNA of non-sorted spermatozoa, as assessed by the sperm chromatin structure assay (SCSA), was high and remained unchanged throughout freeze-thawing and incubation processes. Though a possible interaction between Hoechst 33342 and the SCSA-derived acridine orange was observed in stained and sorted samples, the proportion of sex-sorted, recryopreserved spermatozoa exhibiting denatured DNA was low (6.6±4.1%) at 6 h after the second thawing step and remained unchanged (P>0.05) at 24 h. The viability of sorted spermatozoa was higher (P<0.05) than that of non-sorted spermatozoa across all time points after recryopreservation. Collective results indicate that bottlenose dolphin spermatozoa undergoing cryopreservation, sorting and recryopreservation are of adequate quality for use in AI.

Frozen section evaluation via dynamic real-time non-robotic Telepathology system in a university Cancer center by resident / faculty cooperation team.

PubMed

Vosoughi, Aram; Smith, Paul Taylor; Zeitouni, Joseph A; Sodeman, Gregori M; Jorda, Merce; Gomez-Fernandez, Carmen; Garcia-Buitrago, Monica; Petito, Carol K; Chapman, Jennifer R; Campuzano-Zuluaga, German; Rosenberg, Andrew E; Kryvenko, Oleksandr N

2018-04-30

Frozen section telepathology interpretation experience has been largely limited to practices with locations significantly distant from one another with sporadic need for frozen section diagnosis. In 2010 we established a real-time non-robotic telepathology system in a very active cancer center for daily frozen section service. Herein, we evaluate its accuracy compared to direct microscopic interpretation performed in the main hospital by the same faculty and its cost-efficiency over a 1-year period. From 643 (1416 parts) cases requiring intraoperative consultation, 333 cases (690 parts) were examined by telepathology and 310 cases (726 parts) by direct microscopy. Corresponding discrepancy rates were 2.6% (18 cases: 6 (0.9%) sampling and 12 (1.7%) diagnostic errors) and 3.2% (23 cases: 8 (1.1%) sampling and 15 (2.1%) diagnostic errors), P=.63. The sensitivity and specificity of intraoperative frozen diagnosis were 0.92 and 0.99, respectively, in telepathology, and 0.90 and 0.99, respectively, in direct microscopy. There was no correlation of error incidence with post graduate year level of residents involved in the telepathology service. Cost analysis indicated that the time saved by telepathology was $19691 over one year of the study period while the capital cost for establishing the system was $8924. Thus, real-time non-robotic telepathology is a reliable and easy to use tool for frozen section evaluation in busy clinical settings, especially when frozen section service involves more than one hospital, and it is cost efficient when travel is a component of the service. Copyright © 2018. Published by Elsevier Inc.

The effect of refrigerated and frozen storage on butter flavor and texture.

PubMed

Krause, A J; Miracle, R E; Sanders, T H; Dean, L L; Drake, M A

2008-02-01

Butter is often stored for extended periods of time; therefore, it is important for manufacturers to know the refrigerated and frozen shelf life. The objectives of this study were to characterize the effect of refrigerated and frozen storage on the sensory and physical characteristics of butter. Fresh butter was obtained on 2 occasions from 2 facilities in 113-g sticks and 4-kg bulk blocks (2 facilities, 2 package forms). Butters were placed into both frozen (-20 degrees C) and refrigerated storage (5 degrees C). Frozen butters were sampled after 0, 6, 12, 15, and 24 mo; refrigerated butters were sampled after 0, 3, 6, 9, 12, 15, and 18 mo. Every 3 mo, oxidative stability index (OSI) and descriptive sensory analysis (texture, flavor, and color) were conducted. Every 6 mo, peroxide value (PV), free fatty acid value (FFV), fatty acid profiling, vane, instrumental color, and oil turbidity were examined. A mixed-model ANOVA was conducted to characterize the effects of storage time, temperature, and package type. Storage time, temperature, and package type affected butter flavor, OSI, PV, and FFV. Refrigerated butter quarters exhibited refrigerator/stale off-flavors concurrent with increased levels of oxidation (lower oxidative stability and higher PV and FFV) within 6 mo of refrigerated storage, and similar trends were observed for refrigerated bulk butter after 9 mo. Off-flavors were not evident in frozen butters until 12 or 18 mo for quarters and bulk butters, respectively. Off-flavors in frozen butters were not correlated with instrumental oxidation measurements. Because butter is such a desirable fat source in terms of flavor and textural properties, it is important that manufacturers understand how long their product can be stored before negative attributes develop.

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

NASA Astrophysics Data System (ADS)

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

2006-08-01

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

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

USGS Publications Warehouse

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

2006-01-01

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

Presentation of frozen shoulder among diabetic and non-diabetic patients.

PubMed

Uddin, Mohammad Moin; Khan, Aminuddin A; Haig, Andrew J; Uddin, Mohammad Kafil

2014-12-01

The literature is inconsistent regarding the level of pain and disability in frozen shoulder patients with or without diabetes mellitus. The aim of this study is to evaluate some demographic features of frozen shoulder patients and to look into the disparity of information by comparing the level of pain and disability due to frozen shoulder between diabetic and non-diabetic people. This is a prospective comparative study. People with frozen shoulder attending an outpatient department were selected by consecutive sampling. Disability levels were assessed by the Shoulder Pain & Disability Index (SPADI). Means of pain and disability scores were compared using unpaired t-test. Among 140 persons with shoulder pain 99 (71.4%) had frozen shoulder. From the participating 40 frozen shoulder patients, 26 (65%) were males and 14 (35%) were females. Seventeen participants (42.5%) were diabetic, two (5%) had impaired glucose tolerance and 21 (52.5%) patients were non-diabetic. Mean disability scores (SPADI) were 51 ± 15.5 in diabetic and 57 ± 16 in non-diabetic persons. The differences in pain and disability level were not statistically significance (respectively, p = 0.24 and p = 0.13 at 95% confidence interval). No difference was found in level of pain and disability level between frozen shoulder patients with and without diabetes.

Short communication: The effects of frozen storage on the survival of probiotic microorganisms found in traditionally and commercially manufactured kefir.

PubMed

O'Brien, K V; Aryana, K J; Prinyawiwatkul, W; Ordonez, K M Carabante; Boeneke, C A

2016-09-01

Kefir is a fermented milk traditionally made from a unique starter culture, which consists of numerous bacteria and yeast species bound together in an exopolysaccharide matrix produced by certain lactic acid bacteria. Many health benefits are associated with traditionally produced kefir; however, bulging and leaking packaging, caused by secondary yeast fermentation during storage, has limited large-scale manufacture. Commercial kefir products have been designed to reduce these effects by using a pure starter culture consisting of a mixture of bacteria and yeast species that give a flavor similar to traditional kefir, but some health benefits may be lost in commercial production due to reduced microbial diversity and lack of beneficial exopolysaccharides. In this study, traditional and commercial kefir was frozen to study the effects of frozen storage on the viability of probiotic bacteria over time. Traditional kefir was prepared by inoculating 1L of pasteurized whole goat milk with approximately 30g of kefir grains. Commercial kefir was prepared by inoculating 1L of full-fat, pasteurized goat milk with a commercial kefir starter. The milk was allowed to ferment at room temperature (24-28°C) until pH 4.6 was reached. Samples were frozen (-8 to -14°C) immediately following the completion of fermentation and were thawed and plated for lactobacilli, lactococci, and yeasts on d 0, 7, 14, and 30 of frozen storage. Lactobacilli, lactococci, and yeasts were significantly reduced in number during frozen storage; however, the traditionally produced kefir was shown to have significantly higher counts of bacteria and yeast at each sampling. We concluded that frozen storage and the development of frozen kefir products could eliminate most packaging concerns associated with the large-scale manufacture of traditionally produced kefir, resulting in increased production and marketability of this healthful product. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Impact of Frozen Storage on the Anthocyanin and Polyphenol Content of American Elderberry Fruit Juice

PubMed Central

Johnson, Mitch C.; Thomas, Andrew L.; Greenlief, C. Michael

2015-01-01

The effects of frozen storage on the anthocyanin and polyphenol content of elderberry fruit juice are investigated. Juice from three genotypes of American elderberry (Adams II, Bob Gordon, and Wyldewood) was screened for total phenolic (TP) and total monomeric anthocyanin (TMA) content with spectrophotometric methods. The individual anthocyanin content (IAC) of the juice was tested by coupling solid phase extraction with ultra-performance liquid chromatography/tandem mass spectrometry. Juice samples were tested initially upon harvest, then again after 3, 6, and 9 months of frozen storage. Juice from the three different genotypes had significantly different TP, TMA, and IAC profiles initially (p<0.05). The TP,, TMA, and IAC content of the juice from different genotypes were significantly affected (p<0.05) by the frozen storage time, suggesting that both genotype and length of frozen storage time can affect the anthocyanin content of elderberry fruit juice. PMID:26028422

Effects of ionizing radiation on sensorial, chemical, and microbiological quality of frozen corn and peas.

PubMed

Fan, Xuetong; Sokorai, Kimberly J B

2007-08-01

The effects of irradiation (0, 1.8, and 4.5 kGy) on the quality of frozen corn and peas were investigated during a 12month period of postirradiation storage at -18 degrees C. Irradiation of frozen corn and peas caused a reduction in ascorbic acid content of both vegetables and a loss of texture in peas but had no significant effects on instrumental color parameters (L*, a*, and b*), carotenoid and chlorophyll content, or antioxidant capacity of corn and peas. Irradiation reduced microbial loads of frozen peas and increased display life at 23 degrees C of thawed peas by preserving the green color, apparently because of slower increases in the population of acid-producing microorganisms in the irradiated samples. Overall, irradiation significantly reduced the microbial load and increased the display life of peas and had minimal detrimental effects on the quality of frozen corn and peas.

Effects of type of freeze straw and thaw temperature on the fertilizing capacity of frozen chicken semen.

PubMed

Duplaix, M; Sexton, T J

1984-04-01

Two experiments were conducted to determine the relationship between thawing temperature and the type of straw in which chicken semen was frozen. In Experiment 1, semen was frozen in three different types of plastic straws: US (.5-ml capacity), French (.5-ml capacity), and French mini (.25-ml capacity). Experiment 1 was divided into two trials to compare semen packaged in the different straws and thawed at 15 (Trial 1) or .5 C (Trial 2). Although there were distinguishable features of the freeze and thaw curves between samples frozen in the different straws, the type of freeze straw had no effect on the fertilizing capacity of frozen semen when thaw temperature was held constant: fertility, Days 2 to 4 after artificial insemination, ranged from 16 to 27% for Trial 1 and 45 to 47% for Trial 2. In Experiment 2, semen was frozen in US straws and thawed at either .5 or 15 C to assess the effect of the thaw temperature. Fertility of frozen semen, Days 2 to 4 after artificial insemination, was significantly higher when semen was thawed at .5 than at 15 C (62 vs. 20%).

Anomalous preservation of pure methane hydrate at 1 atm

USGS Publications Warehouse

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

2001-01-01

Direct measurement of decomposition rates of pure, polycrystalline methane hydrate reveals a thermal regime where methane hydrate metastably `preserves' in bulk by as much as 75 K above its nominal equilibrium temperature (193 K at 1 atm). Rapid release of the sample pore pressure at isothermal conditions between 242 and 271 K preserves up to 93% of the hydrate for at least 24 h, reflecting the greatly suppressed rates of dissociation that characterize this regime. Subsequent warming through the H2O ice point then induces rapid and complete dissociation, allowing controlled recovery of the total expected gas yield. This behavior is in marked contrast to that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) test conditions, where dissociation rates increase monotonically with increasing temperature. Anomalous preservation has potential application for successful retrieval of natural gas hydrate or hydrate-bearing sediments from remote settings, as well as for temporary low-pressure transport and storage of natural gas.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Effect of sucrose and pectin addition on physical, chemical, thermal and rheological properties of frozen/thawed pineapple pulps

NASA Astrophysics Data System (ADS)

Conceição, Márcia Cavalcante; Fernandes, Tatiana Nunes; Prado, Mônica Elisabeth Torres; de Resende, Jaime Vilela

2012-09-01

Pectin (0-1.0 g/100 mL) and sucrose (0-20 g/100 mL) were added to pineapple pulp to improve their rheological properties, thermal properties and stability after freezing and thawing processes. The properties of the mixes were characterized before and after freezing and thawing. Samples were frozen at -20°C, and the freeze concentration was evaluated every 60 min. The thawing rate was evaluated at 19°C and quantified by photographic editing and image analysis software. The thawing rates and values for the freeze concentration were leveled out at pectin concentrations above 0.5 g/100 mL pectin, which indicated that pectin functions to maintain structural homogeneity during freezing. In the thawed samples, the plastic viscosity values were leveled out from pectin concentrations (0.25-0.75 g/100 mL) as the sucrose concentration increased when compared to unfrozen samples. The differences between the rheological parameters of the unfrozen and frozen/thawed pulps, the higher yield stress values after thawing were attributed to the size of suspended particles in the pulp. Applications can specify formulations of frozen products containing pectin, where these properties can be handled after thawing the product.

Gas geochemistry of the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: implications for gas hydrate exploration in the Arctic

USGS Publications Warehouse

Lorenson, T.D.; Collett, T.S.; Hunter, R.B.

2011-01-01

Gases were analyzed from well cuttings, core, gas hydrate, and formation tests at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled within the Milne Point Unit, Alaska North Slope. The well penetrated a portion of the Eileen gas hydrate deposit, which overlies the more deeply buried Prudhoe Bay, Milne Point, West Sak, and Kuparuk River oil fields. Gas sources in the upper 200 m are predominantly from microbial sources (C1 isotopic compositions ranging from −86.4 to −80.6‰). The C1 isotopic composition becomes progressively enriched from 200 m to the top of the gas hydrate-bearing sands at 600 m. The tested gas hydrates occur in two primary intervals, units D and C, between 614.0 m and 664.7 m, containing a total of 29.3 m of gas hydrate-bearing sands. The hydrocarbon gases in cuttings and core samples from 604 to 914 m are composed of methane with very little ethane. The isotopic composition of the methane carbon ranges from −50.1 to −43.9‰ with several outliers, generally decreasing with depth. Gas samples collected by the Modular Formation Dynamics Testing (MDT) tool in the hydrate-bearing units were similarly composed mainly of methane, with up to 284 ppm ethane. The methane isotopic composition ranged from −48.2 to −48.0‰ in the C sand and from −48.4 to −46.6‰ in the D sand. Methane hydrogen isotopic composition ranged from −238 to −230‰, with slightly more depleted values in the deeper C sand. These results are consistent with the concept that the Eileen gas hydrates contain a mixture of deep-sourced, microbially biodegraded thermogenic gas, with lesser amounts of thermogenic oil-associated gas, and coal gas. Thermal gases are likely sourced from existing oil and gas accumulations that have migrated up-dip and/or up-fault and formed gas hydrate in response to climate cooling with permafrost formation.

Arrangement of photosystem II and ATP synthase in chloroplast membranes of spinach and pea.

PubMed

Daum, Bertram; Nicastro, Daniela; Austin, Jotham; McIntosh, J Richard; Kühlbrandt, Werner

2010-04-01

We used cryoelectron tomography to reveal the arrangements of photosystem II (PSII) and ATP synthase in vitreous sections of intact chloroplasts and plunge-frozen suspensions of isolated thylakoid membranes. We found that stroma and grana thylakoids are connected at the grana margins by staggered lamellar membrane protrusions. The stacking repeat of grana membranes in frozen-hydrated chloroplasts is 15.7 nm, with a 4.5-nm lumenal space and a 3.2-nm distance between the flat stromal surfaces. The chloroplast ATP synthase is confined to minimally curved regions at the grana end membranes and stroma lamellae, where it covers 20% of the surface area. In total, 85% of the ATP synthases are monomers and the remainder form random assemblies of two or more copies. Supercomplexes of PSII and light-harvesting complex II (LHCII) occasionally form ordered arrays in appressed grana thylakoids, whereas this order is lost in destacked membranes. In the ordered arrays, each membrane on either side of the stromal gap contains a two-dimensional crystal of supercomplexes, with the two lattices arranged such that PSII cores, LHCII trimers, and minor LHCs each face a complex of the same kind in the opposite membrane. Grana formation is likely to result from electrostatic interactions between these complexes across the stromal gap.

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

USGS Publications Warehouse

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

2011-01-01

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

Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder

PubMed Central

Thurber, Kent R.; Tycko, Robert

2009-01-01

Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of 79Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the 79Br NMR frequency to that of 13C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions. PMID:18930418

Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder.

PubMed

Thurber, Kent R; Tycko, Robert

2009-01-01

Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of (79)Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the (79)Br NMR frequency to that of (13)C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions.

Studies of molecular diffusion in single-supported bilayer lipid membranes at low hydration by quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Miskowiec, A.; Bai, M.; Lever, M.; Taub, H.; Hansen, F. Y.; Jenkins, T.; Tyagi, M.; Neumann, D. A.; Diallo, S. O.; Mamontov, E.; Herwig, K. W.

2011-03-01

We have extended our investigation of the quasielastic neutron scattering from single-supported bilayer lipid membranes to a sample of lower hydration using the backscattering spectrometer BASIS at the SNS of ORNL. To focus on the diffusive motion of the water, tail-deuterated DMPC membranes were deposited onto Si O2 -coated Si(100) substrates and characterized by AFM. Compared to a sample of higher hydration, the dryer sample does not have a step-like freezing transition at ~ 267 K and shows less intensity at higher temperatures of a broad Lorentzian component representing bulk-like water. However, the broad component of the ``wet'' and ``dry'' samples behaves similarly at lower temperatures. The dryer sample also shows evidence of a narrow Lorentzian component that has a different temperature dependence than that attributed to conformational changes of the alkyl tails of the lipid molecules in the wet sample. We tentatively identify this slower diffusive motion (time scale ~ 1 ns) with water more tightly bound to the membrane. Supported by NSF Grant No. DMR-0705974.

An experimental challenge: Unraveling the dependencies of ultrasonic and electrical properties of sandy sediments with pore-filling gas hydrates

NASA Astrophysics Data System (ADS)

Heeschen, Katja; Spangenberg, Erik; Seyberth, Karl; Priegnitz, Mike; Schicks, Judith M.

2016-04-01

The accuracy of gas hydrate quantification using seismic or electric measurements fundamentally depends on the knowledge of any factor describing the dependencies of physical properties on gas hydrate saturation. Commonly, these correlations are the result of laboratory measurements on artificially produced gas hydrates of exact saturation. Thus, the production of gas hydrates and accurate determination of gas hydrate concentrations or those of a substitute are a major concern. Here we present data of both, seismic and electric measurements on accurately quantified pore-filling ice as a substitute for natural gas hydrates. The method was validated using selected gas hydrate saturations in the same experimental set-up as well as literature data from glass bead samples [Spangenberg and Kulenkampff, 2006]. The environmental parameters were chosen to fit those of a possible gas hydrate reservoir in the Danube Delta, which is in the focus of models for joint inversions of seismic and electromagnetic data in the SUGAR III project. The small effective pressures present at this site proved to be yet another challenge for the experiments. Using a more powerful pulse generator and a 4 electrode electric measurement, respectively, models for a wide range of gas hydrate saturations between 20 - 90 % vol. could be established. Spangenberg, E. and Kulenkampff, J., Influence of methane hydrate content on electrical sediment properties. Geophysical Research Letters 2006, 33, (24).

Concentration of Nitrate near the Surface of Frozen Salt Solutions

NASA Astrophysics Data System (ADS)

Michelsen, R. R. H.; Marrocco, H. A.

2017-12-01

The photolysis of nitrate near the surface of snow and ice in Earth's environment results in the emission of nitrogen oxides (NO, NO2 and, in acidic snow, HONO) and OH radicals. As a result, nitrate photolysis affects the composition and oxidative capacity of the overlying atmosphere. Photolysis yields depend in part on how much nitrate is close enough to the surface to be photolyzed. These concentrations are assumed to be higher than the concentrations of nitrate that are measured in melted snow and ice samples. However, near-surface concentrations of nitrate have not been directly measured. In this work, laboratory studies of the concentration of nitrate in frozen aqueous solutions are described. Individual aqueous solutions of nitric acid, sodium nitrate, and magnesium nitrate were mixed. Attenuated total reflection infrared spectroscopy was utilized to measure the nitrate and liquid water signals within 200 - 400 nm of the lower surface of frozen samples. Temperature was varied from -18°C to -2°C. In addition to the amount of nitrate observed, changes to the frozen samples' morphology with annealing are discussed. Nitrate concentrations near the lower surface of these frozen solutions are high: close to 1 M at warmer temperatures and almost 4 M at the coldest temperature. Known freezing point depression data describe the observed concentrations better than ideal solution thermodynamics, which overestimate concentration significantly at colder temperatures. The implications for modeling the chemistry of snow are discussed. Extending and relating this work to the interaction of gas-phase nitric acid with the surfaces of vapor-deposited ice will also be explored.

The use of hydrated lime as an antistripping additive : final report.

DOT National Transportation Integrated Search

1987-01-01

The purpose of this investigation was to evaluate the performance of six test sections of asphalt concrete that contained no additive, hydrated lime, and a chemical additive. Tests were also conducted on pavement samples taken periodically to determi...

Microwave absorption in substances that form hydration layers with water

NASA Astrophysics Data System (ADS)

Garner, H. R.; Ohkawa, T.; Tuason, O.; Lee, R. L.

1990-12-01

The microwave absorption of certain water soluble polymers (polyethylene glycol, polyvinyl pyrrolidone, proteins, and DNA) in solution is composed of three parts: absorption in the free water, absorption in the substance, and absorption in the hydration layer. Ethanol, sucrose, glycerol, and sodium acetate, which form weak hydrogen bonds or have an ionic nature in aqueous solutions, also have microwave absorption signatures similar to polymers that form hydration layers. The frequency-dependent absorption of the free water and of the hydration layer water is described by a simple Debye relaxation model. The absorption per unit sample volume attributable to the hydration layer is solute concentration dependent, and a simple model is used to describe the dependence. The hydration-layer relaxation time was found to vary from substance to substance and with solute concentration. The relaxation time was also found to be independent of solute length.

Quasielastic and inelastic neutron scattering study of the hydration of monoclinic and triclinic tricalcium silicate

NASA Astrophysics Data System (ADS)

Peterson, Vanessa K.; Brown, Craig M.; Livingston, Richard A.

2006-08-01

The hydration of Mg-stabilized triclinic and monoclinic tricalcium silicate samples were studied using quasielastic neutron scattering to follow the fixation of hydrogen into the reaction products and by applying hydration models to the data. The quantity of Ca(OH) 2 produced during hydration was also determined using inelastic neutron scattering. The monoclinic form was found to be intrinsically less reactive that the triclinic form. The monoclinic form was also confirmed to produce more product than the triclinic form after 50 h, a process found to occur through a longer, rather than earlier, nucleation and growth regime. Results indicated an increase in the permeability of the hydration layer product relative to the triclinic form and the increase in the length of the nucleation and growth regime was thus attributed to an alteration in morphology or structure of the hydration layer product, extending the time for diffusion limited mechanics to be reached.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

76 FR 31575 - United States Standards for Grades of Frozen Onions

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-01

... processors of frozen onions in the United States. The petition provided information on style, sample size... change in the style designations for minced style, and a correction to the text. The members agreed with the proposed section concerning requirements for Styles, Type I, Whole onions and Type II, Pearl...

Effect of Chitin Isolated from Crustaceans and Cephalopods on Denaturation of Fish Myofibrillar Protein and the State of Water during Frozen Storage

NASA Astrophysics Data System (ADS)

Arredondo Romero, Eduardo; Nakamura, Yukio; Yamashita, Yasumitsu; Ichikawa, Hisashi; Goto, Shingi; Osatomi, Kiyoshi; Nozaki, Yukinori

From the point of view of utilization of shells as a waste product of fishery industry, the cryoprotective effect of chitin made from shell of crustaceans (Japanese fan lobster and Japanese swimming crab) and cartilage of cephalopods (spear squid) are studied. Chitin from the shells and cartilage were added to lizard fish myofibrils, and the changes of unfrozen water in myofibrils and ATPase activity of myofibrillar protein were observed during frozen storage at -250°C for 120days. The amount of unfrozen water were increased by addition of three kinds of chitin, and decreased moderately during forzen storage. Whereas, in the chitin free sample, the amount of unfrozen water were decreased rapidly during frozen storage. Changes of ATPase activity of samples showed similar tendency to that of the amount of unfrozen water. The present moderate cryoprotective effect of chitin and data of unfrozen water and ATPase activity of myofibrillar protein suggest the importance of the amount of unfrozen water in frozen matrix.

Micromechanisms of fatigue crack growth in polycarbonate polyurethane: Time dependent and hydration effects.

PubMed

Ford, Audrey C; Gramling, Hannah; Li, Samuel C; Sov, Jessica V; Srinivasan, Amrita; Pruitt, Lisa A

2018-03-01

Polycarbonate polyurethane has cartilage-like, hygroscopic, and elastomeric properties that make it an attractive material for orthopedic joint replacement application. However, little data exists on the cyclic loading and fracture behavior of polycarbonate polyurethane. This study investigates the mechanisms of fatigue crack growth in polycarbonate polyurethane with respect to time dependent effects and conditioning. We studied two commercially available polycarbonate polyurethanes, Bionate® 75D and 80A. Tension testing was performed on specimens at variable time points after being removed from hydration and variable strain rates. Fatigue crack propagation characterized three aspects of loading. Study 1 investigated the impact of continuous loading (24h/day) versus intermittent loading (8-10h/day) allowing for relaxation overnight. Study 2 evaluated the effect of frequency and study 3 examined the impact of hydration on the fatigue crack propagation in polycarbonate polyurethane. Samples loaded intermittently failed instantaneously and prematurely upon reloading while samples loaded continuously sustained longer stable cracks. Crack growth for samples tested at 2 and 5Hz was largely planar with little crack deflection. However, samples tested at 10Hz showed high degrees of crack tip deflection and multiple crack fronts. Crack growth in hydrated samples proceeded with much greater ductile crack mouth opening displacement than dry samples. An understanding of the failure mechanisms of this polymer is important to assess the long-term structural integrity of this material for use in load-bearing orthopedic implant applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantitative degassing of gas hydrate-bearing pressure cores from Green Canyon 955, Gulf of Mexico

NASA Astrophysics Data System (ADS)

Phillips, S. C.; Holland, M. E.; Flemings, P. B.; Schultheiss, P. J.; Waite, W. F.; Petrou, E. G.; Jang, J.; Polito, P. J.; O'Connell, J.; Dong, T.; Meazell, K.

2017-12-01

We present results from 20 quantitative degassing experiments of pressure-core sections collected during Expedition UT-GOM2-1 from Green Canyon 955 in the northern Gulf of Mexico. These experiments highlight an average pore-space methane hydrate saturation, Sh, of 59% (min: 12%; max 87%) in sediments between 413 and 440 mbsf in 2032 m water depth. There is a strong lithofacies control of hydrate saturation within the reservoir, with a high saturation sandy silt facies (Sh of 65 to 87%) interbedded with a low saturation clayey silt facies (Sh of 12 to 30%). Bedding occurs on the scale of tens of centimeters. Outside of the main hydrate reservoir, methane hydrate occurs in low saturations (Sh of 0.8 to 3%). Hydrate saturations exhibit a strong correlation (R2=0.89) with the average P-wave velocity measured through the degassed sections. These preliminary hydrate saturations were calculated assuming a porosity of 40% with core filling the full internal diameter of the core liner. Gas recovered during these experiments is composed of almost entirely methane, with an average of 94 ppm ethane and detectable, but not quantifiable, propane. Degassed pressure cores were depressurized through a manifold by the stepwise release of fluid, and the volumes of produced gas and water were monitored. The core's hydrostatic pressure was measured and recorded continuously at the manifold. Pressure and temperature were also measured by data storage tags within the sample chambers. Two slow, multi-day degassing experiments were performed to estimate the in situ salinity within core sections. Based on temperature and pressure observations at the point of the initial pressure rebound due to hydrate dissociation, we estimate the salinity within these samples to be between 33 and 42 g kg-1.

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

PubMed

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

2017-05-24

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

The effect of elevated methane pressure on methane hydrate dissociation

USGS Publications Warehouse

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

2004-01-01

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

Effects of frozen storage on survival of Staphylococcus aureus and enterotoxin production in precooked tuna meat.

PubMed

Wu, Xulei; Su, Yi-Cheng

2014-08-01

This study investigated the survival of Staphylococcus aureus in precooked tuna meat for producing canned products during frozen storage (-20 ± 2 °C) as well as its growth and enterotoxin production at 35 to 37 °C after the storage. Samples (50 ± 5 g) of precooked albacore (loin, chunk, and flake) and skipjack (chunk and flake) tuna were inoculated with 5 enterotoxin-producing strains of S. aureus at a level of approximately 3.5 log CFU/g and individually packed in a vacuum bag after 3 h incubation at 35 to 37 °C. Vacuum-packed samples were stored in a freezer (-20 ± 2 °C) for 4 wk. The frozen samples were then thawed in 37 °C circulating water for 2 h and incubated at 35 to 37 °C for 22 h. Populations of S. aureus in all precooked tuna samples decreased slightly (<0.7 log CFU/g) after 4 wk of storage at -20 ± 2 °C, but increased rapidly once the samples were thawed and held at 35 to 37 °C. Total S. aureus counts in albacore and skipjack samples increased by greater than 3 log CFU/g after 6 and 8 h of exposure to 35 to 37 °C, respectively. All samples became spoiled after 10 h of exposure to 35 to 37 °C, while no enterotoxin was detected in any samples. However, enterotoxins were detected in albacore loin and other samples after 12 and 24 h of incubation at 35 to 37 °C, respectively. Frozen precooked tuna meat should be used for producing canned tuna within 6 to 8 h of thawing to avoid product spoilage and potential enterotoxin production by S. aureus in contaminated precooked tuna meat. © 2014 Institute of Food Technologists®

Rehydration properties of hybrid method dried fruit enriched by natural components

NASA Astrophysics Data System (ADS)

Kowalska, Hanna; Marzec, Agata; Kowalska, Jolanta; Ciurzyńska, Agnieszka; Samborska, Kinga; Bialik, Michał; Lenart, Andrzej

2018-04-01

The aim of the study was to determine the impact of osmotic pre-dehydration and drying of fruit on the rehydration properties of dried fruit. Herein, the effect of fruit juice, applied as a natural enriching substance was very important. In addition, the properties of dried fruits obtained through combined air-drying and subsequent microwave-vacuum drying with `puffing' effect were similar to the freeze-dried fruits, but showed other rehydration properties. As raw material, frozen strawberry (Honeoye variety) and fresh apples (Idared variety) were used in the study. The apples and partially defrosted strawberries were prior dehydrated in solutions of sucrose and a mixture of sucrose with chokeberry juice concentrate at 50°C for 2 h. Next, the fruit samples were dried by one of two ways: air-drying (50°C, 5 h) and microwavevacuum drying for about 360 s; and freeze-drying (30°C, 63 Pa, 24 h). The rehydration was carried out in distilled water (20°C, 5 h). The osmotic pre-dehydration hindered fruit drying process. The impact of drying method became particularly evident while examining the kinetics of rehydration. During the rehydration of the pre-dehydrated dried fruit a slower hydration could be observed. Freeze-dried strawberries absorbed 2-3 times more water than those dried by the `puffing' effect.

Sliding-surface-liquefaction of sand-dry ice mixture and submarine landslides

NASA Astrophysics Data System (ADS)

Fukuoka, H.; Tsukui, A.

2010-12-01

In the historic records of off-shore mega-earthquakes along the subduction zone offshore Japan, there are a lot of witnesses about large-scale burning of flammable gas possibly ejected from sea floor. This gas was supposed to be the dissolved methane hydrates (MH), which have been found in the soundings of IODP and other oceanology projects. Since the vast distribution of the BSR in the continental margins, a lot of papers have been published which pointed out the possibilities of that gasification of those hydrates could have triggered gigantic submarine landslides. Global warming or large earthquake or magma intrusion may trigger extremely deep gigantic landslides in continental margins that which could cause catastrophic tsunami. However, recent triaxial compression tests on artificially prepared sand-MH-mixture samples revealed that the they have slightly higher strength than the ones of only sands and MH’s endothermal characteristics may resist against accelerating shear and large-displacement landslides as well. While, the stress-controlled undrained ring shear apparatuses have been developed by Sassa and Fukuoka at Disaster Prevention Research Institute, Kyoto University to reproduce subaerial landslides induced by earthquakes and rainfalls. Using the apparatuses, they found localized liquefaction phenomenon along the deep saturated potential sliding surface due to excess pore pressure generation during the grain crushing induced bulk volume change. This phenomenon was named as “sliding surface liquefaction.” Similar sudden large pore pressure generation was observed in pore pressure control test simulating rain-induced landslides. In this paper, authors examined the shear behavior of the dry sand-dry ice mixture under constant normal stress and shear speed control tests using the latest ring shear apparatus. Sample was mixture of silica sands and dry-ice pellets (frozen carbon-dioxide). Those mixtures are often used for studying the mechanism of the methane hydrates in laboratories because no explosion protection facility is required. In order to prevent rapid gasification, the specimen was prepared without water. Applied total normal stress was 200 kPa and initial normal stress was maintained at about 70 kPa by slightly opening the drainage valve to vent pressured CO2 gas. When the sample was sheared at 30 cm/s, the stress path reached failure line of friction angle of about 37 degrees immediately. However, excess pore air pressure increased soon after and the stress path moved to the origin along the failure line. This means rapid shearing generates frictional heat and it accelerates the gasification of dry ice quickly. On the other hand, crushing of pellets may contribute to increase the total surface area of dry ice and to acceleration of gasification, to some extent. Authors are conducting to examine the velocity weakening characteristics of the samples and upcoming results will give more detail of the mechanism. But this sliding-surface-liquefaction in the mixture supports the possibility of similar accelerating displacement in the sand-MH mixture or boundaries between MH and sand layer induced by certain strong ground motion under sea floor.

INFLUENCE OF INTRAMUSCULAR FAT LEVEL ON ORGANOLEPTIC, PHYSICAL, AND CHEMICAL CHARACTERISTICS OF IRRADIATED PORK. II. LOW-TEMPERATURE LONG-TIME PRE-IRRADIATION HEAT TREATMENT

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

Bray, R.W.; Weckel, K.G.; Evans, G.W.

1964-02-01

Pork muscle (longissimus dorsi) was graded in three marbling levels by both visual appraisal and ether-extraction analysis of total fat. A low- temperature (121 deg F, gradually increasing to 191 deg F), long-time (19-hr) heat treatment was used for enzyme inactivation. Samples were packed under vacuum in rigid containers and irradiated to 4.5 Mrad with gamma radiation. Irradiated and frozen control samples were evaluated at intervals over a 180-day period. The heat treatment caused excessive connective-tissue breakdown as evidenced by a soft, dry texture. Marbling level had no significant effect on consumer-panel judgments of irradiated or frozen control samples (servedmore » plain, without bread). Lower degrees of marbling were preferred in irradiated sandwich items. Irradiated samples were less preferred than frozen control samples in both plain and sandwich form. Hunter L (color) values a/sub L/ (redness), hue, and saturation attributes were increased by irradiation treatment. Hunter L and b/sub L/ (yellowness) values of highly marbled irradiated sample-s were elevated. Highly marbled samples displayed greater tenderness qualities, as evidenced by mechanical tenderness measurements. Expressible moisture values were decreased by marbling degree and radiation treatment and increased by advancing storage time. As a measure of oxidation rancidity, thiobarbituric acid values were increased by increasing levels of marbling and advancing storage time, but were not influenced by preservation method. No significant differences in pH values due to marbling level or preservation method were detected. Bacteriologic counts of randomly selected irradiated samples indicated that they were commercially sterile (average of 57 colonies/g of sample). Methylene blue stains of colonles revealed Micrococcus. Frozen (control) samples contained moderate numbers of colonies (av. 2300 colonies per g of sample). Micrococcus colonies were again predominant, but a few colonles of film yeasts were also seen. Irradiated samples were negative for thermophilic anaerobic spores producing gas. Control samples were positive, containing gram-negative rods, Escherichia coli, and gram- positive cocci. (BBB)« less

Single-layer centrifugation through PureSperm® 80 selects improved quality spermatozoa from frozen-thawed dog semen.

PubMed

Dorado, J; Alcaraz, L; Gálvez, M J; Acha, D; Ortiz, I; Urbano, M; Hidalgo, M

2013-08-01

The aim of this study was to investigate whether single-layer centrifugation (SLC) with PureSperm® 80 could select good quality spermatozoa, including those with specific motility patterns, from doses of frozen dog semen. Semen from 5 dogs was collected and cryopreserved following a standard protocol. After thawing, semen samples were divided into two aliquots: one of them was used as control and the other one processed by SLC. Assessment of sperm motility (assessed by computer-assisted semen analysis), morphology (Diff-Quick staining) and viability (triple fluorescent stain of propidium iodine/isothiocyanate-labeled peanut (Arachis hypogaea) agglutinin/Rhodamine 123), were performed on aliquots of fresh semen, frozen-thawed control and frozen-thawed SLC treated samples. A multivariate clustering procedure separated 26,051 motile spermatozoa into three subpopulations (sP): sP1 consisting of highly active but non-progressive spermatozoa (40.3%), sP2 consisting of spermatozoa with high velocity and progressive motility (30.0%), and sP3 consisting of poorly active and non-progressive spermatozoa (29.7%). SLC with PureSperm® 80 yielded sperm suspensions with improved motility, morphology, viability and acrosome integrity (P<0.001). The frozen-thawed SLC treated samples were enriched in sP2, reaching a proportion of 44.1% of the present spermatozoa. From these results, we concluded that SLC with PureSperm® 80 may be an alternative and successful method for improving the quality of frozen-thawed dog spermatozoa. Moreover, sP2 (high-speed and progressive spermatozoa) was more frequently observed after SLC. Finally, this study also demonstrated that the general motile sperm structure present in dogs remained constant despite the effect caused by either cryopreservation or separation by SLC through PureSperm® 80. Copyright © 2013 Elsevier B.V. All rights reserved.

Deciphering mineralogical changes and carbonation development during hydration and ageing of a consolidated ternary blended cement paste

PubMed Central

Grangeon, Sylvain; De Nolf, Wout; Harker, Nicholas; Boulahya, Faiza; Bourbon, Xavier

2018-01-01

To understand the main properties of cement, a ubiquitous material, a sound description of its chemistry and mineralogy, including its reactivity in aggressive environments and its mechanical properties, is vital. In particular, the porosity distribution and associated sample carbonation, both of which affect cement’s properties and durability, should be quantified accurately, and their kinetics and mechanisms of formation known both in detail and in situ. However, traditional methods of cement mineralogy analysis (e.g. chemical mapping) involve sample preparation (e.g. slicing) that can be destructive and/or expose cement to the atmosphere, leading to preparation artefacts (e.g. dehydration). In addition, the kinetics of mineralogical development during hydration, and associated porosity development, cannot be examined. To circumvent these issues, X-ray diffraction computed tomography (XRD-CT) has been used. This allowed the mineralogy of ternary blended cement composed of clinker, fly ash and blast furnace slag to be deciphered. Consistent with previous results obtained for both powdered samples and dilute systems, it was possible, using a consolidated cement paste (with a water-to-solid ratio akin to that used in civil engineering), to determine that the mineralogy consists of alite (only detected in the in situ hydration experiment), calcite, calcium silicate hydrates (C-S-H), ettringite, mullite, portlandite, and an amorphous fraction of unreacted slag and fly ash. Mineralogical evolution during the first hydration steps indicated fast ferrite reactivity. Insights were also gained into how the cement porosity evolves over time and into associated spatially and time-resolved carbonation mechanisms. It was observed that macroporosity developed in less than 30 h of hydration, with pore sizes reaching about 100–150 µm in width. Carbonation was not observed for this time scale, but was found to affect the first 100 µm of cement located around macropores in a sample cured for six months. Regarding this carbonation, the only mineral detected was calcite. PMID:29765604

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

1993-01-01

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Equivalent formation strength as a proxy tool for exploring the existence and distribution of gas hydrates

NASA Astrophysics Data System (ADS)

Hamada, Y.; Yamada, Y.; Sanada, Y.; Nakamura, Y.; Kido, Y. N.; Moe, K.

2017-12-01

Gas hydrates bearing layer can be normally identified by a basement simulating reflector (BSR) or well logging because of their high acoustic- and electric impedance compared to the surrounding formation. These characteristics of the gas hydrate can also represent contrast of in-situ formation strength. We here attempt to describe gas hydrate bearing layers based on the equivalent strength (EST). The Indian National Gas Hydrate Program (NGHP) Expedition 02 was executed 2015 off the eastern margin of the Indian Peninsula to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. Recorded drilling performance data was converted to the EST, which is a developed mechanical strength calculated only by drilling parameters (top drive torque, rotation per minute , rate of penetration , and drill bit diameter). At a representative site, site 23, the EST shows constant trend of 5 to 10 MPa, with some positive peaks at 0 - 270 mbsf interval, and sudden increase up to 50 MPa above BSR depth (270 - 290 mbsf). Below the BSR, the EST stays at 5-10 MPa down to the bottom of the hole (378 mbsf). Comparison of the EST with logging data and core sample description suggests that the depth profiles of the EST reflect formation lithology and gas hydrate content: the EST increase in the sand-rich layer and the gas hydrate bearing zone. Especially in the gas hydrate zone, the EST curve indicates approximately the same trend with that of P-wave velocity and resistivity measured by downhole logging. Cross plot of the increment of the EST and resistivity revealed the relation between them is roughly logarithmic, indicating the increase and decrease of the EST strongly depend on the saturation factor of gas hydrate. These results suggest that the EST, proxy of in-situ formation strength, can be an indicator of existence and amount of the gas-hydrate layer. Although the EST was calculated after drilling utilizing recorded surface drilling parameter in this study, the EST can be acquired during drilling by using real-time drilling parameters. In addition, the EST only requires drilling performance parameters without any additional tools or measurements, making it a simplified and economical tool for the exploration of gas hydrates.

The impact of milk handling procedures on Ostertagia ostertagi antibody ELISA test results.

PubMed

Vanderstichel, Raphaël; Dohoo, Ian; Stryhn, Henrik

2010-04-19

The impact of various milk handling stressors were analyzed using a commercially available enzyme-linked immunosorbent assay (ELISA) test measuring Ostertagia ostertagi antibodies in milk from dairy cattle (Svanovir). An indirect ELISA has the ability to determine the amount of milk production losses related to intestinal parasitism. The ELISA test recommends fresh defatted milk, however, milk collected from Dairy Herd Improvement (DHI) programs in North America undergo many stressors, including, heating, freezing and are not defatted. Normalized optical density ratios (ODRs) were compared between fresh defatted milk and milk subjected to one or more stressors with a linear mixed model accounting for differences in variation between the fresh and the frozen samples. Concordance correlation coefficients were also analyzed for comparisons to other similar studies. After accounting for random cow and container effects, the treatment factors interacted with each other (p<0.001). Biologically interesting contrasts were created to explain the interaction. The estimated difference in ODR between the milk samples handled according to recommendations of the manufacturers of Svanovir and the whole milk samples that were subjected to the most extreme treatment (heated, frozen, thawed, and re-frozen for 4 weeks) was 0.062 (p<0.001). This difference represented less than 5% of the range, and was thus considered biologically negligible. Frozen whole milk processed by DHI programs, the most likely method of collecting on-farm samples in North America, will likely yield reliable results for the indirect ELISA tests, particularly, Svanovir.

Zernike phase contrast cryo-electron tomography of whole bacterial cells.

PubMed

Guerrero-Ferreira, Ricardo C; Wright, Elizabeth R

2014-01-01

Cryo-electron tomography (cryo-ET) provides three-dimensional (3D) structural information of bacteria preserved in a native, frozen-hydrated state. The typical low contrast of tilt-series images, a result of both the need for a low electron dose and the use of conventional defocus phase-contrast imaging, is a challenge for high-quality tomograms. We show that Zernike phase-contrast imaging allows the electron dose to be reduced. This limits movement of gold fiducials during the tilt series, which leads to better alignment and a higher-resolution reconstruction. Contrast is also enhanced, improving visibility of weak features. The reduced electron dose also means that more images at more tilt angles could be recorded, further increasing resolution. Copyright © 2013 Elsevier Inc. All rights reserved.

Investigation of shallow gas hydrate occurrence and gas seep activity on the Sakhalin continental slope, Russia

NASA Astrophysics Data System (ADS)

Jin, Young Keun; Baranov, Boris; Obzhirov, Anatoly; Salomatin, Alexander; Derkachev, Alexander; Hachikubo, Akihiro; Minami, Hrotsugu; Kuk Hong, Jong

2016-04-01

The Sakhalin continental slope has been a well-known gas hydrate area since the first finding of gas hydrate in 1980's. This area belongs to the southernmost glacial sea in the northern hemisphere where most of the area sea is covered by sea ice the winter season. Very high organic carbon content in the sediment, cold sea environment, and active tectonic regime in the Sakhalin slope provide a very favorable condition for occurring shallow gas hydrate accumulation and gas emission phenomena. Research expeditions under the framework of a Korean-Russian-Japanese long-term international collaboration projects (CHAOS, SSGH-I, SSGH-II projects) have been conducted to investigate gas hydrate occurrence and gas seepage activities on the Sakhalin continental slope, Russia from 2003 to 2015. During the expeditions, near-surface gas hydrate samples at more than 30 sites have been retrieved and hundreds of active gas seepage structures on the seafloor were newly registered by multidisciplinary surveys. The gas hydrates occurrence at the various water depths from about 300 m to 1000 m in the study area were accompanied by active gas seepage-related phenomena in the sub-bottom, on the seafloor, and in the water column: well-defined upward gas migration structures (gas chimney) imaged by high-resolution seismic, hydroacoustic anomalies of gas emissions (gas flares) detected by echosounders, seafloor high backscatter intensities (seepage structures) imaged by side-scan sonar and bathymetric structures (pockmarks and mounds) mapped by single/multi-beam surveys, and very shallow SMTZ (sulphate-methane transition zone) depths, strong microbial activities and high methane concentrations measured in sediment/seawater samples. The highlights of the expeditions are shallow gas hydrate occurrences around 300 m in the water depth which is nearly closed to the upper boundary of gas hydrate stability zone in the area and a 2,000 m-high gas flare emitted from the deep seafloor.

Temperature, pressure, and compositional effects on anomalous or "self" preservation of gas hydrates

USGS Publications Warehouse

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

2003-01-01

We previously reported on a thermal regime where pure, polycrystalline methane hydrate is preserved metastably in bulk at up to 75 K above its nominal temperature stability limit of 193 K at 0.1 MPa, following rapid release of the sample pore pressure. Large fractions (>50 vol.%) of methane hydrate can be preserved for 2-3 weeks by this method, reflecting the greatly suppressed rates of dissociation that characterize this "anomalous preservation" regime. This behavior contrasts that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) isothermal test conditions, where dissociation rates increase monotonically with increasing temperature. Here, we report on recent experiments that further investigate the effects of temperature, pressure, and composition on anomalous preservation behavior. All tests conducted on sI methane hydrate yielded self-consistent results that confirm the highly temperature-sensitive but reproducible nature of anomalous preservation behavior. Temperature-stepping experiments conducted between 250 and 268 K corroborate the relative rates measured previously in isothermal preservation tests, and elevated pore-pressure tests showed that, as expected, dissociation rates are further reduced with increasing pressure. Surprisingly, sII methane-ethane hydrate was found to exhibit no comparable preservation effect when rapidly depressurized at 268 K, even though it is thermodynamically stable at higher temperatures and lower pressures than sI methane hydrate. These results, coupled with SEM imaging of quenched sample material from a variety of dissociation tests, strongly support our earlier arguments that ice-"shielding" effects provided by partial dissociation along hydrate grain surfaces do not serve as the primary mechanism for anomalous preservation. The underlying physical-chemistry mechanism(s) of anomalous preservation remains elusive, but appears to be based more on textural or morphological changes within the hydrate material itself, rather than on compositional zoning or ice-rind development.

Presentation of frozen shoulder among diabetic and non-diabetic patients☆

PubMed Central

Uddin, Mohammad Moin; Khan, Aminuddin A.; Haig, Andrew J.; Uddin, Mohammad Kafil

2014-01-01

Objective The literature is inconsistent regarding the level of pain and disability in frozen shoulder patients with or without diabetes mellitus. The aim of this study is to evaluate some demographic features of frozen shoulder patients and to look into the disparity of information by comparing the level of pain and disability due to frozen shoulder between diabetic and non-diabetic people. Design This is a prospective comparative study. People with frozen shoulder attending an outpatient department were selected by consecutive sampling. Disability levels were assessed by the Shoulder Pain & Disability Index (SPADI). Means of pain and disability scores were compared using unpaired t-test. Results Among 140 persons with shoulder pain 99 (71.4%) had frozen shoulder. From the participating 40 frozen shoulder patients, 26 (65%) were males and 14 (35%) were females. Seventeen participants (42.5%) were diabetic, two (5%) had impaired glucose tolerance and 21 (52.5%) patients were non-diabetic. Mean disability scores (SPADI) were 51 ± 15.5 in diabetic and 57 ± 16 in non-diabetic persons. The differences in pain and disability level were not statistically significance (respectively, p = 0.24 and p = 0.13 at 95% confidence interval). Conclusions No difference was found in level of pain and disability level between frozen shoulder patients with and without diabetes. PMID:25983497

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

PubMed Central

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.

2017-01-01

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 (r2 = 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. PMID:28062483

What is controlling the reflectance spectra (0.35-150 μm) of hydrated (and dehydrated) carbonaceous chondrites?

NASA Astrophysics Data System (ADS)

Beck, Pierre; Maturilli, A.; Garenne, A.; Vernazza, P.; Helbert, J.; Quirico, E.; Schmitt, B.

2018-10-01

In order to determine the controls on the reflectance spectra of hydrated carbonaceous chondrites, reflectance spectra were measured for a series of samples with well-determined mineralogy, water-content, and thermal history. This includes 5 CR chondrites, 11 CM chondrites, and 7 thermally metamorphosed CM chondrites. These samples were characterized over the 0.35-150 μm range by reflectance spectroscopy in order to cover the full spectral range accessible from ground based observation, and that will be determined in the near-future by the Hayabusa-2 and Osiris-REx missions. While spectra show absorption features shortward of 35 μm, no strong absorption bands were identified in this suite of samples longward of 35 μm. This work shows that the 0.7-μm band observed in hydrated carbonaceous chondrites is correlated with the total water content as well as with the band depth at 2.7 μm, confirming the suggestion that they are related to Mg-rich, Fe-bearing phyllosilicates. A feature at 2.3 μm, diagnostic of such phyllosilicates was found for all samples with a detectable 0.7-μm band, also indicative of Mg-rich phyllosilicates. A strong variability is found in the shape of the 3-μm band among CM chondrites, and between CM, CR and thermally metamorphosed CM chondrites. Heavily altered CM chondrites show a single strong band around 2.72 μm while more thermally metamorphosed CM samples show an absorption band at higher wavelength. The CR chondrite GRO 95577 has a 3-μm feature very similar to those of extensively altered CM chondrites while other CR chondrite rather shows goethite-like signatures (possibly due to terrestrial weathering of metals). Thermally metamorphosed CM chondrites all have 3-μm features, which are not purely due to terrestrial adsorbed water. The band shape ranges from heavily altered CM-like to goethite-like. The overall reflectance was found to be significantly higher for CR chondrites than for CM chondrites. This is also true for the hydrated CR chondrite GRO 95577 whose reflectance spectrum is almost identical to spectra obtained for CM chondrites except that it is brighter by about 40% in the visible. Another possibility to distinguish hydrated CM from hydrated CR chondrites is to use the combination of band depths at 0.7 and 2.3 μm. When comparing the spectra obtained with Cg and Cgh spectral end member, it is found that the band depth determined for hydrated chondrites (0.7 and 2.3 μm) are always higher than calculated for these spectral endmembers. If one considers only asteroids with unambiguous hydration detection, band depth at 0.7 μm is of similar value to those measured for hydrated carbonaceous chondrites.

Enhancement of the spectral selectivity of complex samples by measuring them in a frozen state at low temperatures in order to improve accuracy for quantitative analysis. Part II. Determination of viscosity for lube base oils using Raman spectroscopy.

PubMed

Kim, Mooeung; Chung, Hoeil

2013-03-07

The use of selectivity-enhanced Raman spectra of lube base oil (LBO) samples achieved by the spectral collection under frozen conditions at low temperatures was effective for improving accuracy for the determination of the kinematic viscosity at 40 °C (KV@40). A collection of Raman spectra from samples cooled around -160 °C provided the most accurate measurement of KV@40. Components of the LBO samples were mainly long-chain hydrocarbons with molecular structures that were deformable when these were frozen, and the different structural deformabilities of the components enhanced spectral selectivity among the samples. To study the structural variation of components according to the change of sample temperature from cryogenic to ambient condition, n-heptadecane and pristane (2,6,10,14-tetramethylpentadecane) were selected as representative components of LBO samples, and their temperature-induced spectral features as well as the corresponding spectral loadings were investigated. A two-dimensional (2D) correlation analysis was also employed to explain the origin for the improved accuracy. The asynchronous 2D correlation pattern was simplest at the optimal temperature, indicating the occurrence of distinct and selective spectral variations, which enabled the variation of KV@40 of LBO samples to be more accurately assessed.

Successful Application of Microarray Technology to Microdissected Formalin-Fixed, Paraffin-Embedded Tissue

PubMed Central

Coudry, Renata A.; Meireles, Sibele I.; Stoyanova, Radka; Cooper, Harry S.; Carpino, Alan; Wang, Xianqun; Engstrom, Paul F.; Clapper, Margie L.

2007-01-01

The establishment of a reliable method for using RNA from formalin-fixed, paraffin-embedded (FFPE) tissue would provide an opportunity to obtain novel gene expression data from the vast amounts of archived tissue. A custom-designed 22,000 oligonucleotide array was used in the present study to compare the gene expression profile of colonic epithelial cells isolated by laser capture microdissection from FFPE-archived samples with that of the same cell population from matched frozen samples, the preferred source of RNA. Total RNA was extracted from FFPE tissues, amplified, and labeled using the Paradise Reagent System. The quality of the input RNA was assessed by the Bioanalyzer profile, reverse transcriptase-polymerase chain reaction, and agarose gel electrophoresis. The results demonstrate that it is possible to obtain reliable microarray data from FFPE samples using RNA acquired by laser capture microdissection. The concordance between matched FFPE and frozen samples was evaluated and expressed as a Pearson’s correlation coefficient, with values ranging from 0.80 to 0.97. The presence of ribosomal RNA peaks in FFPE-derived RNA was reflected by a high correlation with paired frozen samples. A set of practical recommendations for evaluating the RNA integrity and quality in FFPE samples is reported. PMID:17251338

Mass spectrometric imaging and laser desorption ionization (LDI) with ice as a matrix using femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Berry, Jamal Ihsan

The desorption of biomolecules from frozen aqueous solutions on metal substrates with femtosecond laser pulses is presented for the first time. Unlike previous studies using nanosecond pulses, this approach produces high quality mass spectra of biomolecules repeatedly and reproducibly. This novel technique allows analysis of biomolecules directly from their native frozen environments. The motivation for this technique stems from molecular dynamics computer simulations comparing nanosecond and picosecond heating of water overlayers frozen on Au substrates which demonstrate large water cluster formation and ejection upon substrate heating within ultrashort timescales. As the frozen aqueous matrix and analyte molecules are transparent at the wavelengths used, the laser energy is primarily absorbed by the substrate, causing rapid heating and explosive boiling of the ice overlayer, followed by the ejection of ice clusters and the entrained analyte molecule. Spectral characteristics at a relatively high fluence of 10 J/cm 2 reveal the presence of large molecular weight metal clusters when a gold substrate is employed, with smaller cluster species observed from frozen aqueous solutions on Ag, Cu, and Pb substrates. The presence of the metal clusters is indicative of an evaporative cooling mechanism which stabiles cluster ion formation and the ejection of biomolecules from frozen aqueous solutions. Solvation is necessary as the presence of metal clusters and biomolecular ion signals are not observed from bare metal substrates in absence of the frozen overlayer. The potential for mass spectrometric imaging with femtosecond LDI of frozen samples is also presented. The initial results for the characterization of peptides and peptoids linked to combinatorial beads frozen in ice and the assay of frozen brain tissue from the serotonin transporter gene knockout mouse via LDI imaging are discussed. Images of very good quality and resolution are obtained with 400 nm, 200 fs pulses at a fluence of 1.25 J/cm2 . An attractive feature of this technique is that images are acquired within minutes for large sample areas. Additionally, the images obtained with femtosecond laser desorption are high in lateral resolution with the laser capable of being focused to a spot size of 30 mum. Femtosecond laser desorption from ice is unique in that unlike matrix assisted laser desorption ionization mass spectrometry, it does not employ an organic UV absorbing matrix to desorb molecular ions. Instead, the laser energy is absorbed by the metal substrate causing explosive boiling and ejection of the frozen overlayer. This approach is significant in that femtosecond laser desorption possess the potential of analyzing and assaying biomolecules directly from their frozen native environments. This technique was developed to compliment existing ToF-SIMS imaging capability for analysis of tissue and cells, as well as other biological systems of interest.

Effect of Hydration State of Martian Perchlorate Salts on Their Decomposition Temperatures During Thermal Extraction

NASA Astrophysics Data System (ADS)

Royle, Samuel H.; Montgomery, Wren; Kounaves, Samuel P.; Sephton, Mark A.

2017-12-01

Three Mars missions have analyzed the composition of surface samples using thermal extraction techniques. The temperatures of decomposition have been used as diagnostic information for the materials present. One compound of great current interest is perchlorate, a relatively recently discovered component of Mars' surface geochemistry that leads to deleterious effects on organic matter during thermal extraction. Knowledge of the thermal decomposition behavior of perchlorate salts is essential for mineral identification and possible avoidance of confounding interactions with organic matter. We have performed a series of experiments which reveal that the hydration state of magnesium perchlorate has a significant effect on decomposition temperature, with differing temperature releases of oxygen corresponding to different perchlorate hydration states (peak of O2 release shifts from 500 to 600°C as the proportion of the tetrahydrate form in the sample increases). Changes in crystallinity/crystal size may also have a secondary effect on the temperature of decomposition, and although these surface effects appear to be minor for our samples, further investigation may be warranted. A less than full appreciation of the hydration state of perchlorate salts during thermal extraction analyses could lead to misidentification of the number and the nature of perchlorate phases present.

The strength and rheology of methane clathrate hydrate

USGS Publications Warehouse

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

2003-01-01

Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

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

Finley, P.D.; Krason, J.; Dominic, K.

Multichannel and selected single-channel seismic lines of the continental margin sediments of the Colombia basin display compelling evidence for large accumulations of natural gas hydrate. Seismic bottom simulating reflectors (BSRs), interpreted to mark the base of the hydrate stability zone, are pronounced and very widespread along the entire Panama-Colombia lower continental slope. BSRs have also been identified at two locations on the abyssal plain. Water depths for these suspected hydrate occurrences range from 900 to 4000 m. Although no gas hydrate samples have been recovered from this area, biogenic methane is abundant in Pliocene turbidites underlying the abyssal plain. Moremore » deeply buried rocks beneath the abyssal plain are thermally mature. Thermogenic gas from these rocks may migrate upward along structural pathways into the hydrate stability zone and form hydrate. Impermeable hydrate layers may form caps over large accumulations of free gas, accounting for the very well-defined BSRs in the area. The abyssal plain and the deformed continental margin hold the highest potential for major economic accumulations of gas hydrate in the basin. The extensive continuity of BSRs, relatively shallow water depths, and promixity to onshore production facilities render the marginal deformed belt sediments the most favorable target for future economic development of the gas hydrate resource within the Colombia basin. The widespread evidence of gas hydrates in the Colombia basin suggests a high potential for conventional hydrocarbon deposits offshore of Panama and Colombia.« less

The molecular and crystal structure of dextrans: a combined electron and X-ray diffraction study. II. A low temperature, hydrated polymorph.

PubMed

Guizard, C; Chanzy, H; Sarko, A

1985-06-05

The crystal and molecular structure of a dextran hydrate has been determined through combined electron and X-ray diffraction analysis, aided by stereochemical model refinement. A total of 65 hk0 electron diffraction intensities were measured on frozen single crystals held at the temperature of liquid nitrogen, to a resolution limit of 1.6 A. The X-ray intensities were measured from powder patterns recorded from collections of the single crystals. The structure crystallizes in a monoclinic unit cell with parameters a = 25.71 A, b = 10.21 A, c (chain axis) = 7.76 A and beta = 91.3 degrees. The space group is P2(1) with b axis unique. The unit cell contains six chains and eight water molecules, with three chains of the same polarity and four water molecules constituting the asymmetric unit. Along the chain direction the asymmetric unit is a dimer residue; however, the individual glucopyranose residues are very nearly related by a molecular 2-fold screw axis. The conformation of the chain is very similar to that in the anhydrous structure, but the chain packing differs in the two structures in that the rotational positions of the chains about the helix axes (the chain setting angles) are considerably different. The chains still pack in the form of sheets that are separated by water molecules. The difference in the chain setting angles between the anhydrous and hydrate structures corresponds to the angle between like unit cell axes observed in the diffraction diagrams recorded from hybrid crystals containing both polymorphs. Despite some beam damage effects, the structure was determined to a satisfactory degree of agreement, with the residuals R''(electron diffraction) = 0.258 and R(X-ray) = 0.127.

Conservation science in a terrorist age: the impact of airport security screening on the viability and DNA integrity of frozen felid spermatozoa.

PubMed

Gloor, Kayleen T; Winget, Doug; Swanson, William F

2006-09-01

In response to growing terrorism concerns, the Transportation Security Administration now requires that all checked baggage at U.S. airports be scanned through a cabinet x-ray system, which may increase risk of radiation damage to transported biologic samples and other sensitive genetic material. The objective of this study was to investigate the effect of these new airport security regulations on the viability and DNA integrity of frozen felid spermatozoa. Semen was collected from two domestic cats (Felis silvestris catus) and one fishing cat (Prionailurus viverrinus), cryopreserved in plastic freezing straws, and transferred into liquid nitrogen dry shippers for security screening. Treatment groups included frozen samples from each male scanned once or three times using a Transportation Security Administration-operated cabinet x-ray system, in addition to non-scanned samples (i.e., negative control) and samples previously scanned three times and exposed to five additional high-intensity x-ray bursts (i.e., positive control). Dosimeters placed in empty dry shippers were used to quantify radiation exposure. Following treatment, straws were thawed and spermatozoa analyzed for post-thaw motility (percentage motile and rate of progressive movement), acrosome status, and DNA integrity using single-cell gel electrophoresis (i.e., the comet assay). Dosimeter measurements determined that each airport screening procedure produced approximately 16 mrem of radiation exposure. Our results indicated that all levels of radiation exposure adversely affected (P < 0.05) post-thaw sperm motility, but the percentage of acrosome-intact spermatozoa did not differ (P > 0.05) among treatment groups. Results also showed that the amount of double-stranded DNA damage was greater (P < 0.05) in sperm samples from both cat species scanned three times compared to samples scanned once or negative controls. Findings suggest that new airport security measures may cause radiation-induced damage to frozen spermatozoa and other valuable biologic samples transported on passenger aircraft and that alternative modes of sample transportation should be used whenever possible.

The effect of Taro (Colocasia esculenta L.) and Lesser Yam flour (Dioscorea esculenta L.) as thickener agent on physical characteristics of frozen wheygurt

NASA Astrophysics Data System (ADS)

Nurhartadi, E.; Utami, R.; Widowati, E.; Karunawati, B. M.

2017-11-01

The results showed that the addition ratio of taro and lesser yam flour affected to the physical characteristics of frozen wheygurt. The addition of lesser yam flour increased total soluble solids until the addition ratio of 2:2 due to the higher ash content of lesser yam (2.87%) than taro (0.44%). Sample with addition ratio of 1:3 and 0:4 significantly different compared to other samples, due to the starch content difference between taro (70-80%) and lesser yam (51.34%). Addition ratio of taro and lesser yam flour do not have a significant effect on the viscosity of the frozen wheygurt, due to both starch have similar setback viscosity. Lesser yam setback viscosity was 684.8 cP, while taro was 838.3 cP. Setback viscosity showed a high tendency of retrogradation. The addition ratio of taro and lesser yam flour have a significant effect to the overrun of frozen wheygurt. Addition ratio of taro and lesser yam flour have a significant effect to melting rate of frozen wheygurt. This result was caused by higher peak viscosity of taro starch compared to lesser yam, thus produced thicker gel than lesser yam. This lead increased water contents in the mixtures entrapped and slows down water mobility, hence melting rate would decrease.

The Pyrolytic Profile of Lyophilized and Deep-Frozen Compact Part of the Human Bone

PubMed Central

Lodowska, Jolanta; Wolny, Daniel; Kurkiewicz, Sławomir; Węglarz, Ludmiła

2012-01-01

Background. Bone grafts are used in the treatment of nonunion of fractures, bone tumors and in arthroplasty. Tissues preserved by lyophilization or deep freezing are used as implants nowadays. Lyophilized grafts are utilized in the therapy of birth defects and bone benign tumors, while deep-frozen ones are applied in orthopedics. The aim of the study was to compare the pyrolytic pattern, as an indirect means of the analysis of organic composition of deep-frozen and lyophilized compact part of the human bone. Methods. Samples of preserved bone tissue were subjected to thermolysis and tetrahydroammonium-hydroxide- (TMAH-) associated thermochemolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Results. Derivatives of benzene, pyridine, pyrrole, phenol, sulfur compounds, nitriles, saturated and unsaturated aliphatic hydrocarbons, and fatty acids (C12–C20) were identified in the pyrolytic pattern. The pyrolyzates were the most abundant in derivatives of pyrrole and nitriles originated from proteins. The predominant product in pyrolytic pattern of the investigated bone was pyrrolo[1,2-α]piperazine-3,6-dione derived from collagen. The content of this compound significantly differentiated the lyophilized graft from the deep-frozen one. Oleic and palmitic acid were predominant among fatty acids of the investigated samples. The deep-frozen implants were characterized by higher percentage of long-chain fatty acids than lyophilized grafts. PMID:22619606

High pressure treatments combined with sodium lactate to inactivate Escherichia coli O157:H7 and spoilage microbiota in cured beef carpaccio.

PubMed

Masana, Marcelo Oscar; Barrio, Yanina Ximena; Palladino, Pablo Martín; Sancho, Ana Maria; Vaudagna, Sergio Ramón

2015-04-01

High-pressure treatments (400 and 600 MPa) combined with the addition of sodium lactate (1 and 3%) were tested to reduce Escherichia coli O157:H7 (STEC O157) and spoilage microbiota contamination in a manufactured cured beef carpaccio in fresh or frozen conditions. Counts of spoilage microorganisms and STEC O157 were also examined during the curing step to prepare the carpaccio. STEC O157 counts remained almost unchanged through the curing process performed at 1 ± 1 °C for 12 days, with a small decrease in samples with 3% of sodium lactate. High-pressure treatments at 600 MPa for 5 min achieved an immediate reduction of up to 2 logarithmic units of STEC O157 in frozen carpaccio, and up to 1.19 log in fresh condition. Counts of spoilage bacteria diminished below detection limits in fresh or frozen carpaccio added with sodium lactate by the application of 400 and 600 MPa. Maximum injury on STEC O157 cells was observed at 600 MPa in carpaccio in fresh condition without added sodium lactate. Lethality of high-pressure treatments on STEC O157 was enhanced in frozen carpaccio, while the addition of sodium lactate at 3% reduced the lethality on STEC O157 in frozen samples, and the degree of injury in fresh carpaccio. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of sample preparation method on sensory quality of cooked chicken breast fillets processed for food service

USDA-ARS?s Scientific Manuscript database

Chicken fillets (Pectoralis major) are one of popular items for food service. In the store, especially in fast food service stores, ready-to-cook meat products are commonly stored in freezers before use. The frozen meat can be cooked either directly from a frozen stage or after thawing. However, the...

Dynamics of lipid saccharide nanoparticles by quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Di Bari, M. T.; Gerelli, Y.; Sonvico, F.; Deriu, A.; Cavatorta, F.; Albanese, G.; Colombo, P.; Fernandez-Alonso, F.

2008-04-01

Nano- and microparticles composed of saccharide and lipid systems are extensively investigated for applications as highly biocompatible drug carriers. A detailed understanding of particle-solvent interactions is of key importance in order to tailor their characteristics for delivering drugs with specific chemical properties. Here we report results of a quasielastic neutron scattering (QENS) investigation on lecithin/chitosan nanoparticles prepared by autoassembling the two components in an aqueous solution. The measurements were performed at room temperature on lyophilized and H 2O hydrated nanoparticles ( h = 0.47 w H 2O/w hydrated sample). In the latter, hydration water is mostly enclosed inside the nanoparticles; its dynamics is similar to that of bulk water but with a significant decrease in diffusivity. The scattering from the nanoparticles can be described by a simple model of confined diffusion. In the lyophilized state only hydrogens belonging to the polar heads are seen as mobile within the experimental time-window. In the hydrated sample the diffusive dynamics involves also a significant part of the hydrogens in the lipid tails.

The Guanine Cation Radical: Investigation of Deprotonation States by ESR and DFT

PubMed Central

Adhikary, Amitava; Kumar, Anil; Becker, David; Sevilla, Michael D.

2008-01-01

This work reports ESR studies that identify the favored site of deprotonation of the guanine cation radical (G•+) in an aqueous medium at 77 K. Using ESR and UV-visible spectroscopy, one-electron oxidized guanine is investigated in frozen aqueous D2O solutions of 2′-deoxyguanosine (dGuo) at low temperatures at various pHs at which the guanine cation, G•+ (pH 3–5), singly deprotonated species, G(-H)• (pH 7–9) and doubly deprotonated species, G(-2H)•− (pH>11) are found. C-8-deuteration of dGuo to give 8-D-dGuo removes the major proton hyperfine coupling at C-8. This isolates the anisotropic nitrogen couplings for each of the three species and aids our analyses. These anisotropic nitrogen couplings were assigned to specific nitrogen sites by use of 15N substituted derivatives at N1, N2 N3 atoms in dGuo. Both ESR and UV-visible spectra are reported for each of the species: G•+, G(-H)•, and G(-2H)•−. The experimental anisotropic ESR hyperfine couplings are compared to those obtained from DFT calculations for the various tautomers of G(-H)•. Using the B3LYP/6–31G(d) method, the geometries and energies of G•+ and its singly deprotonated state in its two tautomeric forms, G(N1-H)• and G(N2-H)•, were investigated. In a non-hydrated state G(N2-H)• is found to be more stable than G(N1-H)• but on hydration with 7 water molecules G(N1-H)• is found to be more stable than G(N2-H)•. The theoretically calculated hyperfine coupling constants (HFCC) of G•+, G(N1-H)• and G(-2H)•− match the experimentally observed HFCCs best on hydration with 7 or more waters. For G(-2H)•−, the hyperfine coupling constant (HFCC) at the exocyclic nitrogen atom (N2) is especially sensitive to the number of hydrating water molecules; good agreement with experiment is not obtained until 9 or 10 waters of hydration are included. PMID:17125389

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

PubMed

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

2009-05-21

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

Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

From Black Hole to Hydrate Hole: Gas hydrates, authigenic carbonates and vent biota as indicators of fluid migration at pockmark sites of the Northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, S.; Schneider, R.; Spiess, V.; Cruise Participants Of M56b

2003-04-01

A recent high-resolution seismic, echosounder and video survey combined with detailed geological and geochemical sampling of pockmark sites on the Northern Congo Fan was carried out with RV Meteor in November/December 2002 in the frame of the project "CONGO" (BMBF/BEO "Geotechnologien"). These investigations revealed the extensive occurrence of surface and sub-surface gas hydrates as well as characteristic features of fluid venting such as clams (Calyptogena), tube worms (Pogonophera) and huge amounts of authigenic carbonates. In a first approach the patchyness in the occurrence of these features was mapped in relation to pockmark structure and seismic reflectors. Detailed sampling of three pockmarks by gravity corer showed that gas hydrates are present at and close to the sediment surface and often occur as several distinct layers and/or veins intercalated with hemipelagic muds. The depth of the upper boundary of these hydrate-bearing sediments increases from the center towards the edge of the pockmark structures. Pore water concentration profiles of sulfate and methane document the process of anaerobic methane oxidation above the hydrate-bearing layers. For those cores which contained several gas hydrate layers preliminary pore water profiles suggest the occurrence of more than one zone of anaerobic methane oxidation. Authigenic carbonates are found in high abundance, irregularly distributed within the pockmarks close to the sediment surface. These carbonates occur in a wide variety with respect to size, shape, structure and mineralogy. Their formation is associated with high amounts of bicarbonate released by the process of anaerobic methane oxidation. In the gravity cores authigenic carbonates are always present above hydrate-bearing sections. However, the quantities and characteristics of these authigenic minerals in relation to venting and microbial activity as well as to gas hydrate dissociation are not clear yet. Unraveling this relationship will be a major target of further investigation. By means of detailed studies of the sedimentary solid-phase, authigenic carbonates, clam layers and molecular biomarkers we will also try to reconstruct the history of venting and the dynamics of gas hydrate formation and decomposition in the Northern Congo fan area.

Qualitative and quantitative assessment of DNA quality of frozen beef based on DNA yield, gel electrophoresis and PCR amplification and their correlations to beef quality.

PubMed

Zhao, Jing; Zhang, Ting; Liu, Yongfeng; Wang, Xingyu; Zhang, Lan; Ku, Ting; Quek, Siew Young

2018-09-15

Freezing is a practical method for meat preservation but the quality of frozen meat can deteriorate with storage time. This research investigated the effect of frozen storage time (up to 66 months) on changes in DNA yield, purity and integrity in beef, and further analyzed the correlation between beef quality (moisture content, protein content, TVB-N value and pH value) and DNA quality in an attempt to establish a reliable, high-throughput method for meat quality control. Results showed that frozen storage time influenced the yield and integrity of DNA significantly (p < 0.05). The DNA yield decreased as frozen storage time increased due to DNA degradation. The half-life (t 1/2  = ln2/0.015) was calculated as 46 months. The DNA quality degraded dramatically with the increased storage time based on gel electrophoresis results. Polymerase chain reaction (PCR) products from both mitochondrial DNA (mtDNA) and nuclear DNA (nDNA) were observed in all frozen beef samples. Using real-time PCR for quantitative assessment of DNA and meat quality revealed that correlations could be established successfully with mathematical models to evaluate frozen beef quality. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

USGS Publications Warehouse

Torres, M.E.; Trehu, A.M.; Cespedes, N.; Kastner, M.; Wortmann, U.G.; Kim, J.-H.; Long, P.; Malinverno, A.; Pohlman, J.W.; Riedel, M.; Collett, T.

2008-01-01

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8??km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49??mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23??cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63????m) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245??mbsf. ?? 2008 Elsevier B.V.

Gas hydrates of outer continental margins

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

Kvenvolden, K.A.

1990-05-01

Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf ofmore » Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.« less

Crystalline phases involved in the hydration of calcium silicate-based cements: Semi-quantitative Rietveld X-ray diffraction analysis.

PubMed

Grazziotin-Soares, Renata; Nekoofar, Mohammad H; Davies, Thomas; Hübler, Roberto; Meraji, Naghmeh; Dummer, Paul M H

2017-08-30

Chemical comparisons of powder and hydrated forms of calcium silicate cements (CSCs) and calculation of alterations in tricalcium silicate (Ca 3 SiO 5 ) calcium hydroxide (Ca(OH) 2 ) are essential for understanding their hydration processes. This study aimed to evaluate and compare these changes in ProRoot MTA, Biodentine and CEM cement. Powder and hydrated forms of tooth coloured ProRoot MTA, Biodentine and CEM cement were subjected to X-ray diffraction (XRD) analysis with Rietveld refinement to semi-quantitatively identify and quantify the main phases involved in their hydration process. Data were reported descriptively. Reduction in Ca 3 SiO 5 and formation of Ca(OH) 2 were seen after the hydration of ProRoot MTA and Biodentine; however, in the case of CEM cement, no reduction of Ca 3 SiO 5 and no formation of Ca(OH) 2 were detected. The highest percentages of amorphous phases were seen in Biodentine samples. Ettringite was detected in the hydrated forms of ProRoot MTA and CEM cement but not in Biodentine. © 2017 Australian Society of Endodontology Inc.

Investigation of hydrate formation in the system H2-CH4-H2O at a pressure up to 250 MPa.

PubMed

Skiba, Sergei S; Larionov, Eduard G; Manakov, Andrey Y; Kolesov, Boris A; Kosyakov, Viktor I

2007-09-27

Phase equilibria in the system H2-CH4-H2O are investigated by means of differential thermal analysis within hydrogen concentration range 0-70 mol % and at a pressure up to 250 MPa. All the experiments were carried out under the conditions of gas excess. With an increase in hydrogen concentration in the initial gas mixture, decomposition temperature of the formed hydrates decreased. X-ray diffraction patterns and Raman spectra of the quenched hydrate samples obtained at a pressure of 20 MPA from a gas mixture containing 40 mol % hydrogen were recorded. It turned out that the hydrate has cubic structure I under these conditions. The Raman spectra showed that hydrogen molecules are not detected in the hydrate within the sensitivity of the method, that is, almost pure methane hydrate is formed. The general view of the phase diagram of the investigated system is proposed. A thermodynamic model was proposed to explain a decrease in hydrate decomposition temperature in the system with an increase in the concentration of hydrogen in the initial mixture.

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.

Effect of different concentrations of soybean lecithin and virgin coconut oil in Tris-based extender on the quality of chilled and frozen-thawed bull semen

PubMed Central

Tarig, A. A.; Wahid, H.; Rosnina, Y.; Yimer, N.; Goh, Y. M.; Baiee, F. H.; Khumran, A. M.; Salman, H.; Assi, M. A.; Ebrahimi, M.

2017-01-01

Aim: The objective of this study was to evaluate the effects of different concentrations of soybean lecithin (SL) and virgin coconut oil (VCO) in Tris-based extender on chilled and frozen-thawed bull semen quality parameters. Materials and Methods: A total of 24 ejaculates were collected from four bulls via an electroejaculator. Semen samples were diluted with 2% VCO in Tris-based extender which consists of various concentrations of SL (1, 1.25, 1.5, and 1.75%). A 20% egg yolk in Tris used as a positive control (C+). The diluted semen samples were divided into two fractions; one for chilling which were stored at 4°C for 24, 72, and 144 h before evaluated for semen quality parameters. The second fraction used for freezing was chilled for 3 h at 4°C, packed into 0.25 mL straws and then cryopreserved in liquid nitrogen. The samples were then evaluated after 7 and 14 days. Chilled and frozen semen samples were thawed at 37°C and assessed for general motility using computer-assisted semen analysis, viability, acrosome integrity and morphology (eosin-nigrosin stain), membrane integrity, and lipid peroxidation using thiobarbituric acid reaction test. Results: The results showed that all the quality parameters assessed were significantly (p<0.05) improved at 1.5% SL concentration in chilled semen. Treatment groups of 1, 1.25, 1.5, and 1.75% SL were higher in quality parameters than the control group (C+) in chilled semen. However, all the quality parameters in frozen-thawed semen were significantly higher in the C+ than the treated groups. Conclusion: In conclusion, supplementation of 1.5% SL in 2% VCO Tris-based extender enhanced the chilled bull semen. However, there was no marked improvement in the frozen-thawed quality parameters after treatment. PMID:28717321

Effect of different concentrations of soybean lecithin and virgin coconut oil in Tris-based extender on the quality of chilled and frozen-thawed bull semen.

PubMed

Tarig, A A; Wahid, H; Rosnina, Y; Yimer, N; Goh, Y M; Baiee, F H; Khumran, A M; Salman, H; Assi, M A; Ebrahimi, M

2017-06-01

The objective of this study was to evaluate the effects of different concentrations of soybean lecithin (SL) and virgin coconut oil (VCO) in Tris-based extender on chilled and frozen-thawed bull semen quality parameters. A total of 24 ejaculates were collected from four bulls via an electroejaculator. Semen samples were diluted with 2% VCO in Tris-based extender which consists of various concentrations of SL (1, 1.25, 1.5, and 1.75%). A 20% egg yolk in Tris used as a positive control (C+). The diluted semen samples were divided into two fractions; one for chilling which were stored at 4°C for 24, 72, and 144 h before evaluated for semen quality parameters. The second fraction used for freezing was chilled for 3 h at 4°C, packed into 0.25 mL straws and then cryopreserved in liquid nitrogen. The samples were then evaluated after 7 and 14 days. Chilled and frozen semen samples were thawed at 37°C and assessed for general motility using computer-assisted semen analysis, viability, acrosome integrity and morphology (eosin-nigrosin stain), membrane integrity, and lipid peroxidation using thiobarbituric acid reaction test. The results showed that all the quality parameters assessed were significantly (p<0.05) improved at 1.5% SL concentration in chilled semen. Treatment groups of 1, 1.25, 1.5, and 1.75% SL were higher in quality parameters than the control group (C+) in chilled semen. However, all the quality parameters in frozen-thawed semen were significantly higher in the C+ than the treated groups. In conclusion, supplementation of 1.5% SL in 2% VCO Tris-based extender enhanced the chilled bull semen. However, there was no marked improvement in the frozen-thawed quality parameters after treatment.

Breed differences of bull frozen-thawed semen.

PubMed

Ntemka, A; Tsousis, G; Brozos, C; Kiossis, E; Boscos, C M; Tsakmakidis, I A

2016-12-01

The objective of this study was to investigate the quality of frozen-thawed semen from different bull breeds. Commercial frozen-thawed bull semen samples (26 per breed, 130 totally) of five breeds (Holstein [Η], Brown Swiss [BS], Limousin [L], Belgian Blue [BB], Blonde d' Aquitaine [BA]) were used. After thawing, each semen sample was subjected to thermal resistance test (TR) for 0.5 and 1 hr at 38°C and hypo-osmotic swelling test (HOST) for 1 hr at 150 mOsm at 37°C. Additionally, all samples were evaluated at times 0 hr (thawing), 0.5 hr (TR), 1 hr (TR) for kinetics by CASA [progressive, immotile, rapid, medium, slow moving spermatozoa, curvilinear velocity (VCL), average path velocity (VAP), straight line velocity (VSL), linearity (LIN), straightness (STR), beat cross-frequency (BCF), amplitude of lateral head displacement (ALH), wobble (WOB)]. Moreover, directly after thawing, all semen samples were evaluated for morphometry, morphology, viability and DNA fragmentation. Statistical analysis was conducted using a mixed model for repeated measures. The results showed (a) higher VCL after thawing in H, L breeds compared to BB and BA, (b) higher VAP after thawing in L compared to BB, BA, (c) higher values of progressive spermatozoa after TR in H, BS compared to BB, BA, (d) higher values of rapid spermatozoa after thawing and 0.5 hr of TR in H, BS, L compared to BB, BA, (e) lower viability in BA after thawing compared to H, BS, BB, (f) lower morphological abnormalities in H compared to L, BB, (g) higher head length in Η compared to BB. No significant differences were observed in the results from HOST and DNA fragmentation between breeds. In conclusion, quality characteristics of frozen-thawed bull semen are dependent on the breed. Frozen semen from BB and BA breeds should be handled more carefully after thawing, as it is more sensitive to stress. © 2016 Blackwell Verlag GmbH.

On the compressibility and temperature boundary of warm frozen soils

NASA Astrophysics Data System (ADS)

Qi, Jilin; Dang, Boxiang; Guo, Xueluan; Sun, Xiaoyu; Yan, Xu

2017-04-01

A silty-clay obtained along the Qinghai-Tibetan railway and a standard Chinese sand were taken as study objects. Saturated frozen soil samples were prepared for testing. Step-load was used and confined compression was carried out on the soils under different temperatures. Compression index and pseudo-preconsolidation pressure (PPC) were obtained. Unlike unfrozen soils, PPC is not associated with stress history. However, it is still the boundary of elastic and plastic deformations. Different compression indexes can be obtained from an individual compression curve under pressures before and after PPC. The parameters at different thermal and stress conditions were analyzed. It is found that temperature plays a critical role in mechanical behaviours of frozen soils. Efforts were then made on the silty-clay in order to suggest a convincing temperature boundary in defining warm frozen soil. Three groups of ice-rich samples with different ice contents were prepared and tested under confined compression. The samples were compressed under a constant load and with 5 stepped temperatures. Strain rates at different temperatures were examined. It was found that the strain rate at around -0.6°C increased abruptly. Analysis of compression index was performed on the data both from our own testing program and from the literature, which showed that at about -1°C was a turning point in the curves for compression index against temperature. Based on both our work and taking into account the unfrozen water content vs. temperature, the range of -1°C to -0.5°C seems to be the temperature where the mechanical properties change greatly. For convenience, -1.0°C can be defined as the boundary for warm frozen soils.

Effect of cooling rate on sperm quality of cryopreserved Andalusian donkey spermatozoa.

PubMed

Demyda-Peyrás, S; Bottrel, M; Acha, D; Ortiz, I; Hidalgo, M; Carrasco, J J; Gómez-Arrones, V; Gósalvez, J; Dorado, J

2018-06-01

The aim of this study was to evaluate the effect of different cooling rates on post-thaw quality of cryopreserved donkey spermatozoa. Eighteen ejaculates from six adult Andalusian donkeys (three ejaculates per donkey) were collected using an artificial vagina. Pooled semen samples (two ejaculates per pool) were divided into three aliquots, and frozen in Gent freezing extender using three different cryopreservation protocols (P): P1 (conventional slow freezing, as control): semen pre-cooled in an Equitainer for 2 h and frozen in liquid nitrogen (LN 2 ) vapour; P2 (controlled pre-freeze cooling rate): semen pre-cooled at a controlled rate for 73 min and frozen in LN 2 vapour; and P3 (rapid freezing) semen frozen immediately in LN 2 vapour. After thawing at 37 °C for 30 s, semen samples were assessed for motility, morphology, acrosome and plasma membrane integrity; spermatozoa were also tested for DNA integrity. Significant (P < 0.01) differences were found between the cryopreservation protocols for all sperm parameters evaluated, except for DNA integrity. Semen samples frozen using P2 showed significantly (P < 0.01) higher values for sperm motility, morphology, sperm membrane integrity, and acrosome integrity. On the contrary, P3 reduced sperm motility (P < 0.01) and increased the percentage of spermatozoa with damaged plasma membrane (P < 0.001). In our study, we demonstrated that the sperm of Andalusian donkey is particularly sensitive to the cooling rate used before freezing. Furthermore, Andalusian donkey semen can be successfully cryopreserved using controlled cooling rates combined with freezing in LN 2 vapour. Copyright © 2018 Elsevier B.V. All rights reserved.

Spawn viability in edible mushrooms after freezing in liquid nitrogen without a cryoprotectant.

PubMed

Mata, Gerardo; Pérez-Merlo, Rosalía

2003-08-01

Five strains of edible mushrooms (Lentinula boryana, Lentinula edodes, Pleurotus djamor, Pleurotus pulmonarius, and Volvariella volvacea) were studied. Spawn were prepared from sorghum seeds and then incubated for 14 days under optimum conditions for each species. Once covered by mycelia, the sorghum seeds were placed in polycarbonate vials for freezing in liquid nitrogen. The effect of adding a cryoprotective solution before freezing (either 10% glycerol v/v or 5% dimethylsulfoxide v/v) was evaluated as a function of mycelial growth and percent viability. Three main treatments were undertaken: (1) freezing with a glycerol or dimethylsulfoxide cryoprotectant, (2) freezing with water and (3) freezing without cryoprotectant or water. Samples were maintained frozen for a week, after which time they were thawed (10 min at 30 degrees C) and the seeds placed in Petri dishes with a culture medium. A recovery rate of 96.8% was obtained for the total number of samples summed over all strains and treatments. In contrast, 99.2% of the samples frozen without cryoprotectant were recovered. The recovery of frozen mycelia was delayed with respect to a control group, which was not frozen. However, no difference was observed in percent recovery and mycelial diameter when a new series of spawn was prepared from mycelia that had been previously frozen. Results obtained from this experiment demonstrate that an adequate recovery of mycelia can be obtained without using a cryoprotectant. This capacity might enable large quantities of commercial mushroom strains to be handled at reduced production costs. It is suggested that the mycelia survived freezing without cryoprotectants because they were embedded and protected within the sorghum seeds used to elaborate the spawn.

Characterisation of Asphalt Concrete Using Nanoindentation

PubMed Central

Barbhuiya, Salim; Caracciolo, Benjamin

2017-01-01

In this study, nanoindentation was conducted to extract the load-displacement behaviour and the nanomechanical properties of asphalt concrete across the mastic, matrix, and aggregate phases. Further, the performance of hydrated lime as an additive was assessed across the three phases. The hydrated lime containing samples have greater resistance to deformation in the mastic and matrix phases, in particular, the mastic. There is strong evidence suggesting that hydrated lime has the most potent effect on the mastic phase, with significant increase in hardness and stiffness. PMID:28773181

Morphology of methane hydrate host sediments

USGS Publications Warehouse

Jones, K.W.; Feng, H.; Tomov, S.; Winters, W.J.; Eaton, M.; Mahajan, D.

2005-01-01

The morphological features including porosity and grains of methane hydrate host sediments were investigated using synchrotron computed microtomography (CMT) technique. The sediment sample was obtained during Ocean Drilling Program Leg 164 on the Blake Ridge at water depth of 2278.5 m. The CMT experiment was performed at the Brookhaven National Synchrotron Light Source facility. The analysis gave ample porosity, specific surface area, mean particle size, and tortuosity. The method was found to be highly effective for the study of methane hydrate host sediments.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

The impact of permafrost-associated microorganisms on hydrate formation kinetics

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Quality Evaluation of Pork with Various Freezing and Thawing Methods

PubMed Central

2014-01-01

In this study, the physicochemical and sensory quality characteristics due to the influence of various thawing methods on electro-magnetic and air blast frozen pork were examined. The packaged pork samples, which were frozen by air blast freezing at −45℃ or electro-magnetic freezing at −55℃, were thawed using 4 different methods: refrigeration (4±1℃), room temperature (RT, 25℃), cold water (15℃), and microwave (2450 MHz). Analyses were carried out to determine the drip and cooking loss, water holding capacity (WHC), moisture content and sensory evaluation. Frozen pork thawed in a microwave indicated relatively less thawing loss (0.63-1.24%) than the other thawing methods (0.68-1.38%). The cooking loss after electro-magnetic freezing indicated 37.4% by microwave thawing, compared with 32.9% by refrigeration, 36.5% by RT, and 37.2% by cold water in ham. The thawing of samples frozen by electro-magnetic freezing showed no significant differences between the methods used, while the moisture content was higher in belly thawed by microwave (62.0%) after electro-magnetic freezing than refrigeration (54.8%), RT (61.3%), and cold water (61.1%). The highest overall acceptability was shown for microwave thawing after electro-magnetic freezing but there were no significant differences compared to that of the other samples. PMID:26761493

PRODUCTION OF HYDRATED ELECTRONS FROM PHOTOIONIZATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS

EPA Science Inventory

Under UV irradiation, an important primary photochemical reaction of colored dissolved organic matter (CDOM) is electron ejection, producing hydrated electrons (e-aq). The efficiency of this process has been studied in both fresh and seawater samples with both steady-state scave...

Impact of water extractable arabinoxylan from rye bran on the frozen steamed bread dough quality.

PubMed

Wang, Pei; Tao, Han; Jin, Zhengyu; Xu, Xueming

2016-06-01

Impact of water extractable arabinoxylan from rye bran on frozen steamed bread dough quality was investigated in terms of the bread characteristics, ice crystallization, yeast activity as well as the gluten molecular weight distribution and glutenin macropolymer content in the present study. Results showed that water extractable arabinoxylan significantly improved bread characteristics during the 60-day frozen storage. Less water was crystallized in the water extractable arabinoxylan dough during storage, which could explain the alleviated yeast activity loss. For all the frozen dough samples, more soluble high molecular weight (Mw ≈ 91,000-688,000) and low molecular weight (Mw ≈ 91,000-16,000) proteins were derived from glutenin macropolymer depolymerization. Nevertheless, water extractable arabinoxylan dough developed higher glutenin macropolymer content with lowered level of soluble low molecular weight proteins throughout the storage. This study suggested water extractable arabinoxylan from rye bran had great potential to be served as an effective frozen steamed bread dough improver. Copyright © 2016 Elsevier Ltd. All rights reserved.

Intracytoplasmic sperm injection outcomes with cryopreserved testicular sperm aspiration samples.

PubMed

Roque, M; Valle, M; Marques, F; Sampaio, M; Geber, S

2016-04-01

Intracytoplasmic sperm injection (ICSI) may be performed with testicular frozen-thawed spermatozoa in patients with nonobstructive azoospermia (NOA). Sperm retrieval can be performed in advance of oocyte aspiration, as it may avoid the possibility of no recovery of spermatozoa on the day of oocyte pickup. There are few studies available in the literature concerning the use of frozen-thawed spermatozoa obtained from testicular sperm aspiration (TESA). To evaluate the effects and the outcomes of ICSI with frozen-thawed spermatozoa obtained by TESA, we performed a retrospective analysis of 43 ICSI cycles using frozen-thawed TESA. We obtained acceptable results with a fertilisation rate of 67.9%, an implantation rate (IR) of 17.1%, and clinical and ongoing pregnancy rates of 41.9% and 37.2% respectively. The results of this study suggest that performing ICSI using cryopreserved frozen-thawed testicular spermatozoa with TESA as a first option is a viable, safe, economic and effective method for patients with NOA. © 2015 Blackwell Verlag GmbH.

Effect of freezing of sputum samples on flow cytometric analysis of lymphocyte subsets.

PubMed

Jaksztat, E; Holz, O; Paasch, K; Kelly, M M; Hargreave, F E; Cox, G; Magnussen, H; Jörres, R A

2004-08-01

Sputum samples should be processed shortly after induction to prevent cell degradation. For intermediate storage, freezing of homogenised samples or immediate fixation have been shown to be suitable for cytospins. The aim of this study was to investigate whether freezing or immediate fixation of sputum affect the analysis of lymphocyte subsets by flow cytometry. Selected plugs from 24 sputum samples were homogenised. One aliquot was processed immediately and analysed by flow cytometry. A second aliquot was homogenised, frozen at -20 C after addition of dimethylsulfoxide and stored for a median time of 6 days. In six samples a third aliquot was fixed in formalin after induction and stored for up to 72 h before further processing. Compared to immediate processing, percentages of total lymphocytes and T-suppressor cells were elevated after being frozen, with a minor decrease in the T4/T8 ratio. Proportions of total lymphocytes, T-helper and T-suppressor cells correlated between native and frozen samples, intra-class correlation coefficients being 0.74, 0.85 and 0.70, respectively. The formalin-fixed aliquots could not be analysed with the antibodies used. In conclusion, freezing seems to be a suitable technique to store sputum samples for flow cytometry of CD3, CD4 and CD8 lymphocyte subsets. Its effects were minor compared to the variation between subjects.

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.

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

NASA Astrophysics Data System (ADS)

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

2007-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

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.

Training effect of the exchange bias in sputter deposited Fe3O4 thin films with varying thickness

NASA Astrophysics Data System (ADS)

Muhammed Shameem, P. V.; Senthil Kumar, M.

2018-07-01

The training effect property of the exchange bias in the reactively sputtered polycrystalline Fe3O4 thin films of varying thicknesses in the range 25-200 nm are studied. Structural studies by X-ray diffraction, X-ray photoelectron spectroscopy and selected area electron diffraction confirm the formation of single phase Fe3O4. The scanning electron spectroscopy images show that the grains are uniformly distributed. All the samples show clear and consistent exchange bias training behaviour due to the dynamics of the spins at the interface of the ferrimagnetic core and the spin glass-like surface of the grains. The analysis of the training effect data of the exchange bias field HE measured at 2 K by using three different models show that the model based on the relaxation of the frozen and rotatable spin components at the interface gives the best description for all the samples. From this model, it is found that the reversible interface spins relax around 7 times faster than the frozen interface spins at 2 K for all the samples and that their relative relaxation rates are independent of the sample thickness. This constancy show that the relative relaxation rates of the interfacial frozen and rotatable spin components is a material dependent property. The frozen component of the interfacial spins of each sample is found to be dominated at the initial stage of the training. A direct equivalence between the HE and remanence asymmetry ME is observed. Above the spin freezing temperature, the training effect measurements at 75 K show that the HE decreases sharply with successive field cycling as compared to the measurements made at 2 K and the HE vanishes after first few cycles.

Combustion of Methane Hydrate

NASA Astrophysics Data System (ADS)

Roshandell, Melika

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

Comparison of cook loss, shear force, and sensory descriptive profiles of boneless skinless white meat cooked from a frozen or thawed state.

PubMed

Zhuang, Hong; Savage, Elizabeth M

2013-11-01

Four replications were conducted to compare quality measurements, cook loss, shear force, and sensory quality attributes of cooked boneless skinless white meat, broiler breast fillets (pectoralis major) prepared directly from a frozen state or prepared from a thawed state. In each replication, fresh broiler fillets (removed from carcasses 6-8 h postmortem) were procured from a local commercial processing plant and stored in a -20°C freezer until use. On the sensory evaluation date, fillets were cooked to an endpoint temperature of 78°C either directly from the frozen state (thawing during cooking) or after the frozen samples were thawed in a refrigerator (2°C) overnight (thawing before cooking). Cook loss and Warner-Bratzler (WB) shear force were used as indicators for instrumental quality measurements. Sensory quality measurements were conducted by trained descriptive panelists using 0 to 15 universal intensity scales for 8 texture and 10 flavor attributes. Results show that there were no differences (P > 0.05) in measurements for sensory descriptive flavor attributes of cooked fillets between the 2 sample thawing methods, indicating that the sensory flavor profiles of both methods were similar to each other. However, WB shear force (36.98 N), cook loss (21.2%), sensory texture attributes of cohesiveness (intensity score was 5.59), hardness (5.14), rate of breakdown (5.50), and chewiness (5.21) of the breast fillets cooked directly from the frozen state were significantly higher (P < 0.05) than those of the breast meat cooked after being thawed (30.56 N, 19.0%, 5.19, 4.78, 5.29, and 5.02, respectively). These results indicate that cookery directly from frozen boneless skinless white meat can result in different measurement values of cook loss, shear force, and sensory descriptive texture attributes compared with cookery after frozen fillets are thawed.

Do's and don'ts of cryo-electron microscopy: a primer on sample preparation and high quality data collection for macromolecular 3D reconstruction.

PubMed

Cabra, Vanessa; Samsó, Montserrat

2015-01-09

Cryo-electron microscopy (cryoEM) entails flash-freezing a thin layer of sample on a support, and then visualizing the sample in its frozen hydrated state by transmission electron microscopy (TEM). This can be achieved with very low quantity of protein and in the buffer of choice, without the use of any stain, which is very useful to determine structure-function correlations of macromolecules. When combined with single-particle image processing, the technique has found widespread usefulness for 3D structural determination of purified macromolecules. The protocol presented here explains how to perform cryoEM and examines the causes of most commonly encountered problems for rational troubleshooting; following all these steps should lead to acquisition of high quality cryoEM images. The technique requires access to the electron microscope instrument and to a vitrification device. Knowledge of the 3D reconstruction concepts and software is also needed for computerized image processing. Importantly, high quality results depend on finding the right purification conditions leading to a uniform population of structurally intact macromolecules. The ability of cryoEM to visualize macromolecules combined with the versatility of single particle image processing has proven very successful for structural determination of large proteins and macromolecular machines in their near-native state, identification of their multiple components by 3D difference mapping, and creation of pseudo-atomic structures by docking of x-ray structures. The relentless development of cryoEM instrumentation and image processing techniques for the last 30 years has resulted in the possibility to generate de novo 3D reconstructions at atomic resolution level.

GHASTLI-determining physical properties of sediment containing natural and laboratory-formed gas hydrate: Chapter 24

USGS Publications Warehouse

Winters, William J.; Dillon, William P.; Pecher, Ingo A.; Mason, David H.; Max, Michael D.

2003-01-01

Gas-hydrate samples have been recovered at about 16 areas worldwide (Booth et al., 1996). However, gas hydrate is known to occur at about 50 locations on continental margins (Kvenvolden, 1993) and is certainly far more widespread so it may represent a potentially enormous energy resource (Kvenvolden, 1988). But adverse effects related to the presence of hydrate do occur. Gas hydrate appears to have caused slope instabilities along continental margins (Booth et al., 1994; Dillon et al., 1998; Mienert et al., 1998; Paull & Dillon, (Chapter 12; Twichell & Cooper, 2000) and it has also been responsible for drilling accidents (Yakushev and Collett, 1992). Uncontrolled release of methane could affect global climate (Chapter 11), because methane is 15–20 times more effective as a “greenhouse gas” than an equivalent concentration of carbon dioxide. Clearly, a knowledge of gas-hydrate properties is necessary to safely explore the possibility of energy recovery and to understand its past and future impact on the geosphere.

Geomechanical Behaviors of Laboratory-Formed Non-Cementing Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Seol, Y.

2015-12-01

Natural hydrate-bearing sediments (HBS) have been known to exist with non-cementing pore habits, i.e., pore-filling, load-bearing, or patchy type. However, few laboratory studies have been conducted to characterize geomechanical behaviors of non-cementing CH4-HBS, which are of great importance in engineering the process of drilling and gas production in natural hydrate reservoir. In this study, we conducted multi-stage drained triaxial tests on laboratory synthesized CH4-HBS samples, which were formed in sand-clay mixtures (5%wt kaolinite) to have non-cementing habits. Three different effective confining stresses, σ3' = 0.69, 1.38, and 2.76 MPa, were applied on the HBS with the hydrate saturation, Sh, in the range of 0 to ~ 40%. The result confirms that the strength and stiffness of HBS increases with effective confining stress and hydrate saturation. It is also demonstrated that when compared to the cementing HBS, the non-cementing HBS has lower strength and cohesion, owing to less inter-particle adhesion effects from non-cementing hydrate.

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

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

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

2012-01-15

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

Detection of Cryptosporidium oocysts in fresh and frozen cattle faeces: comparison of three methods.

PubMed

Brook, E J; Christley, R M; French, N P; Hart, C A

2008-01-01

The aim of this study was to compare the performance of three commonly used screening tests for Cryptosporidium oocysts in fresh and frozen cattle faeces. Twenty-nine freshly voided faecal samples were collected from calves from three farms in the northwest of England. Three diagnostic tests for Cryptosporidium were carried out on each sample both before and after freezing - the modified Ziehl-Neelsen (MZN) and auramine phenol (APh) stains and a commercial enzyme immunoassay (EIA) kit, the ProSpecT Cryptosporidium Microplate assay (Remel, Lenexa, KS). Twelve samples were deemed positive by the reference standard (polymerase chain reaction, PCR). There were some discrepancies between the results of the screening tests and the levels of agreement were quantified. The sensitivity and specificity of each method was determined, with PCR as the gold standard. Sensitivity and specificity of the MZN stain was optimized when samples with fewer than two oocyst-like bodies were classified as negative. All three screening methods used were effective in detecting Cryptosporidium infection in both fresh and frozen calf faeces. This study has highlighted the value of determining characteristics of tests used for diagnosis and epidemiological studies.

Influence of freeze-thawing on hyaluronic acid binding of human spermatozoa.

PubMed

Nijs, Martine; Creemers, Eva; Cox, Annemie; Janssen, Mia; Vanheusden, Elke; Castro-Sanchez, Yovanna; Thijs, Herbert; Ombelet, Willem

2009-08-01

Mature human spermatozoa have at least three specific hyaluronic acid (HA) binding proteins present on their sperm membrane. These receptors play a role in the acrosome reaction, hyaluronidase activity, hyaluronan-mediated motility and sperm-zona and sperm-oolemmal binding. Cryopreservation of spermatozoa can cause ultrastructural and even molecular damage. The aim of this study was to investigate if HA binding receptors of human spermatozoa remain functional after freeze-thawing. Forty patients were enrolled in the study. Semen samples were analysed before and after cryopreservation. Parameters analysed included concentration, motility, morphology and hyaluronan binding. Samples were frozen in CBS straws using a glycerol-glucose-based cryoprotectant. HA binding was studied using the sperm-hyaluronan binding assay. Freeze-thawing resulted in a significant decline in motility: the percentage of motile spermatozoa reduced from 50.6 to 30.3% (P < 0.001). HA binding properties of frozen-thawed spermatozoa remained unchanged after the freeze-thawing process: 68.5 +/- 17.1% spermatozoa of the neat sample were bound to HA, as were 71.3 +/- 20.4 of the frozen-thawed sample. This study indicates that freeze-thawing did not alter the functional hyaluronan binding sites of mature motile spermatozoa, and therefore will not alter their fertilizing potential.

An evaluation of Brix refractometry instruments for measurement of colostrum quality in dairy cattle.

PubMed

Bielmann, V; Gillan, J; Perkins, N R; Skidmore, A L; Godden, S; Leslie, K E

2010-08-01

Acquisition of high quality colostrum is an important factor influencing neonatal calf health. Many methods have been used to assess the Ig concentration of colostrum; however, improved, validated evaluation tools are needed. The aims of this study were to evaluate both optical and digital Brix refractometer instruments for the measurement of Ig concentration of colostrum as compared with the gold standard radial immunodiffusion assay laboratory assessment and to determine the correlation between Ig measurements taken from fresh and frozen colostrum samples for both Brix refractometer instruments. This research was completed using 288 colostrum samples from 3 different farms. It was concluded that the optical and digital Brix refractometers were highly correlated for both fresh and frozen samples (r=0.98 and r=0.97, respectively). Correlation between both refractometer instruments for fresh and frozen samples and the gold standard radial immunodiffusion assay were determined to be very similar, with a correlation coefficient between 0.71 and 0.74. Both instruments exhibited excellent test characteristics, indicating an appropriate cut-off point of 22% Brix score for the identification of good quality colostrum. Copyright (c) 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

The Change of Total Anthocyanins in Blueberries and Their Antioxidant Effect After Drying and Freezing

PubMed Central

Srzednicki, George

2004-01-01

This study examined the effects of freezing, storage, and cabinet drying on the anthocyanin content and antioxidant activity of blueberries (Vaccinium corymbosum L). Fresh samples were stored for two weeks at 5°C while frozen samples were kept for up to three months at −20°C. There were two drying treatments, one including osmotic pretreatment followed by cabinet drying and the other involving only cabinet drying. Total anthocyanins found in fresh blueberries were 7.2 ± 0.5 mg/g dry matter, expressed as cyanidin 3-rutinoside equivalents. In comparison with fresh samples, total anthocyanins in untreated and pretreated dried blueberries were significantly reduced to 4.3 ± 0.1 mg/g solid content, 41% loss, and 3.7 ± 0.2 mg/g solid content, 49% loss, respectively. Osmotic treatment followed by a thermal treatment had a greater effect on anthocyanin loss than the thermal treatment alone. In contrast, the frozen samples did not show any significant decrease in anthocyanin level during three months of storage. Measurement of the antioxidant activity of anthocyanin extracts from blueberries showed there was no significant difference between fresh, dried, and frozen blueberries. PMID:15577185

Biologically active antimicrobial and antioxidant substances in the Helianthus annuus L. bee pollen.

PubMed

Fatrcová-Šramková, Katarína; Nôžková, Janka; Máriássyová, Magda; Kačániová, Miroslava

2016-01-01

The objective of this study was to measure the content of flavonoids, polyphenols, and carotenoids in the Helianthus annuus L. bee pollen. It was also to evaluate the ability of the dried, frozen, and freeze-dried extracts of sunflower (H. annuus) pollen, its scavenged free radicals and reducing action. Another aim of this study was to investigate the antimicrobial in vitro action of the H. annuus pollen extracts against the Gram-positive and Gram-negative bacteria and fungi. All pollen extracts showed medium antiradical activity and reductive ability. The most effective was the freeze-dried extract in both evaluation systems. The evaluation of the protective effects of DNA using a biosensor showed an opposite trending-frozen ˃ dried ˃ freeze-dried pollen. For the evaluation of antiradical activity, the DPPH method was used, and reductive ability was assessed by means of phosphomolybdic complex formation. The comparison of the polyphenols content shows higher values in freeze-dried bee pollen than in the dried and frozen pollen. The highest content of flavonoids was found in the frozen samples and the most carotenoids were present in the dried samples. In our study, the best antibacterial effects of the dried sunflower bee pollen extracts were found against Paenibacillus larvae, Pseudomonas aeruginosa, and Enterococcus raffinosus. The best inhibitory properties of the frozen sunflower bee pollen extracts were found against Escherichia coli, Pseudomonas aeruginosa, and Paenibacillus larvae. Very good inhibitory effects of freeze-dried sunflower bee pollen were found against Paenibacillus larvae, Brochotrix thermosphacta, and Enterococcus raffinosus. The best antifungal activity of the sunflower bee pollen was found in the frozen bee pollen extracts against Aspergillus ochraceus and freeze-dried bee pollen extracts against Aspergillus niger.

Effect of different procedures of ejaculate collection, extenders and packages on DNA integrity of boar spermatozoa following freezing-thawing.

PubMed

Fraser, L; Strzezek, J

2007-06-01

Whole ejaculate or sperm-rich fraction, collected from four sexually mature boars, was frozen in an extender containing lactose-hen egg yolk with glycerol (lactose-HEY-G) or extender containing lactose, lyophilized lipoprotein fractions isolated from ostrich egg yolk and glycerol (lactose-LPFo-G), and Orvus Es Paste, respectively. The sperm samples were also frozen in a standard boar semen extender (Kortowo-3), without the addition of cryoprotective substances. Sperm DNA integrity was assessed using a modified neutral comet assay. Sperm characteristics such as motility, plasma membrane integrity (SYBR-14/PI), mitochondrial function (rhodamine 123) and acrosome integrity were monitored. Freezing-thawing caused a significant increase (P<0.05) in sperm DNA fragmentation, irrespective of the procedures of ejaculate collection and extender type. Sperm DNA fragmentation was significantly lower (P<0.05) in the whole ejaculate compared with the sperm-rich fraction, indicating that spermatozoa maintained in the whole seminal plasma prior to its removal for freezing-thawing procedure were less vulnerable to cryo-induced DNA fragmentation. Furthermore, spermatozoa frozen in lactose-HEY-G or lactose-LPFo-G extender exhibited lower (P<0.05) DNA fragmentation than those frozen in the absence of cryoprotective substances. The levels of sperm DNA damage, as expressed by comet tail length and tail moment values, were significantly higher (P<0.05) in sperm samples frozen in the absence of cryoprotective substances. The deterioration in post-thaw sperm DNA integrity was concurrent with reduced sperm characteristics. It can be suggested that evaluation of DNA integrity, coupled with different sperm characteristics such as motility, plasma membrane integrity and mitochondrial function, may aid in determining the quality of frozen-thawed boar semen.

Inactivation kinetics of Vibrio vulnificus in phosphate-buffered saline at different freezing and storage temperatures and times.

PubMed

Seminario, Diana M; Balaban, Murat O; Rodrick, Gary

2011-03-01

Vibrio vulnificus (Vv) is a pathogen that can be found in raw oysters. Freezing can reduce Vv and increase the shelf life of oysters. The objective of this study was to develop predictive inactivation kinetic models for pure cultures of Vv at different frozen storage temperatures and times. Vv was diluted in phosphate-buffered saline (PBS) to obtain about 10(7) CFU/mL. Samples were frozen at -10, -35, and -80 °C (different freezing rates), and stored at different temperatures. Survival of Vv was followed after freezing and storage at -10 °C (0, 3, 6, and 9 d) and at -35 and -80 °C (every week for 6 wk). For every treatment, time-temperature data was obtained using thermocouples in blank vials. Predictive models were developed using first-order, Weibull and Peleg inactivation kinetics. Different freezing temperatures did not significantly (α = 0.05) affect survival of Vv immediately after freezing. The combined effect of freezing and 1 wk frozen storage resulted in 1.5, 2.6, and 4.9 log10 reductions for samples stored at -80, -35, and -10 °C, respectively. Storage temperature was the critical parameter in survival of Vv. A modified Weibull model successfully predicted Vv survival during frozen storage: log10 Nt = log 10No - 1.22 - ([t/10{-1.163-0.0466T}][0.00025T(2) + 0.049325]). N(o) and N(t) are initial and time t (d) survival counts, T is frozen storage temperature, Celsius degree. Vibrio vulnificus can be inactivated by freezing. Models to predict survival of V. vulnificus at different freezing temperatures and times were developed. This is the first step towards the prediction of V. vulnificus related safety of frozen oysters.

Effect of Holder pasteurization and frozen storage on macronutrients and energy content of breast milk.

PubMed

García-Lara, Nadia Raquel; Vieco, Diana Escuder; De la Cruz-Bértolo, Javier; Lora-Pablos, David; Velasco, Noelia Ureta; Pallás-Alonso, Carmen Rosa

2013-09-01

The aim of this study was to explore the effect of Holder pasteurization and frozen storage at -20°C after pasteurization on fat, total nitrogen, lactose, and energy content of breast milk. Both procedures are routinely practiced in human milk banks. A total of 34 samples of frozen breast milk, donated by 28 women, were collected. Once thawed, an aliquot of each sample was analyzed before pasteurization; the remaining milk was pasteurized (Holder method) and split into 8 aliquots. One aliquot was analyzed after pasteurization and the remainder frozen at -20°C and analyzed 30, 60, 90, 120, and 180 days later. For every aliquot, fat, total nitrogen, lactose, and energy content were determined using the device human Milk Analyzer. We observed a significant reduction in fat (3.5%; -0.17 (-0.29; -0.04) g/dL) and energy content (2.8%; -2.03 (-3.60; -0.46) g/dL) after pasteurization. A significant decrease over time was observed for fat, lactose and energy content. No significant changes were observed for nitrogen content. Mean differences between day 0 postpasteurization and day 180 were -0.13 (-0.21; -0.06) g/dL for fat, -0.08 (-0.13; -0.03) g/dL for lactose, and -1.55 (-2.38; -0.71) kcal/dL for energy content. The relative decreases were 2.8%, 1.7%, and 2.2%, respectively. Overall (postpasteurization + frozen storage), a 6.2% and 5% decrease were observed for fat and energy, respectively. Holder pasteurization decreased fat and energy content of human milk. Frozen storage at -20°C of pasteurized milk significantly reduced fat, lactose, and energy content of human milk.

Influence of Freezing and Storage Procedure on Human Urine Samples in NMR-Based Metabolomics

PubMed Central

Rist, Manuela J.; Muhle-Goll, Claudia; Görling, Benjamin; Bub, Achim; Heissler, Stefan; Watzl, Bernhard; Luy, Burkhard

2013-01-01

It is consensus in the metabolomics community that standardized protocols should be followed for sample handling, storage and analysis, as it is of utmost importance to maintain constant measurement conditions to identify subtle biological differences. The aim of this work, therefore, was to systematically investigate the influence of freezing procedures and storage temperatures and their effect on NMR spectra as a potentially disturbing aspect for NMR-based metabolomics studies. Urine samples were collected from two healthy volunteers, centrifuged and divided into aliquots. Urine aliquots were frozen either at −20 °C, on dry ice, at −80 °C or in liquid nitrogen and then stored at −20 °C, −80 °C or in liquid nitrogen vapor phase for 1–5 weeks before NMR analysis. Results show spectral changes depending on the freezing procedure, with samples frozen on dry ice showing the largest deviations. The effect was found to be based on pH differences, which were caused by variations in CO2 concentrations introduced by the freezing procedure. Thus, we recommend that urine samples should be frozen at −20 °C and transferred to lower storage temperatures within one week and that freezing procedures should be part of the publication protocol. PMID:24957990

Influence of Freezing and Storage Procedure on Human Urine Samples in NMR-Based Metabolomics.

PubMed

Rist, Manuela J; Muhle-Goll, Claudia; Görling, Benjamin; Bub, Achim; Heissler, Stefan; Watzl, Bernhard; Luy, Burkhard

2013-04-09

It is consensus in the metabolomics community that standardized protocols should be followed for sample handling, storage and analysis, as it is of utmost importance to maintain constant measurement conditions to identify subtle biological differences. The aim of this work, therefore, was to systematically investigate the influence of freezing procedures and storage temperatures and their effect on NMR spectra as a potentially disturbing aspect for NMR-based metabolomics studies. Urine samples were collected from two healthy volunteers, centrifuged and divided into aliquots. Urine aliquots were frozen either at -20 °C, on dry ice, at -80 °C or in liquid nitrogen and then stored at -20 °C, -80 °C or in liquid nitrogen vapor phase for 1-5 weeks before NMR analysis. Results show spectral changes depending on the freezing procedure, with samples frozen on dry ice showing the largest deviations. The effect was found to be based on pH differences, which were caused by variations in CO2 concentrations introduced by the freezing procedure. Thus, we recommend that urine samples should be frozen at -20 °C and transferred to lower storage temperatures within one week and that freezing procedures should be part of the publication protocol.

Gravimetric analysis and differential scanning calorimetric studies on glycerin-induced skin hydration.

PubMed

Lee, Ae-Ri Cho; Moon, Hee Kyung

2007-11-01

A thermal gravimetric analysis (TGA) and a differential scanning calorimetry (DSC) were carried out to characterize the water property and an alteration of lipid phase transition of stratum corneum (SC) by glycerin. In addition, the relationship between steady state skin permeation rate and skin hydration in various concentrations of glycerin was investigated. Water vapor absorption-desorption was studied in the hairless mouse stratum corneum. Dry SC samples were exposed to different conc. of glycerin (0-50%) followed by exposure to dry air and the change in weight property was monitored over time by use of TGA. In DSC study, significant decrease in DeltaH of the lipid transition in 10% glycerin and water treated sample: the heat of lipid transition of normal, water, 10% glycerin treated SC were 6.058, 4.412 and 4.316 mJ/mg, respectively. In 10% glycerin treated SCs, the Tc of water shifts around 129 degrees C, corresponding to the weakly bound secondary water. In 40% glycerin treated SC, the Tc of water shifts to 144 degrees C corresponding to strongly bound primary water. There was a good correlation between the hydration property of the skin and the steady state skin flux with the correlation coefficient (r2=0.94). As the hydration increased, the steady state flux increased. As glycerin concentration increased, hydration property decreased. High diffusivity induced by the hydration effect of glycerin and water could be the major contributing factor for the enhanced skin permeation of nicotinic acid (NA).

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

USGS Publications Warehouse

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

2004-01-01

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

Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.

2008-01-01

Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

Scientific results of the Second Gas Hydrate Drilling Expedition in the Ulleung Basin (UBGH2)

USGS Publications Warehouse

Ryu, Byong-Jae; Collett, Timothy S.; Riedel, Michael; Kim, Gil-Young; Chun, Jong-Hwa; Bahk, Jang-Jun; Lee, Joo Yong; Kim, Ji-Hoon; Yoo, Dong-Geun

2013-01-01

As a part of Korean National Gas Hydrate Program, the Second Ulleung Basin Gas Hydrate Drilling Expedition (UBGH2) was conducted from 9 July to 30 September, 2010 in the Ulleung Basin, East Sea, offshore Korea using the D/V Fugro Synergy. The UBGH2 was performed to understand the distribution of gas hydrates as required for a resource assessment and to find potential candidate sites suitable for a future offshore production test, especially targeting gas hydrate-bearing sand bodies in the basin. The UBGH2 sites were distributed across most of the basin and were selected to target mainly sand-rich turbidite deposits. The 84-day long expedition consisted of two phases. The first phase included logging-while-drilling/measurements-while-drilling (LWD/MWD) operations at 13 sites. During the second phase, sediment cores were collected from 18 holes at 10 of the 13 LWD/MWD sites. Wireline logging (WL) and vertical seismic profile (VSP) data were also acquired after coring operations at two of these 10 sites. In addition, seafloor visual observation, methane sensing, as well as push-coring and sampling using a Remotely Operated Vehicle (ROV) were conducted during both phases of the expedition. Recovered gas hydrates occurred either as pore-filling medium associated with discrete turbidite sand layers, or as fracture-filling veins and nodules in muddy sediments. Gas analyses indicated that the methane within the sampled gas hydrates is primarily of biogenic origin. This paper provides a summary of the operational and scientific results of the UBGH2 expedition as described in 24 papers that make up this special issue of the Journal of Marine and Petroleum Geology.

Mathematical modelling of liquid transport in swelling pharmaceutical immediate release tablets.

PubMed

Markl, Daniel; Yassin, Samy; Wilson, D Ian; Goodwin, Daniel J; Anderson, Andrew; Zeitler, J Axel

2017-06-30

Oral dosage forms are an integral part of modern health care and account for the majority of drug delivery systems. Traditionally the analysis of the dissolution behaviour of a dosage form is used as the key parameter to assess the performance of a drug product. However, understanding the mechanisms of disintegration is of critical importance to improve the quality of drug delivery systems. The disintegration performance is primarily impacted by the hydration and subsequent swelling of the powder compact. Here we compare liquid ingress and swelling data obtained using terahertz pulsed imaging (TPI) to a set of mathematical models. The interlink between hydration kinetics and swelling is described by a model based on Darcy's law and a modified swelling model based on that of Schott. Our new model includes the evolution of porosity, pore size and permeability as a function of hydration time. Results obtained from two sets of samples prepared from pure micro-crystalline cellulose (MCC) indicate a clear difference in hydration and swelling for samples of different porosities and particle sizes, which are captured by the model. Coupling a novel imaging technique, such as TPI, and mathematical models allows better understanding of hydration and swelling and eventually tablet disintegration. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Formation pressure testing at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Operational summary, history matching, and interpretations

USGS Publications Warehouse

Anderson, B.; Hancock, S.; Wilson, S.; Enger, C.; Collett, T.; Boswell, R.; Hunter, R.

2011-01-01

In February 2007, the U.S. Department of Energy, BP Exploration (Alaska), and the U.S. Geological Survey, collected open-hole pressure-response data, as well as gas and water sample collection, in a gas hydrate reservoir (the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well) using Schlumberger's Modular Dynamics Formation Tester (MDT) wireline tool. Four such MDT tests, ranging from six to twelve hours duration, and including a series of flow, sampling, and shut-in periods of various durations, were conducted. Locations for the testing were selected based on NMR and other log data to assure sufficient isolation from reservoir boundaries and zones of excess free water. Test stages in which pressure was reduced sufficiently to mobilize free water in the formation (yet not cause gas hydrate dissociation) produced readily interpretable pressure build-up profiles. Build-ups following larger drawdowns consistently showed gas-hydrate dissociation and gas release (as confirmed by optical fluid analyzer data), as well as progressive dampening of reservoir pressure build-up during sequential tests at a given MDT test station.History matches of one multi-stage, 12-h test (the C2 test) were accomplished using five different reservoir simulators: CMG-STARS, HydrateResSim, MH21-HYDRES, STOMP-HYD, and TOUGH. +. HYDRATE. Simulations utilized detailed information collected across the reservoir either obtained or determined from geophysical well logs, including thickness (11.3. m, 37 ft.), porosity (35%), hydrate saturation (65%), both mobile and immobile water saturations, intrinsic permeability (1000 mD), pore water salinity (5 ppt), and formation temperature (3.3-3.9 ??C). This paper will present the approach and preliminary results of the history-matching efforts, including estimates of initial formation permeability and analyses of the various unique features exhibited by the MDT results. ?? 2010 Elsevier Ltd.

Physical and Mechanical Properties of Surface Sediments and methane hydrate-bearing sediments in the Shenhu area of South China Sea

NASA Astrophysics Data System (ADS)

Jiang, J.; Shen, Z.; Jia, Y.

2017-12-01

Methane hydrates are superior energy resources and potential predisposing factors of geohazard. With the success in China's persistent exploitation of methane hydrates in the Shenhu area of South China Sea for 60 days, there is an increasing demand for detailed knowledge of sediment properties and hazard assessment in this area. In this paper, the physical and mechanical properties of both the surface sediments and methane hydrate-bearing sediments (MHBS) in the exploitation area, the Shenhu area of South China Sea, were investigated using laboratory geotechnical experiments, and triaxial tests were carried out on remolded sediment samples using a modified triaxial apparatus. The results show that sediments in this area are mainly silt with high moisture content, high plasticity, low permeability and low shear strength. The moisture content and permeability decrease while the shear strength increases with the increasing depth. The elastic modulus and peak strength of MHBS increase with the increasing effective confining pressure and higher hydrate saturation. The cohesion increases with higher hydrate saturation while the internal friction angle is barely affected by hydrate saturation. The obtained results demonstrate clearly that methane hydrates have significant impacts on the physical and mechanical properties of sediments and there is still a wide gap in knowledge about MHBS.

Comparison of Collection Methods for Fecal Samples in Microbiome Studies

PubMed Central

Vogtmann, Emily; Chen, Jun; Amir, Amnon; Shi, Jianxin; Abnet, Christian C.; Nelson, Heidi; Knight, Rob; Chia, Nicholas; Sinha, Rashmi

2017-01-01

Prospective cohort studies are needed to assess the relationship between the fecal microbiome and human health and disease. To evaluate fecal collection methods, we determined technical reproducibility, stability at ambient temperature, and accuracy of 5 fecal collection methods (no additive, 95% ethanol, RNAlater Stabilization Solution, fecal occult blood test cards, and fecal immunochemical test tubes). Fifty-two healthy volunteers provided fecal samples at the Mayo Clinic in Rochester, Minnesota, in 2014. One set from each sample collection method was frozen immediately, and a second set was incubated at room temperature for 96 hours and then frozen. Intraclass correlation coefficients (ICCs) were calculated for the relative abundance of 3 phyla, 2 alpha diversity metrics, and 4 beta diversity metrics. Technical reproducibility was high, with ICCs for duplicate fecal samples between 0.64 and 1.00. Stability for most methods was generally high, although the ICCs were below 0.60 for 95% ethanol in metrics that were more sensitive to relative abundance. When compared with fecal samples that were frozen immediately, the ICCs were below 0.60 for the metrics that were sensitive to relative abundance; however, the remaining 2 alpha diversity and 3 beta diversity metrics were all relatively accurate, with ICCs above 0.60. In conclusion, all fecal sample collection methods appear relatively reproducible, stable, and accurate. Future studies could use these collection methods for microbiome analyses. PMID:27986704

Development and characterization of a stable adhesive bond between a poly(dimethylsiloxane) catheter material and a bacterial biofilm resistant acrylate polymer coating

PubMed Central

Tyler, Bonnie J.; Hook, Andrew; Pelster, Andreas; Williams, Paul; Alexander, Morgan; Arlinghaus, Heinrich F.

2017-01-01

Catheter associated urinary tract infections are the most common health related infections worldwide, contributing significantly to patient morbidity and mortality and increased health care costs. To reduce the incidence of these infections, new materials that resist bacterial biofilm formation are needed. A composite catheter material, consisting of bulk poly(dimethylsiloxane) (PDMS) coated with a novel bacterial biofilm resistant polyacrylate [ethylene glycol dicyclopentenyl ether acrylate (EGDPEA)-co-di(ethyleneglycol) methyl ether methacrylate (DEGMA)], has been proposed. The coated material shows excellent bacterial resistance when compared to commercial catheter materials, but delamination of the EGDPEA-co-DEGMA coatings under mechanical stress presents a challenge. In this work, the use of oxygen plasma treatment to improve the wettability and reactivity of the PDMS catheter material and improve adhesion with the EGDPEA-co-DEGMA coating has been investigated. Argon cluster three dimensional-imaging time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to probe the buried adhesive interface between the EGDPEA-co-DEGMA coating and the treated PDMS. ToF-SIMS analysis was performed in both dry and frozen-hydrated states, and the results were compared to mechanical tests. From the ToF-SIMS data, the authors have been able to observe the presence of PDMS, silicates, salt particles, cracks, and water at the adhesive interface. In the dry catheters, low molecular weight PDMS oligomers at the interface were associated with poor adhesion. When hydrated, the hydrophilic silicates attracted water to the interface and led to easy delamination of the coating. The best adhesion results, under hydrated conditions, were obtained using a combination of 5 min O2 plasma treatment and silane primers. Cryo-ToF-SIMS analysis of the hydrated catheter material showed that the bond between the primed PDMS catheter and the EGDPEA-co-DEGMA coating was stable in the presence of water. The resulting catheter material resisted Escherichia coli and Proteus mirabilis biofilm colonization by up to 95% compared with uncoated PDMS after 10 days of continuous bacterial exposure and had the mechanical properties necessary for use as a urinary catheter. PMID:28535686

Implications of the pH and temperature of diluted, cooled boar semen on fresh and frozen-thawed sperm motility characteristics.

PubMed

Purdy, P H; Tharp, N; Stewart, T; Spiller, S F; Blackburn, H D

2010-10-15

Boar semen is typically collected, diluted and cooled for AI use over numerous days, or frozen immediately after shipping to capable laboratories. The storage temperature and pH of the diluted, cooled boar semen could influence the fertility of boar sperm. Therefore, the purpose of this study was to determine the effects of pH and storage temperature on fresh and frozen-thawed boar sperm motility end points. Semen samples (n = 199) were collected, diluted, cooled and shipped overnight to the National Animal Germplasm Program laboratory for freezing and analysis from four boar stud facilities. The temperature, pH and motility characteristics, determined using computer automated semen analysis, were measured at arrival. Samples were then cryopreserved and post-thaw motility determined. The commercial stud was a significant source of variation for mean semen temperature and pH, as well as total and progressive motility, and numerous other sperm motility characteristics. Based on multiple regression analysis, pH was not a significant source of variation for fresh or frozen-thawed boar sperm motility end points. However, significant models were derived which demonstrated that storage temperature, boar, and the commercial stud influenced sperm motility end points and the potential success for surviving cryopreservation. We inferred that maintaining cooled boar semen at approximately 16 °C during storage will result in higher fresh and frozen-thawed boar sperm quality, which should result in greater fertility. Copyright © 2010 Elsevier Inc. All rights reserved.

New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

NASA Astrophysics Data System (ADS)

Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

2016-05-01

The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

Preliminary Measurements of the Attenuation Properties of Polycrystalline Water Ice and CO2 Clathrate Hydrates at the Tidal Frequencies of Europa and Enceladus

NASA Astrophysics Data System (ADS)

Choukroun, M.; Castillo, J. C.; Young, J. B.; Mielke, R.

2009-12-01

We will report measurements of the attenuation properties of polycrystalline water ice and CO2 clathrate hydrates samples obtained in the frequency range 3x10-6 to 10-2 Hz, which encompasses the tidal frequencies of Europa and Enceladus. Previous attenuation measurements obtained on a variety of planetary materials have demonstrated that the mechanisms driving attenuation in the frequency range 10-4 to 1 Hz are controlled by the same parameters controlling the creep properties of these materials: temperature, stress, microstructure (including grain size), and the presence of second-phase impurities. Thus, accurate control and characterization of the microstructure and composition of tested samples are key steps toward the development of empirical relationships describing the mechanical response of these materials. This is the reason why we have invested significant effort in the development of synthesis procedures for the production of our samples. Both water ice and clathrate hydrate samples are grown from H2O ice seeds, which are produced by grinding ice crystals pre-grown at -30°C from pure de-ionized liquid water. A high pressure - low temperature vessel, which achieves pressures up to 200 bars and temperatures within the range -50 - +50 °C, is used for the growth of clathrate hydrates. These are synthesized by reaction of ice seeds with CO2 at temperatures close to the melting point of ice in order to improve reaction kinetics. Characterization of the samples composition and microstructure is carried out via crossed-polarized cryo-microscopic observations, and via imaging with a Scanning Electron Microprobe equipped with a liquid - nitrogen cooled stage (CryoSEM). The Energy Dispersive Spectrometer capability of the SEM provides elemental composition for verification of the purity of the samples. For clathrate hydrates, Raman microspectroscopy is also used to ensure the homogeneity of sample composition. We will show that the grain size of the ice seeds is not affected by the transformation into clathrate hydrates. However, the sub-grain structure obviously undergoes significant changes, which might be reflected in the mechanical behavior. In order to remove microporosity, a compaction system has been implemented, which consists to the application of high pressures under vacuum and at very low temperatures. We will show the result of compaction experiments in terms of residual porosity and microstructure evolution. We will also present initial measurements on the attenuation properties of polycrystalline water ice and CO2 clathrate hydrates at the stress conditions and tidal frequencies approaching those of icy satellites such as Europa and Enceladus. Acknowledgements: We gratefully acknowledge C. McCarthy and H. Engelhardt for technical advise and support. MC is supported by a NASA Postdoctoral Fellowship, administered by Oak Ridge Associated Universities. This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA. Copyright 2009, California Institute of Technology. Government sponsorship acknowledged.

Combining CO2 sequestration and CH4 production by means of guest exchange in a gas hydrate reservoir: two pilot scale experiments

NASA Astrophysics Data System (ADS)

Heeschen, Katja U.; Spangenberg, Erik; Schicks, Judith M.; Deusner, Christian; Priegnitz, Mike; Strauch, Bettina; Bigalke, Nikolaus; Luzi-Helbing, Manja; Kossel, Elke; Haeckel, Matthias; Wang, Yi

2017-04-01

Methane (CH4) hydrates are considered as a player in the field of energy supply and - if applied as such - as a possible sink for the greenhouse gas carbon dioxide (CO2). Next to the more conventional production methods depressurization and thermal stimulation, an extraction of CH4 by means of CO2 injection is investigated. The method is based on the chemical potential gradient between the CH4 hydrate phase and the injected CO2 phase. Results from small-scale laboratory experiments on the replacement method indicate recovery ratios of up to 66% CH4 but also encounter major discrepancies in conversion rates. So far it has not been demonstrated with certainty that the process rates are sufficient for an energy and cost effective production of CH4 with a concurrent sequestration of CO2. In a co-operation of GFZ and GEOMAR we used LARS (Large Scale Reservoir Simulator) to investigate the CO2-CH4-replacement method combined with thermal stimulation. LARS accommodates a sample volume of 210 l and allows for the simulation of in situ conditions typically found in gas hydrate reservoirs. Based on the sample size, diverse transport mechanisms could be simulated, which are assumed to significantly alter process yields. Temperature and pressure data complemented by a high resolution electrical resistivity tomography (ERT), gas chromatography, and flow measurements serve to interpret the experiments. In two experiments 50 kg heated CO2 was injected into sediments with CH4 hydrate saturations of 50%. While in the first experiment the CO2 was injected discontinuously in a so called "huff'n puff" manner, the second experiment saw a continuous injection. Conditions within LARS were set to 13 MPa and 8˚ C, which allow for stability of pure CO2 and CH4 hydrates as well as mixed hydrates. The CO2 was heated and entered the sediment sample with temperatures of approximately 30˚ C. In this presentation we will discuss the results from the large-scale experiments and compare them with data from small-scale experiments.

Cellular Electron Cryotomography: Toward Structural Biology In Situ.

PubMed

Oikonomou, Catherine M; Jensen, Grant J

2017-06-20

Electron cryotomography (ECT) provides three-dimensional views of macromolecular complexes inside cells in a native frozen-hydrated state. Over the last two decades, ECT has revealed the ultrastructure of cells in unprecedented detail. It has also allowed us to visualize the structures of macromolecular machines in their native context inside intact cells. In many cases, such machines cannot be purified intact for in vitro study. In other cases, the function of a structure is lost outside the cell, so that the mechanism can be understood only by observation in situ. In this review, we describe the technique and its history and provide examples of its power when applied to cell biology. We also discuss the integration of ECT with other techniques, including lower-resolution fluorescence imaging and higher-resolution atomic structure determination, to cover the full scale of cellular processes.

Apparatus for X-ray diffraction microscopy and tomography of cryo specimens

DOE PAGES

Beetz, T.; Howells, M. R.; Jacobsen, C.; ...

2005-03-14

An apparatus for diffraction microscopy of biological and materials science specimens is described. In this system, a coherent soft X-ray beam is selected with a pinhole, and the illuminated specimen is followed by an adjustable beamstop and CCD camera to record diffraction data from non-crystalline specimens. In addition, a Fresnel zone plate can be inserted to allow for direct imaging. The system makes use of a cryogenic specimen holder with cryotransfer capabilities to allow frozen hydrated specimens to be loaded. The specimen can be tilted over a range of ± 80 ° degrees for three-dimensional imaging; this is done bymore » computer-controlled motors, enabling automated alignment of the specimen through a tilt series. The system is now in use for experiments in soft X-ray diffraction microscopy.« less

X-ray microanalysis in the scanning electron microscope.

PubMed

Roomans, Godfried M; Dragomir, Anca

2014-01-01

X-ray microanalysis conducted using the scanning electron microscope is a technique that allows the determination of chemical elements in bulk or semi-thick specimens. The lowest concentration of an element that can be detected is in the order of a few mmol/kg or a few hundred parts per million, and the smallest amount is in the order of 10(-18) g. The spatial resolution of the analysis depends on the thickness of the specimen. For biological specimen analysis, care must be taken to prevent displacement/loss of the element of interest (usually ions). Protocols are presented for the processing of frozen-hydrated and freeze-dried specimens, as well as for the analysis of small volumes of fluid, cell cultures, and other specimens. Aspects of qualitative and quantitative analysis are covered, including limitations of the technique.

X-ray microanalysis in the scanning electron microscope.

PubMed

Roomans, Godfried M; Dragomir, Anca

2007-01-01

X-ray microanalysis conducted using the scanning electron microscope is a technique that allows the determination of chemical elements in bulk or semithick specimens. The lowest concentration of an element that can be detected is in the order of a few mmol/kg or a few hundred parts per million, and the smallest amount is in the order of 10(-18) g. The spatial resolution of the analysis depends on the thickness of the specimen. For biological specimen analysis, care must be taken to prevent displacement/loss of the element of interest (usually ions). Protocols are presented for the processing of frozen-hydrated and freeze-dried specimens, as well as for the analysis of small volumes of fluid, cell cultures and other specimens. Aspects of qualitative and quantitative analysis are covered, including limitations of the technique.

7 CFR 91.20 - Shipping.

Code of Federal Regulations, 2013 CFR

2013-01-01

... refrigerated samples should contain ice or ice packs to maintain temperatures of 0° to 5 °C, unless a different temperature is required for the sample to be tested. (d) Containers for frozen samples should contain dry ice...

7 CFR 91.20 - Shipping.

Code of Federal Regulations, 2012 CFR

2012-01-01

... refrigerated samples should contain ice or ice packs to maintain temperatures of 0° to 5 °C, unless a different temperature is required for the sample to be tested. (d) Containers for frozen samples should contain dry ice...

7 CFR 91.20 - Shipping.

Code of Federal Regulations, 2014 CFR

2014-01-01

... refrigerated samples should contain ice or ice packs to maintain temperatures of 0° to 5 °C, unless a different temperature is required for the sample to be tested. (d) Containers for frozen samples should contain dry ice...

7 CFR 91.20 - Shipping.

Code of Federal Regulations, 2011 CFR

2011-01-01

... refrigerated samples should contain ice or ice packs to maintain temperatures of 0° to 5 °C, unless a different temperature is required for the sample to be tested. (d) Containers for frozen samples should contain dry ice...

7 CFR 91.20 - Shipping.

Code of Federal Regulations, 2010 CFR

2010-01-01

... refrigerated samples should contain ice or ice packs to maintain temperatures of 0° to 5 °C, unless a different temperature is required for the sample to be tested. (d) Containers for frozen samples should contain dry ice...

Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone

USGS Publications Warehouse

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

1998-01-01

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment - water interface at 2-19 m below the seafloor, (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2-to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ???17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperature of the recovered core ranged from 2 to - 18??C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (??34S, +27.4???) were released. The ??13C values of the CH4 in the gas hydrate, -64.5 to -67.5???(PDB), together with ??D values of - 197 to - 199???(SMOW) indicate a primarily microbial source for the CH4. The ??18O value of the hydrate H2O is +2.9???(SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a ???99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, technically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone. ?? 1998 Elsevier Science B.V. All rights reserved.

Formation of natural gas hydrates in marine sediments. Gas hydrate growth and stability conditioned by host sediment properties

USGS Publications Warehouse

Clennell, M.B.; Henry, P.; Hovland, M.; Booth, J.S.; Winters, W.J.; Thomas, M.

2000-01-01

The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine-grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.

High-Explosive Cratering a Frozen and Unfrozen Soils in Alaska

DTIC Science & Technology

1980-02-01

SAMPLES I DEPTH TO .... T 24 DATE HOLEIROUN - S]T AR ED adO~ ________ F __24_ad_2____________7 EL . ITHOE (4IQ1 ~.0oioy Section ChlofRrndotboelI a...MotorIoI. Bronco Dno 20 f t.D. FREDRICKSON DEPTH %WATER SAI.IPLE SOIL MAAX FEET .4CtENT NO LEGEND CLASSIFICATION IZE F G i Silty Sandy Gravel Brown, Frozen

Broken rice kernels and the kinetics of rice hydration and texture during cooking.

PubMed

Saleh, Mohammed; Meullenet, Jean-Francois

2013-05-01

During rice milling and processing, broken kernels are inevitably present, although to date it has been unclear as to how the presence of broken kernels affects rice hydration and cooked rice texture. Therefore, this work intended to study the effect of broken kernels in a rice sample on rice hydration and texture during cooking. Two medium-grain and two long-grain rice cultivars were harvested, dried and milled, and the broken kernels were separated from unbroken kernels. Broken rice kernels were subsequently combined with unbroken rice kernels forming treatments of 0, 40, 150, 350 or 1000 g kg(-1) broken kernels ratio. Rice samples were then cooked and the moisture content of the cooked rice, the moisture uptake rate, and rice hardness and stickiness were measured. As the amount of broken rice kernels increased, rice sample texture became increasingly softer (P < 0.05) but the unbroken kernels became significantly harder. Moisture content and moisture uptake rate were positively correlated, and cooked rice hardness was negatively correlated to the percentage of broken kernels in rice samples. Differences in the proportions of broken rice in a milled rice sample play a major role in determining the texture properties of cooked rice. Variations in the moisture migration kinetics between broken and unbroken kernels caused faster hydration of the cores of broken rice kernels, with greater starch leach-out during cooking affecting the texture of the cooked rice. The texture of cooked rice can be controlled, to some extent, by varying the proportion of broken kernels in milled rice. © 2012 Society of Chemical Industry.

Automated tilt series alignment and tomographic reconstruction in IMOD.

PubMed

Mastronarde, David N; Held, Susannah R

2017-02-01

Automated tomographic reconstruction is now possible in the IMOD software package, including the merging of tomograms taken around two orthogonal axes. Several developments enable the production of high-quality tomograms. When using fiducial markers for alignment, the markers to be tracked through the series are chosen automatically; if there is an excess of markers available, a well-distributed subset is selected that is most likely to track well. Marker positions are refined by applying an edge-enhancing Sobel filter, which results in a 20% improvement in alignment error for plastic-embedded samples and 10% for frozen-hydrated samples. Robust fitting, in which outlying points are given less or no weight in computing the fitting error, is used to obtain an alignment solution, so that aberrant points from the automated tracking can have little effect on the alignment. When merging two dual-axis tomograms, the alignment between them is refined from correlations between local patches; a measure of structure was developed so that patches with insufficient structure to give accurate correlations can now be excluded automatically. We have also developed a script for running all steps in the reconstruction process with a flexible mechanism for setting parameters, and we have added a user interface for batch processing of tilt series to the Etomo program in IMOD. Batch processing is fully compatible with interactive processing and can increase efficiency even when the automation is not fully successful, because users can focus their effort on the steps that require manual intervention. Copyright © 2016 Elsevier Inc. All rights reserved.

Annealing to optimize the primary drying rate, reduce freezing-induced drying rate heterogeneity, and determine T(g)' in pharmaceutical lyophilization.

PubMed

Searles, J A; Carpenter, J F; Randolph, T W

2001-07-01

In a companion paper we show that the freezing of samples in vials by shelf-ramp freezing results in significant primary drying rate heterogeneity because of a dependence of the ice crystal size on the nucleation temperature during freezing.1 The purpose of this study was to test the hypothesis that post-freezing annealing, in which the product is held at a predetermined temperature for a specified duration, can reduce freezing-induced heterogeneity in sublimation rates. In addition, we test the impact of annealing on primary drying rates. Finally, we use the kinetics of relaxations during annealing to provide a simple measurement of T(g)', the glass transition temperature of the maximally freeze-concentrated amorphous phase, under conditions and time scales most appropriate for industrial lyophilization cycles. Aqueous solutions of hydroxyethyl starch (HES), sucrose, and HES:sucrose were either frozen by placement on a shelf while the temperature was reduced ("shelf-ramp frozen") or by immersion into liquid nitrogen. Samples were then annealed for various durations over a range of temperatures and partially lyophilized to determine the primary drying rate. The morphology of fully dried liquid nitrogen-frozen samples was examined using scanning electron microscopy. Annealing reduced primary drying rate heterogeneity for shelf-ramp frozen samples, and resulted in up to 3.5-fold increases in the primary drying rate. These effects were due to increased ice crystal sizes, simplified amorphous structures, and larger and more numerous holes on the cake surface of annealed samples. Annealed HES samples dissolved slightly faster than their unannealed counterparts. Annealing below T(g)' did not result in increased drying rates. We present a simple new annealing-lyophilization method of T(g)' determination that exploits this phenomenon. It can be carried out with a balance and a freeze-dryer, and has the additional advantage that a large number of candidate formulations can be evaluated simultaneously.

High-speed shaking of frozen blood clots for extraction of human and malaria parasite DNA.

PubMed

Lundblom, Klara; Macharia, Alex; Lebbad, Marianne; Mohammed, Adan; Färnert, Anna

2011-08-08

Frozen blood clots remaining after serum collection is an often disregarded source of host and pathogen DNA due to troublesome handling and suboptimal outcome. High-speed shaking of clot samples in a cell disruptor manufactured for homogenization of tissue and faecal specimens was evaluated for processing frozen blood clots for DNA extraction. The method was compared to two commercial clot protocols based on a chemical kit and centrifugation through a plastic sieve, followed by the same DNA extraction protocol. Blood clots with different levels of parasitaemia (1-1,000 p/μl) were prepared from parasite cultures to assess sensitivity of PCR detection. In addition, clots retrieved from serum samples collected within two epidemiological studies in Kenya (n = 630) were processed by high speed shaking and analysed by PCR for detection of malaria parasites and the human α-thalassaemia gene. High speed shaking succeeded in fully dispersing the clots and the method generated the highest DNA yield. The level of PCR detection of P. falciparum parasites and the human thalassaemia gene was the same as samples optimally collected with an anticoagulant. The commercial clot protocol and centrifugation through a sieve failed to fully dissolve the clots and resulted in lower sensitivity of PCR detection. High speed shaking was a simple and efficacious method for homogenizing frozen blood clots before DNA purification and resulted in PCR templates of high quality both from humans and malaria parasites. This novel method enables genetic studies from stored blood clots.

Analytical study of comet nucleus samples

NASA Technical Reports Server (NTRS)

Albee, A. L.

1989-01-01

Analytical procedures for studying and handling frozen (130 K) core samples of comet nuclei are discussed. These methods include neutron activation analysis, x ray fluorescent analysis and high resolution mass spectroscopy.

A preliminary result of three-dimensional microarray technology to gene analysis with endoscopic ultrasound-guided fine-needle aspiration specimens and pancreatic juices

PubMed Central

2010-01-01

Background Analysis of gene expression and gene mutation may add information to be different from ordinary pathological tissue diagnosis. Since samples obtained endoscopically are very small, it is desired that more sensitive technology is developed for gene analysis. We investigated whether gene expression and gene mutation analysis by newly developed ultra-sensitive three-dimensional (3D) microarray is possible using small amount samples from endoscopic ultrasound-guided fine-needle aspiration (EUS-FNA) specimens and pancreatic juices. Methods Small amount samples from 17 EUS-FNA specimens and 16 pancreatic juices were obtained. After nucleic acid extraction, the samples were amplified with labeling and analyzed by the 3D microarray. Results The analyzable rate with the microarray was 46% (6/13) in EUS-FNA specimens of RNAlater® storage, and RNA degradations were observed in all the samples of frozen storage. In pancreatic juices, the analyzable rate was 67% (4/6) in frozen storage samples and 20% (2/10) in RNAlater® storage. EUS-FNA specimens were classified into cancer and non-cancer by gene expression analysis and K-ras codon 12 mutations were also detected using the 3D microarray. Conclusions Gene analysis from small amount samples obtained endoscopically was possible by newly developed 3D microarray technology. High quality RNA from EUS-FNA samples were obtained and remained in good condition only using RNA stabilizer. In contrast, high quality RNA from pancreatic juice samples were obtained only in frozen storage without RNA stabilizer. PMID:20416107

Effects of yeast, fermentation time, and preservation methods on tarhana.

PubMed

Gurbuz, Ozan; Gocmen, Duygu; Ozmen, Nese; Dagdelen, Fatih

2010-01-01

The physicochemical properties of tarhana soup produced with different dough treatments, fermentation times, and preservation methods were examined. Tarhana doughs were prepared with yogurt (control) or baker's yeast (Saccharomyces cerevisiae) and fermented for 3 days. Samples were taken at 24, 48, and 72 hr. Samples were then preserved via one of four methods: sun dried, dried in the shade, vacumn dried, and frozen. Frozen samples produced lower organic acid levels after 72 hr of fermentation in both control (0.68 g/100 g) and yeast (0.61 g/100 g) applications than samples that were dried (0.94 g/100 g control samples; 0.81 g/100 g samples with yeast). Increasing fermentation time resulted in a significant effect on the formation of organic acid in the tarhana (p < .01). At 72 hr of fermentation, total acidity increased 11%, 17%, and 23% for tarhana samples vacumn-dried, sun-dried, and dried in the shade, respectively. Preservation methods also affected the moisture, ash, crude protein, total acidity, pH, salt, fat, reducing sugar levels, and the sensory assestment of tarhana soup (p < .01). Sensory characteristics were not significantly affected by baker's yeast in any of the preservation methods used (p > .01). However, sensory scores for tarhana prepared from the samples dried in a sheltered area showed a reduction in color desireablilty as the fermentation time increased. The soup prepared from frozen tarhana (72 hr fermentation, with yeast) had the highest scores with respect to color, mouth feel, flavor, and overall acceptability. Vacuum-dried samples' scores in these areas were also high in comparison to the two other drying methods.

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

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

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

DOE PAGES

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

2015-10-14

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

THCM Coupled Model for Hydrate-Bearing Sediments: Data Analysis and Design of New Field Experiments (Marine and Permafrost Settings)

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

Sanchez, Marcelo J.; Santamarina, J. Carlos

Gas hydrates are solid compounds made of water molecules clustered around low molecular weight gas molecules such as methane, hydrogen, and carbon dioxide. Methane hydrates form under pressure (P) and temperature (T) conditions that are common in sub-permafrost layers and in deep marine sediments. Stability conditions constrain the occurrence of gas hydrates to submarine sediments and permafrost regions. The amount of technically recoverable methane trapped in gas hydrate may exceed 104tcf. Gas hydrates are a potential energy resource, can contribute to climate change, and can cause large-scale seafloor instabilities. In addition, hydrate formation can be used for CO2 sequestration (alsomore » through CO2-CH4 replacement), and efficient geological storage seals. The experimental study of hydrate bearing sediments has been hindered by the very low solubility of methane in water (lab testing), and inherent sampling difficulties associated with depressurization and thermal changes during core extraction. This situation has prompted more decisive developments in numerical modeling in order to advance the current understanding of hydrate bearing sediments, and to investigate/optimize production strategies and implications. The goals of this research has been to addresses the complex thermo-hydro-chemo-mechanical THCM coupled phenomena in hydrate-bearing sediments, using a truly coupled numerical model that incorporates sound and proven constitutive relations, satisfies fundamental conservation principles. Analytical solutions aimed at verifying the proposed code have been proposed as well. These tools will allow to better analyze available data and to further enhance the current understanding of hydrate bearing sediments in view of future field experiments and the development of production technology.« less

Comparison of biochemical values in serum and plasma, fresh and frozen plasma, and hemolyzed samples from orange-winged Amazon parrots (Amazona amazonica).

PubMed

Hawkins, Michelle G; Kass, Philip H; Zinkl, Joseph G; Tell, Lisa A

2006-06-01

To the authors' knowledge, on the basis of sample type, storage condition, or hemolysis, differences in serum and plasma biochemical values have not been evaluated in orange-winged Amazon parrots (Amazona amazonica). The purpose of this study was to compare values for biochemical analytes in serum vs plasma, fresh vs frozen plasma, and nonhemolyzed vs hemolyzed samples in orange-winged Amazon parrots. We also compared differences in serum and plasma yield from whole-blood aliquots. Fifteen biochemical analytes were evaluated in paired serum and plasma, fresh and frozen plasma, nonhemolyzed and hemolyzed serum and plasma samples from orange-winged Amazon parrots (n = 10) using a wet reagent analyzer. Hemolysis was assessed qualitatively (visually) and quantitatively (hemoglobin [Hgb] measured spectrophotometrically). Serum and plasma yields from 500-microl whole-blood aliquots were determined from centrifuged samples. Analyte values significantly differed among sample groups, but were still within published reference intervals, with the exception of increases in potassium concentration in markedly hemolyzed serum and plasma samples. Clinically important changes in hemolyzed serum and plasma samples included increases in potassium, phosphorus, and albumin concentrations and lactate dehydrogenase activity. The degree of hemolysis assigned qualitatively did not correlate with quantitative Hgb concentration. A significantly greater yield of plasma (288 +/- 13 microL) than serum (241 +/- 44 microL) was obtained. Significant differences may occur in different sample types, however, only changes in potassium, phosphorus, albumin, and lactate dehydrogenase values in hemolyzed samples were considered clinically relevant. Lack of agreement between qualitative and quantitative Hgb concentration indicates the unreliability of visual estimation. Based on higher sample yield, and lack of clinically relevant differences from serum, plasma is a better sample choice for clinical chemistry analysis in birds.

Molecular level studies on interfacial hydration of zwitterionic and other antifouling polymers in situ.

PubMed

Leng, Chuan; Sun, Shuwen; Zhang, Kexin; Jiang, Shaoyi; Chen, Zhan

2016-08-01

Antifouling polymers have wide applications in biomedical engineering and marine industry. Recently, zwitterionic materials have been reported as promising candidates for antifouling applications, while strong hydration is believed to be the key antifouling mechanism. Zwitterionic materials can be designed with various molecular structures, which affect their hydration and antifouling performance. Although strong hydration has been proposed to occur at the material surfaces, probing the solid material/water interfaces is challenging with traditional analytical techniques. Here in this review, we will review our studies on surface hydration of zwitterionic materials and other antifouling materials by using sum frequency generation (SFG) vibrational spectroscopy, which provides molecular understanding of the water structures at various material surfaces. The materials studied include zwitterionic polymer brushes with different molecular structures, amphiphilic polymers with zwitterionic groups, uncharged hydrophilic polymer brushes, amphiphilic polypeptoids, and widely used antifouling material poly(ethylene glycol). We will compare the differences among zwitterionic materials with various molecular structures as well as the differences between antifouling materials and fouling surfaces of control samples. We will also discuss the effects of pH and biological molecules like proteins on the surface hydration of the zwitterionic materials. Using SFG spectroscopy, we have measured the hydration layers of antifouling materials and found that strong hydrogen bonds are key to the formation of strong hydration layers preventing protein fouling at the polymer interfaces. Antifouling polymers have wide applications in biomedical engineering and marine industry. Recently, zwitterionic materials have been reported as promising candidates for antifouling applications, while strong hydration is believed to be the key antifouling mechanism. However, zwitterionic materials can be designed with various molecular structures, which affect their hydration and antifouling performance. Moreover, although strong hydration has been proposed to occur at the material surfaces, probing the solid material/water interfaces is challenging with traditional analytical techniques. Here in this manuscript, we will review our studies on surface hydration of zwitterionic materials and other antifouling materials by using sum frequency generation (SFG) vibrational spectroscopy, which provides molecular understanding of the water structures at various material surfaces. The materials studied include zwitterionic polymer brushes with different molecular structures, amphiphilic polymers with zwitterionic groups, uncharged hydrophilic polymer brushes, amphiphilic polypeptoids, and widely used antifouling material poly(ethylene glycol). We will compare the differences among zwitterionic materials with various molecular structures as well as the differences between antifouling materials and fouling surfaces of control samples. We will also discuss the effects of pH and biological molecules like proteins on the surface hydration of the zwitterionic materials. All the SFG results indicate that strongly hydrogen-bonded water at the materials' surfaces (strong surface hydration) is closely correlated to the good antifouling properties of the materials. This review will be widely interested by readers of Acta Biomaterialia and will impact many different research fields in chemistry, materials, engineering, and beyond. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Simulating the gas hydrate production test at Mallik using the pilot scale pressure reservoir LARS

NASA Astrophysics Data System (ADS)

Heeschen, Katja; Spangenberg, Erik; Schicks, Judith M.; Priegnitz, Mike; Giese, Ronny; Luzi-Helbing, Manja

2014-05-01

LARS, the LArge Reservoir Simulator, allows for one of the few pilot scale simulations of gas hydrate formation and dissociation under controlled conditions with a high resolution sensor network to enable the detection of spatial variations. It was designed and built within the German project SUGAR (submarine gas hydrate reservoirs) for sediment samples with a diameter of 0.45 m and a length of 1.3 m. During the project, LARS already served for a number of experiments simulating the production of gas from hydrate-bearing sediments using thermal stimulation and/or depressurization. The latest test simulated the methane production test from gas hydrate-bearing sediments at the Mallik test site, Canada, in 2008 (Uddin et al., 2011). Thus, the starting conditions of 11.5 MPa and 11°C and environmental parameters were set to fit the Mallik test site. The experimental gas hydrate saturation of 90% of the total pore volume (70 l) was slightly higher than volumes found in gas hydrate-bearing formations in the field (70 - 80%). However, the resulting permeability of a few millidarcy was comparable. The depressurization driven gas production at Mallik was conducted in three steps at 7.0 MPa - 5.0 MPa - 4.2 MPa all of which were used in the laboratory experiments. In the lab the pressure was controlled using a back pressure regulator while the confining pressure was stable. All but one of the 12 temperature sensors showed a rapid decrease in temperature throughout the sediment sample, which accompanied the pressure changes as a result of gas hydrate dissociation. During step 1 and 2 they continued up to the point where gas hydrate stability was regained. The pressure decreases and gas hydrate dissociation led to highly variable two phase fluid flow throughout the duration of the simulated production test. The flow rates were measured continuously (gas) and discontinuously (liquid), respectively. Next to being discussed here, both rates were used to verify a model of gas hydrate dissociation applying the foamy oil approach, a method earlier adopted to model the Mallik production test (see abstract Abendroth et al., this volume). Combined with a dense set of data from a cylindrical electrical resistance tomography (ERT) array (see abstract Priegnitz et al., this volume), very valuable information were gained on the spatial as well as temporal formation and dissociation of gas hydrates as well as changes in permeability and resulting pathways for the fluid flow. Here we present the set-up and execution of the experiment and discuss the results from temperature and flow measurements with respect to the gas hydrate dissociation and characteristics of resulting fluid flow. Uddin, M., Wright, F., and Coombe, D. 2011. Numerical Study of Gas Evolution and Transport Behaviours in Natural Gas-Hydrate Reservoirs. Journal of Canadian Petroleum Technology 50, 70-89.

Cisplatin enhances the formation of DNA single- and double-strand breaks by hydrated electrons and hydroxyl radicals.

PubMed

Rezaee, Mohammad; Sanche, Léon; Hunting, Darel J

2013-03-01

The synergistic interaction of cisplatin with ionizing radiation is the clinical rationale for the treatment of several cancers including head and neck, cervical and lung cancer. The underlying molecular mechanism of the synergy has not yet been identified, although both DNA damage and repair processes are likely involved. Here, we investigate the indirect effect of γ rays on strand break formation in a supercoiled plasmid DNA (pGEM-3Zf-) covalently modified by cisplatin. The yields of single- and double-strand breaks were determined by irradiation of DNA and cisplatin/DNA samples with (60)Co γ rays under four different scavenging conditions to examine the involvement of hydrated electrons and hydroxyl radicals in inducing the DNA damage. At 5 mM tris in an N2 atmosphere, the presence of an average of two cisplatins per plasmid increased the yields of single- and double-strand breaks by factors of 1.9 and 2.2, respectively, relative to the irradiated unmodified DNA samples. Given that each plasmid of 3,200 base pairs contained an average of two cisplatins, this represents an increase in radiosensitivity of 3,200-fold on a per base pair basis. When hydrated electrons were scavenged by saturating the samples with N2O, these enhancement factors decreased to 1.5 and 1.2, respectively, for single- and double-strand breaks. When hydroxyl radicals were scavenged using 200 mM tris, the respective enhancement factors were 1.2 and 1.6 for single- and double-strand breaks, respectively. Furthermore, no enhancement in DNA damage by cisplatin was observed after scavenging both hydroxyl radicals and hydrated electrons. These findings show that hydrated electrons can induce both single- and double-strand breaks in the platinated DNA, but not in unmodified DNA. In addition, cisplatin modification is clearly an extremely efficient means of increasing the formation of both single- and double-strand breaks by the hydrated electrons and hydroxyl radicals created by ionizing radiation.

Testing a thermo-chemo-hydro-geomechanical model for gas hydrate-bearing sediments using triaxial compression laboratory experiments

NASA Astrophysics Data System (ADS)

Gupta, S.; Deusner, C.; Haeckel, M.; Helmig, R.; Wohlmuth, B.

2017-09-01

Natural gas hydrates are considered a potential resource for gas production on industrial scales. Gas hydrates contribute to the strength and stiffness of the hydrate-bearing sediments. During gas production, the geomechanical stability of the sediment is compromised. Due to the potential geotechnical risks and process management issues, the mechanical behavior of the gas hydrate-bearing sediments needs to be carefully considered. In this study, we describe a coupling concept that simplifies the mathematical description of the complex interactions occurring during gas production by isolating the effects of sediment deformation and hydrate phase changes. Central to this coupling concept is the assumption that the soil grains form the load-bearing solid skeleton, while the gas hydrate enhances the mechanical properties of this skeleton. We focus on testing this coupling concept in capturing the overall impact of geomechanics on gas production behavior though numerical simulation of a high-pressure isotropic compression experiment combined with methane hydrate formation and dissociation. We consider a linear-elastic stress-strain relationship because it is uniquely defined and easy to calibrate. Since, in reality, the geomechanical response of the hydrate-bearing sediment is typically inelastic and is characterized by a significant shear-volumetric coupling, we control the experiment very carefully in order to keep the sample deformations small and well within the assumptions of poroelasticity. The closely coordinated experimental and numerical procedures enable us to validate the proposed simplified geomechanics-to-flow coupling, and set an important precursor toward enhancing our coupled hydro-geomechanical hydrate reservoir simulator with more suitable elastoplastic constitutive models.

Hydration of calcium sulfoaluminate cements - Experimental findings and thermodynamic modelling

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

Winnefeld, Frank, E-mail: Frank.Winnefeld@empa.c; Lothenbach, Barbara

Calcium sulfoaluminate cements (CSA) are a promising low-CO{sub 2} alternative to ordinary Portland cements and are as well of interest concerning their use as binder for waste encapsulation. In this study, the hydration of two CSA cements has been investigated experimentally and by thermodynamic modelling between 1 h and 28 days at w/c ratios of 0.72 and 0.80, respectively. The main hydration product of CSA is ettringite, which precipitates together with amorphous Al(OH){sub 3} until the calcium sulfate is consumed after around 1-2 days of hydration. Afterwards, monosulfate is formed. In the presence of belite, straetlingite occurs as an additionalmore » hydration product. The pore solution analysis reveals that straetlingite can bind a part of the potassium ions, which are released by the clinker minerals. The microstructure of both cements is quite dense even after 16 h of hydration, with not much pore space available at a sample age of 28 days. The pore solution of both cements is dominated during the first hours of hydration by potassium, sodium, calcium, aluminium and sulfate; the pH is around 10-11. When the calcium sulfate is depleted, the sulfate concentration drops by a factor of 10. This increases pH to around 12.5-12.8. Based on the experimental data, a thermodynamic hydration model for CSA cements based on cement composition, hydration kinetics of clinker phases and calculations of thermodynamic equilibria by geochemical speciation has been established. The modelled phase development with ongoing hydration agrees well with the experimental findings.« less

A Taphonomic Study Exploring the Differences in Decomposition Rate and Manner between Frozen and Never Frozen Domestic Pigs (Sus scrofa).

PubMed

Roberts, Lindsey G; Dabbs, Gretchen R

2015-05-01

This research examined differences in decomposition rate and manner of domestic pig subjects (Sus scrofa) in never frozen (control) and previously frozen (experimental) research conditions. Eight control and experimental subjects were placed in an identical outdoor research environment. Daily quantitative and qualitative measurements were collected: abdominal circumference, total body score (TBS), temperature, photographs, descriptive decomposition stages, and visual observations. Field necropsies were performed at accumulated degree days (ADD) between 50 and 300 (Celsius). Paired samples t-tests of ADD to TBS >3.0, TBS >9.5, and TBS >16.0 indicate the rate of decomposition of experimental subjects was significantly slower than controls at both TBS >3 and >9.5 (p = 0.003 and p = 0.002, respectively). A suite of qualitative indicators of predecomposition freezing is also reported. The differences between experimental and control subjects suggest previously frozen subjects should not be used in taphonomic research, as results do not accurately reflect the "normal" taphonomic condition. © 2015 American Academy of Forensic Sciences.

Presence and dehydration of ikaite, calcium carbonate hexahydrate, in frozen shrimp shell.

PubMed

Mikkelsen, A; Andersen, A B; Engelsen, S B; Hansen, H C; Larsen, O; Skibsted, L H

1999-03-01

Ikaite, calcium carbonate hexahydrate, has by means of X-ray diffraction analyses of frozen samples been identified as the mineral component of the white spots formed in the shell of frozen shrimp during storage. When the shrimp thaw and the shell material is dried and kept at room temperature, ikaite rapidly transforms into a mixture of anhydrous calcium carbonate forms. X-ray diffraction analyses and Raman spectra of synthetic ikaite as well as the dehydration product confirm the assignments, and the rate constant for dehydration is approximately 7 x 10(-)(4) s(-)(1) at ambient temperature. Differential scanning calorimetry showed that dehydration of synthetic ikaite is an entropy-driven, athermal process and confirms that a single first-order reaction is rate-determining. Ikaite is found to be stable in aqueous solution at temperatures below 5 degrees C and in the shell of frozen shrimps but decomposes on thawing to form anhydrous calcium carbonates.

Hydration Free Energy from Orthogonal Space Random Walk and Polarizable Force Field.

PubMed

Abella, Jayvee R; Cheng, Sara Y; Wang, Qiantao; Yang, Wei; Ren, Pengyu

2014-07-08

The orthogonal space random walk (OSRW) method has shown enhanced sampling efficiency in free energy calculations from previous studies. In this study, the implementation of OSRW in accordance with the polarizable AMOEBA force field in TINKER molecular modeling software package is discussed and subsequently applied to the hydration free energy calculation of 20 small organic molecules, among which 15 are positively charged and five are neutral. The calculated hydration free energies of these molecules are compared with the results obtained from the Bennett acceptance ratio method using the same force field, and overall an excellent agreement is obtained. The convergence and the efficiency of the OSRW are also discussed and compared with BAR. Combining enhanced sampling techniques such as OSRW with polarizable force fields is very promising for achieving both accuracy and efficiency in general free energy calculations.

Entropy from State Probabilities: Hydration Entropy of Cations

PubMed Central

2013-01-01

Entropy is an important energetic quantity determining the progression of chemical processes. We propose a new approach to obtain hydration entropy directly from probability density functions in state space. We demonstrate the validity of our approach for a series of cations in aqueous solution. Extensive validation of simulation results was performed. Our approach does not make prior assumptions about the shape of the potential energy landscape and is capable of calculating accurate hydration entropy values. Sampling times in the low nanosecond range are sufficient for the investigated ionic systems. Although the presented strategy is at the moment limited to systems for which a scalar order parameter can be derived, this is not a principal limitation of the method. The strategy presented is applicable to any chemical system where sufficient sampling of conformational space is accessible, for example, by computer simulations. PMID:23651109

Thermal stress control using waste steel fibers in massive concretes

NASA Astrophysics Data System (ADS)

Sarabi, Sahar; Bakhshi, Hossein; Sarkardeh, Hamed; Nikoo, Hamed Safaye

2017-11-01

One of the important subjects in massive concrete structures is the control of the generated heat of hydration and consequently the potential of cracking due to the thermal stress expansion. In the present study, using the waste turnery steel fibers in the massive concretes, the amount of used cement was reduced without changing the compressive strength. By substituting a part of the cement with waste steel fibers, the costs and the generated hydration heat were reduced and the tensile strength was increased. The results showed that by using 0.5% turnery waste steel fibers and consequently, reducing to 32% the cement content, the hydration heat reduced to 23.4% without changing the compressive strength. Moreover, the maximum heat gradient reduced from 18.5% in the plain concrete sample to 12% in the fiber-reinforced concrete sample.

Comparison of intracellular water content measurements by dark-field imaging and EELS in medium voltage TEM

NASA Astrophysics Data System (ADS)

Terryn, C.; Michel, J.; Kilian, L.; Bonhomme, P.; Balossier, G.

2000-09-01

Knowledge of the water content at the subcellular level is important to evaluate the intracellular concentration of either diffusible or non-diffusible elements in the physiological state measured by the electron microprobe methods. Water content variations in subcellular compartments are directly related to secretion phenomena and to transmembrane exchange processes, which could be attributed to pathophysiological states. In this paper we will describe in details and compare two local water measurement methods using analytical electron microscopy. The first one is based on darkfield imaging. It is applied on freeze-dried biological cryosections; it allows indirect measurement of the water content at the subcellular level from recorded maps of darkfield intensity. The second method uses electron energy loss spectroscopy. It is applied to hydrated biological cryosections. It is based on the differences that appear in the electron energy loss spectra of macromolecular assemblies and vitrified ice in the 0-30 eV range. By a multiple least squares (MLS) fit between an experimental energy loss spectrum and reference spectra of both frozen-hydrated ice and macromolecular assemblies we can deduce directly the local water concentration in biological cryosections at the subcellular level. These two methods are applied to two test specimens: human erythrocytes in plasma, and baker's yeast (Saccharomyses Cerevisiae) cryosections. We compare the water content measurements obtained by these two methods and discuss their advantages and drawbacks.

DSC investigation of bovine hide collagen at varying degrees of crosslinking and humidities.

PubMed

Schroepfer, Michaela; Meyer, Michael

2017-10-01

Bovine hide collagen (nonCLC; non-CrossLinked Collagen) was analysed by differential scanning calorimetry (DSC) at different hydration degrees and compared with hide collagen samples crosslinked with glutaraldehyde (CLC-GA) and chromium(III) ions (CLC-Cr), respectively. Crosslinking and drying were confirmed to increase the denaturation temperature. Different regions were assigned, that reflect the variation of the influence of water on the denaturation temperature. Furthermore, at moderate hydration degrees, the enthalpies of non-crosslinked collagen increase compared to the fully hydrated state. This reflects a glue-like action of water in the range of 25% hydration. Crosslinking of bovine hide collagen decreases the enthalpy by 25% in the fully hydrated state, even at very low levels of crosslinking This can be explained by intensive effects of the crosslinking agent on the hydration network of the collagen molecules, assuming that the enthalpies are principally a result of hydrogen bonding. At very low water contents DSC peaks of CLC-Cr completely disappear. This could be explained by competition between hydroxosulfochromate(III) complexes and collagen for water. Copyright © 2017 Elsevier B.V. All rights reserved.

Pathways through equilibrated states with coexisting phases for gas hydrate formation

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

Malolepsza, Edyta; Keyes, Tom

Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less

Pathways through equilibrated states with coexisting phases for gas hydrate formation

DOE PAGES

Malolepsza, Edyta; Keyes, Tom

2015-12-01

Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less