Effect of Ultrasonic Extraction on Production and Structural Changes of C-Phycocyanin from Marine Spirulina maxima

Directory of Open Access Journals (Sweden)

Woon Yong Choi

2018-01-01

Full Text Available This work first showed that very high amounts of phycocyanins, such as 11.3 mg/mL C-phycocyanin (C-PC, 3.1 mg/mL allophycocyanin (APC, and 0.8 mg/mL phycoerythrin (PE, can be obtained using an ultrasonic extraction process (UE with a 60 kHz frequency and 3 h of process time at 25 °C, without any other pretreatments. These yields were higher than those from most conventional water extractions at 4 °C for 24 h (Control condition or at 25 °C for 24 h (WE, namely, 9.8 and 5.7 mg/mL C-PC, 2.3 and 1.2 mg/mL APC, and 0.7 and 0.3 mg/mL PE, respectively. These yields were also shown to be even higher than yields from other reported data. Structural changes in C-PC in the extracts were also found for the first time, according to extraction conditions, showing that the total concentration of C-PC and of the α-subunit of C-PC in the UE were much higher than in the WE, with little difference in the amount of β-subunit of C-PC in the UE or WE. It was also shown that the structural changes in C-PC in the WE decreased both antioxidant and anti-inflammation activities—29.83% vs. 32.09% of α,α-diphenyl-β-picrylhydrazyl (DPPH scavenging activity and 8.21 vs. 7.25 µM of NO production for the WE and UE, respectively—while the UE, with similar patterns to standard C-PC, showed very high biological effects, which may suggest that the biologically active part is the α-subunit of C-PC, not the β-subunit.

Medical Application of Spirulina platensis Derived C-Phycocyanin

Directory of Open Access Journals (Sweden)

Qian Liu

2016-01-01

Full Text Available Along with the development of marine biological pharmaceutical research, high-effective and low-toxic drugs and functional foods isolated from marine organisms have become a new field of pharmacy and bromatology. The pharmacological actions, such as anti-inflammation, antioxidation, antitumor, immunological enhancement, and hepatorenal protection of C-phycocyanin (C-PC from Spirulina platensis, have been reported, and C-PC has important value of development and utilization either as drug or as functional food. There are many researches about the various pharmacological actions and mechanisms of C-PC, but related reports are only to some extent integrated deeply and accurately enough, which put some limitations to the further application of C-PC in medicine. Particularly, with the improvement of living standards and attention to health issues, C-PC being a functional food is preferred by more and more people. C-PC is easy to get, safe, and nontoxic; thus, it has a great potential of research and development as a drug or functional food. Here, the separation and purification, physicochemical properties, physiological and pharmacological activities, safety, and some applications are reviewed to provide relevant basis for the development of natural medicine and applied products.

OPTIMALISASI EKSTRAKSI DAN UJI STABILITAS PHYCOCYANIN DARI MIKROALGA Spirulina platensis

Directory of Open Access Journals (Sweden)

Bakti Jos

2012-02-01

Full Text Available The growing awareness of the importance of natural colours especially food and cosmetic colorants has placedgreat demand on biological sources of natural colours. It is for this reason that the phycobiliproteins inSpirulina platensis is gaining increasing attention as an alternative colour for these products. Numerousscientific reports confirm the fact that Phycocyanin from Spirulina platensis, is not only an effective naturalblue colorant, but also a compound that is beneficial to the health of the consumer. The aim of this research is toconduct evaluation studies phycocyanin production by extraction with polar solvents at various concentrationsto obtain extracts for maximum yield. The methods in this study has several stages, namely preparation ofmaterials, extraction, solubility studies of phycocyanin, phycocyanin’s stability test. Changing variables in thisstudy are water, acetic acid 70%, 75%, 80%, ammonium sulphate 50%, 55%, 60%. The analysis of the extractsof phycocyanin’s content using spectrophotometric methods. The observations produces a blue pigment whichhas the highest color intensity with maximum absorbance of 620 nm. Acetic acid 80% is the most effectivesolvent to extract the blue pigment phycocyanin than water and ammonium sulfate. Extraction is influenced bythe pH of the increase in absorption (absorbance with increasing pH and was not influenced by storagetemperature and time

Optimizing the bio-optical algorithm for estimating chlorophyll-a and phycocyanin concentrations in inland waters in Korea

Science.gov (United States)

Several bio-optical algorithms were developed to estimate the chlorophyll-a (Chl-a) and phycocyanin (PC) concentrations in inland waters. This study aimed at identifying the influence of the algorithm parameters and wavelength bands on output variables and searching optimal parameter values. The opt...

Effects of C-phycocyanin and Spirulina on Salicylate-Induced Tinnitus, Expression of NMDA Receptor and Inflammatory Genes

Science.gov (United States)

Hwang, Juen-Haur; Chen, Jin-Cherng; Chan, Yin-Ching

2013-01-01

Effects of C-phycocyanin (C-PC), the active component of Spirulina platensis water extract on the expressions of N-methyl D-aspartate receptor subunit 2B (NR2B), tumor necrosis factor–α (TNF-α), interleukin-1β (IL-1β), and cyclooxygenase type 2 (COX-2) genes in the cochlea and inferior colliculus (IC) of mice were evaluated after tinnitus was induced by intraperitoneal injection of salicylate. The results showed that 4-day salicylate treatment (unlike 4-day saline treatment) caused a significant increase in NR2B, TNF-α, and IL-1β mRNAs expression in the cochlea and IC. On the other hand, dietary supplementation with C-PC or Spirulina platensis water extract significantly reduced the salicylate-induced tinnitus and down-regulated the mRNAs expression of NR2B, TNF-α, IL-1β mRNAs, and COX-2 genes in the cochlea and IC of mice. The changes of protein expression levels were generally correlated with those of mRNAs expression levels in the IC for above genes. PMID:23533584

Effects of C-phycocyanin and Spirulina on salicylate-induced tinnitus, expression of NMDA receptor and inflammatory genes.

Directory of Open Access Journals (Sweden)

Juen-Haur Hwang

Full Text Available Effects of C-phycocyanin (C-PC, the active component of Spirulina platensis water extract on the expressions of N-methyl D-aspartate receptor subunit 2B (NR2B, tumor necrosis factor-α (TNF-α, interleukin-1β (IL-1β, and cyclooxygenase type 2 (COX-2 genes in the cochlea and inferior colliculus (IC of mice were evaluated after tinnitus was induced by intraperitoneal injection of salicylate. The results showed that 4-day salicylate treatment (unlike 4-day saline treatment caused a significant increase in NR2B, TNF-α, and IL-1β mRNAs expression in the cochlea and IC. On the other hand, dietary supplementation with C-PC or Spirulina platensis water extract significantly reduced the salicylate-induced tinnitus and down-regulated the mRNAs expression of NR2B, TNF-α, IL-1β mRNAs, and COX-2 genes in the cochlea and IC of mice. The changes of protein expression levels were generally correlated with those of mRNAs expression levels in the IC for above genes.

Enhancement of antioxidant activity of C-phycocyanin of Spirulina powder treated with supercritical fluid carbon dioxide

Directory of Open Access Journals (Sweden)

Monchai Dejsungkranont

2017-10-01

Full Text Available The functionality and activity of proteins can be modified by supercritical fluid CO2 (SCFCO2. The objectives of this study were to investigate the possibility of enhanced antioxidant activity of C-phycocyanin (C-PC proteins from light-harvested Spirulina maxima powder using the SCFCO2 pretreatment and to optimize the SCFCO2 pretreatment conditions enhancing the antioxidant activity of C-PC. The Taguchi method was used to determine the optimum conditions for the SCFCO2 pretreatment. The experimental factors were the pretreatment temperature, pressure, pretreatment mode (static, dynamic and conjugated and duration. The optimal conditions of SCFCO2 pretreatment were: 60 °C, 24.13 MPa and 60 min in static batch mode. Using these pretreatment conditions, the maximum antioxidant activity of C-PC from the treated residual biomass was 410.1 μmole trolox/mg, which was 1.7-fold higher than the untreated biomass (control. The factor that most affected the antioxidant activity of C-PC was temperature (59%. A high pretreatment temperature could damage C-PC, but promoted antioxidant activity. Of note is that this work was the first to explore SCFCO2 treatment enhancing the antioxidant activity of C-PC in Spirulina sp. powder. Keywords: Antioxidant activity, C-phycocyanin, Spirulina sp., Supercritical fluid carbon dioxide pretreatment, Taguchi method

Desalination of Produced Water via Gas Hydrate Formation and Post Treatment

OpenAIRE

Niu, Jing

2012-01-01

This study presents a two-step desalination process, in which produced water is cleaned by forming gas hydrate in it and subsequently dewatering the hydrate to remove the residual produced water trapped in between the hydrate crystals. All experiments were performed with pressure in the range of 450 to 800psi and temperature in the range of -1 to 1°C using CO? as guest molecule for the hydrate crystals. The experiments were conducted using artificial produced waters containing different amoun...

Characterization of water in hydrated Bombyx mori silk fibroin fiber and films by 2H NMR relaxation and 13C solid state NMR.

Science.gov (United States)

Asakura, Tetsuo; Isobe, Kotaro; Kametani, Shunsuke; Ukpebor, Obehi T; Silverstein, Moshe C; Boutis, Gregory S

2017-03-01

The mechanical properties of Bombyx mori silk fibroin (SF), such as elasticity and tensile strength, change remarkably upon hydration. However, the microscopic interaction with water is not currently well understood on a molecular level. In this work, the dynamics of water molecules interacting with SF was studied by 2 H solution NMR relaxation and exchange measurements. Additionally, the conformations of hydrated [3- 13 C]Ala-, [3- 13 C]Ser-, and [3- 13 C]Tyr-SF fibers and films were investigated by 13 C DD/MAS NMR. Using an inverse Laplace transform algorithm, we were able to identify four distinct components in the relaxation times for water in SF fiber. Namely, A: bulk water outside the fiber, B: water molecules trapped weakly on the surface of the fiber, C: bound water molecules located in the inner surface of the fiber, and D: bound water molecules located in the inner part of the fiber were distinguishable. In addition, four components were also observed for water in the SF film immersed in methanol for 30s, while only two components for the film immersed in methanol for 24h. The effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and non-crystalline domains of 13 C selectively labeled SF, respectively, could be determined independently. Our measurements provide new insight relating the characteristics of water and the hydration structure of silk, which are relevant in light of current interest in the design of novel silk-based biomaterials. The mechanical properties of Bombyx mori silk fibroin (SF) change remarkably upon hydration. However, the microscopic interaction between SF and water is not currently well understood on a molecular level. We were able to identify four distinct components in the relaxation times for water in SF fiber by 2 H solution NMR relaxation and exchange measurements. In addition, the effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and

Hydration kinetics of cement composites with varying water-cement ratio using terahertz spectroscopy

Science.gov (United States)

Ray, Shaumik; Dash, Jyotirmayee; Devi, Nirmala; Sasmal, Saptarshi; Pesala, Bala

2015-03-01

Cement is mixed with water in an optimum ratio to form concrete with desirable mechanical strength and durability. The ability to track the consumption of major cement constituents, viz., Tri- and Dicalcium Silicates (C3S, C2S) reacting with water along with the formation of key hydration products, viz., Calcium-Silicate-Hydrate (C-S-H) which gives the overall strength to the concrete and Calcium Hydroxide (Ca(OH)2), a hydration product which reduces the strength and durability, using an efficient technique is highly desirable. Optimizing the amount of water to be mixed with cement is one of the main parameters which determine the strength of concrete. In this work, THz spectroscopy has been employed to track the variation in hydration kinetics for concrete samples with different water-cement ratios, viz., 0.3, 0.4, 0.5 and 0.6. Results show that for the sample with water-cement ratio of 0.3, significant amount of the C3S and C2S remain unreacted even after the initial hydration period of 28 days while for the cement with water-cement ratio of 0.6, most of the constituents get consumed during this stage. Analysis of the formation of Ca(OH)2 has been done which shows that the concrete sample with water-cement ratio of 0.6 produces the highest amount of Ca(OH)2 due to higher consumption of C3S/C2S in presence of excess water which is not desirable. Samples with water-cement ratio of 0.4 and 0.5 show more controlled reaction during the hydration which can imply formation of an optimized level of desired hydration products resulting in a more mechanically strong and durable concrete.

Isolation and antibacterial activity of anabaena phycocyanin

African Journals Online (AJOL)

Taghwo

2013-04-10

Apr 10, 2013 ... (Yoshida et al., 1996) due to their antioxidant and anti- inflammatory ... studies indicated that phycocyanin from spirulina have obvious curative effect on .... phycocyanin from spirulina platensis using expanded bed adsorption.

Investigation of the Structure and Element Composition of C-Phycocyanin Extracted from the Microalgae Spirulina platensis

CERN Document Server

Mosulishvili, L M; Kirkesali, E I; Khizanishvili, A I; Frontasyeva, M V; Pavlov, S S; Gundorina, S F

2002-01-01

The structure and element composition of C-phycocyanin (C-PC) extracted from the blue-green alga Spirulina platensis were studied. The behavior of structural subunits forming phycobilisomes in the purification process was studied by capillary electrophoresis. Their proportion in high-purity C-PC was determined. The element composition of C-PC of different purity was studied by means of epithermal neutron activation analysis, and metals which may form macromolecular complexes with C-PC were determined (Zn, Cr, Ni, Co, As, Sr, Mo, Ag, Hg). It was shown that contents of toxic metals did not exceed accepted permissible levels for the human organism.

The Application of Microencapsulated Phycocyanin as a Blue Natural Colorant to the Quality of Jelly Candy

Science.gov (United States)

Dewi, E. N.; Kurniasih, R. A.; Purnamayati, L.

2018-02-01

Phycocyanin is a blue color pigment which can be extracted from Spirulina sp. makes it potential to use as an alternative natural dye in the food product. The aim of this research was to determine the application of microencapsulated phycocyanin processed using spray dried method to the jelly candy. As a natural blue colorant, phycocyanin was expected to be safe for the consumer. The jelly candy was evaluated on the characteristics of its moisture, ash, Aw, pH, color appearance, and phycocyanin spectra with FTIR. The phycocyanin was microencapsulated using maltodextrin and Na-alginate as the coating materials (maltodextrin and Na-alginate in ratio 9:1.0 w/w). The spray drying process was operated with an inlet temperature of 80°C. The various concentrations of microencapsulated phycocyanin were added to the jelly candy such as 0%, 1%, 3%, 5% and jelly candy with brilliant blue used as comparison, each called PC, PS, PT, PL, and PB. The results showed that the various concentrations of phycocyanin added on the jelly product had significantly different on moisture content, Aw, and blue color. The FTIR spectra indicated that phycocyanin still persisted on the jelly candy. PL was the best jelly candy with the bluest color under PB.

Phycocyanin-encapsulating hyalurosomes as carrier for skin delivery and protection from oxidative stress damage.

Science.gov (United States)

Castangia, Ines; Manca, Maria Letizia; Catalán-Latorre, Ana; Maccioni, Anna Maria; Fadda, Anna Maria; Manconi, Maria

2016-04-01

The phycobiliprotein phycocyanin, extracted from Klamath algae, possesses important biological properties but it is characterized by a low bioavailability due to its high molecular weight. To overcome the bioavailability problems, phycocyanin was successfully encapsulated, using an environmentally-friendly method, into hyalurosomes, a new kind of phospholipid vesicles immobilised with hyaluronan sodium salt by the simple addition of drug/sodium hyaluronate water dispersion to phospholipids. Liposomes were used as a comparison. Vesicles were small in size and homogeneously dispersed, being the mean size always smaller than 150 nm and PI never higher than 0.31. Liposomes were unilamellar and spherical, the addition of the polymer slightly modify the vesicular shape which remain spherical, while the addition of PEG improve the lamellarity of vesicles being multilamellar vesicles. In all cases phycocyanin was encapsulated in good amount especially using hyalurosomes and PEG hyalurosomes (65 and 61% respectively). In vitro penetration studies suggested that hyalurosomes favoured the phycocyanin deposition in the deeper skin layers probably thanks to their peculiar hyaluronan-phospholipid structure. Moreover, hyalurosomes were highly biocompatible and improved phycocyanin antioxidant activity on stressed human keratinocytes respect to the drug solution.

Fast cleavage of phycocyanobilin from phycocyanin for use in food colouring

DEFF Research Database (Denmark)

Roda-Serrat, Maria Cinta; Christensen, Knud Villy; El-Houri, Rime

2018-01-01

Phycocyanins from cyanobacteria are possible sources for new natural blue colourants. Their chromophore, phycocyanobilin (PCB), was cleaved from the apoprotein by solvolysis in alcohols and alcoholic aqueous solutions. In all cases two PCB isomers were obtained, while different solvent adducts were......, and microwave assisted reaction. The sealed vessel method is a new approach for fast cleavage of PCB from phycocyanin and gave at 120°C the same yield within 30 min compared to 16 hours by the conventional reflux method (P

Protective effects of C-phycocyanin on alcohol-induced acute liver injury in mice

Science.gov (United States)

Xia, Dong; Liu, Bing; Luan, Xiying; Sun, Junyan; Liu, Nana; Qin, Song; Du, Zhenning

2016-03-01

Excessive alcohol consumption leads to liver disease. Extensive evidence suggests that C-phycocyanin (C-PC), a chromophore phycocyanobilin derived from Spirulina platensis, exerts protective effects against chemical-induced organ damage. In this study, we investigated whether C-PC could protect against ethanol-induced acute liver injury. Serum alanine aminotransferase (ALT), aspartate aminotransferase (AST), triglyceride (TG), total cholesterol (CHOL), low-density lipoprotein (LDL), liver homogenate malondialdehyde (MDA), superoxide dismutase (SOD) content were measured, and pathological examination of liver sections were examined. C-PC showed obvious inhibitory effects on serum ALT, AST, TG, CHOL, LDL and MDA, and SOD content significantly increased in the liver. The structure of hepatic lobules was clear, liver sinus returned to normal, and liver cell cords were arranged in neat rows. Cloudiness, swelling, inflammatory cell infiltration and spotty necrosis of liver cells were significantly reduced. Therefore, C-PC can significantly protect against ethanol-induced acute liver injury.

Optimization growth of Spirulina platensis in bean sprouts extract medium with urea fertilizer for phycocyanin production as antioxidant

Science.gov (United States)

Dianursanti, Taurina, Zarahmaida; Indraputri, Claudia Maya

2018-02-01

Spirulina platensis has the potential to be developed because of essential chemical compounds in the form of phycocyanin that can be used as an antioxidant. The growth of microalgae and phycocyanin depends on the availability of nutrition contained in culture medium. The cultivation will be carried out at 1 L reactor with continuous aeration, light intensity is 3000-4000 lux, and temperature is 27-30°C. Phycocyanin is obtained by liquid-liquid extraction method using phosphate buffer pH 7. Phycocyanin test performed by using UV-Vis spectrophotometry. The result show that the highest dry biomass is obtained on bean sprouts extract medium 8% (v/v) with the addition of urea fertilizer 120 ppm. The highest content of phycocyanin is obtained on bean sprouts extract medium 8% (v/v) with the addition of urea fertilizer 100 ppm with phycocyanin concentration of 257.12 mg/L.

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

Science.gov (United States)

Sirotkin, Vladimir A; Kuchierskaya, Alexandra A

2017-10-01

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

Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

International Nuclear Information System (INIS)

Li, Gang; Li, Xiao-Sen; Li, Bo; Wang, Yi

2014-01-01

The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

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

Science.gov (United States)

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.

Vibrational dynamics of hydration water in amylose

CERN Document Server

Cavatorta, F; Albanese, G; Angelini, N

2002-01-01

We present a study of the dynamical properties of hydration water associated with amylose helices, based on low-temperature vibrational spectra collected using the TOSCA inelastic spectrometer at ISIS. The structural constraints of the polysaccharidic chains favour the formation of a high-density structure for water, which has been suggested by Imberty and Perez on the basis of conformational analysis. According to this model, hydration water can only enter the pores formed by six adjacent helices and completely fills the pores at a hydration level of about 0.27-g water/g dry amylose. Our measurements show that the dynamical behaviour of hydration water is similar to that observed in high-density amorphous ice. (orig.)

Comparison of skin hydration in combination and single use of common moisturizers (cream, toner, and spray water).

Science.gov (United States)

Yuanxi, Li; Wei, Hua; Lidan, Xiiong; Li, Li

2016-01-01

This study aims to assess the moisturization in combination or single use (including seven general applications) of three common moisturizers: cream, toner, and spray water. Groups were set as C: cream only; T: toner only; C+T, T+C: cream or toner applied successively within a few minutes; C-T, C-S: cream applied with repeated toner or spray water every 2 h; T-T: toner applied with repeated toner every 2 h; and N: untreated group. Outcomes were the change in skin hydration from baseline at 2, 4, 6, and 8 h after applications. All treated zones displayed a significantly higher degree of hydration compared with the untreated zone ( p skin (hydration value at baseline >35 a.u.), C-T led to greatest hydration change rate compared with others, followed by C+T, T+C, and C. Those three applications exhibited analogous hydration at each test point ( p > 0.05). The hydration rate of C-S differed slightly from T-T, followed by those four mentioned above, with T being the last. For dry skin (hydration value at baseline 0.05), the other results were identical. When cream and toner were applied successively, the application order has little effect on skin hydration. The application of cream only was an effective and brief way to achieve favorable moisturization especially for dry skin. As a complement, repeated application of toner rather than spray water is efficacious for skin hydration.

Water Dynamics in the Hydration Shells of Biomolecules

Science.gov (United States)

2017-01-01

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

CD59 Underlines the Antiatherosclerotic Effects of C-Phycocyanin on Mice

Directory of Open Access Journals (Sweden)

Bing Li

2013-01-01

Full Text Available The effects of C-phycocyanin (C-PC on atherosclerosis and the regulatory effects of CD59 gene on anti-atherosclerotic roles of C-PC were investigated. Apolipoprotein E knockout (ApoE(−/− mice were randomly divided into four groups: control group, C-PC treatment group, CD59 transfection group and C-PC+CD59 synergy group. The mice were fed with high-fat-diet and treated with drug intervention at the same time. Results showed the atherosclerotic mouse model was successfully established. CD59 was over-expressed in blood and tissue cells. Single CD59 or C-PC could reduce blood lipid levels and promote the expression of anti-apoptotic Bcl-2 but inhibit pro-apoptotic Fas proteins in endothelial cells. The expression levels of cell cycle protein D1 (Cyclin D1 and mRNA levels of cyclin dependent protein kinase 4 (CDK4 in smooth muscle cells were restrained by CD59 and C-PC. CD59 or C-PC alone could inhibit the formation of atherosclerotic plaque by suppressing MMP-2 protein expression. In addition, C-PC could promote CD59 expression. So both CD59 and C-PC could inhibit the progress of atherosclerosis, and the anti-atherosclerotic effects of C-PC might be fulfilled by promoting CD59 expression, preventing smooth muscle cell proliferation and the apoptosis of endothelial cells, reducing blood fat levels, and at last inhibiting the development of atherosclerosis.

Method and apparatus for detecting phycocyanin-pigmented algae and bacteria from reflected light

Science.gov (United States)

Vincent, Robert (Inventor)

2013-01-01

The present invention relates to a method of detecting phycocyanin algae or bacteria in water from reflected light, and also includes devices for the measurement, calculation and transmission of data relating to that method.

Separation of water through gas hydrate formation

DEFF Research Database (Denmark)

Boch Andersen, Torben; Thomsen, Kaj

2009-01-01

Gas hydrate is normally recognized as a troublemaker in the oil and gas industry. However, gas hydrate has some interesting possibilities when used in connection with separation of water. Nordic Sugar has investigated the possibility of using gas hydrates for concentration of sugar juice. The goal...... of the project was to formulate an alternative separation concept, which can replace the traditional water evaporation process in the sugar production. Work with the separation concept showed that gas hydrates can be used for water separation. The process is not suitable for sugar production because of large...... volumes and the needs for high pressure. The process could be interesting for concentration of heat sensitive, high value products...

Stable Isolation of Phycocyanin from Spirulina platensis Associated with High-Pressure Extraction Process

Directory of Open Access Journals (Sweden)

Kyung-Hwan Jung

2013-01-01

Full Text Available A method for stably purifying a functional dye, phycocyanin from Spirulina platensis was developed by a hexane extraction process combined with high pressure. This was necessary because this dye is known to be very unstable during normal extraction processes. The purification yield of this method was estimated as 10.2%, whose value is 3%–5% higher than is the case from another conventional separation method using phosphate buffer. The isolated phycocyanin from this process also showed the highest purity of 0.909 based on absorbance of 2.104 at 280 nm and 1.912 at 620 nm. Two subunits of phycocyanin namely α-phycocyanin (18.4 kDa and β-phycocyanin (21.3 kDa were found to remain from the original mixtures after being extracted, based on SDS-PAGE analysis, clearly demonstrating that this process can stably extract phycocyanin and is not affected by extraction solvent, temperature, etc. The stability of the extracted phycocyanin was also confirmed by comparing its DPPH (α,α-diphenyl-β-picrylhydrazyl scavenging activity, showing 83% removal of oxygen free radicals. This activity was about 15% higher than that of commercially available standard phycocyanin, which implies that the combined extraction method can yield relatively intact chromoprotein through absence of degradation. The results were achieved because the low temperature and high pressure extraction effectively disrupted the cell membrane of Spirulina platensis and degraded less the polypeptide subunits of phycocyanin (which is a temperature/pH-sensitive chromoprotein as well as increasing the extraction yield.

Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

International Nuclear Information System (INIS)

Mendoza, Oscar; Giraldo, Carolina; Camargo, Sergio S.; Tobón, Jorge I.

2015-01-01

This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure

Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

Energy Technology Data Exchange (ETDEWEB)

Mendoza, Oscar, E-mail: oamendoz@unal.edu.co [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia); Giraldo, Carolina [Cementos Argos S.A., Medellín (Colombia); Camargo, Sergio S. [Engenharia Metalúrgica e de Materiais, Universidade Federal do Rio de Janeiro/COPPE, Rio de Janeiro (Brazil); Tobón, Jorge I. [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia)

2015-08-15

This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure.

Improvement of Stability and Antioxidant Activities by Using Phycocyanin - Chitosan Encapsulation Technique

Science.gov (United States)

Suzery, Meiny; Hadiyanto; Majid, Dian; Setyawan, Deny; Sutanto, Heri

2017-02-01

Encapsulation is a coating process to improve the stability of bioactive compounds. Phycocyanin with high antioxidant activity has been encapsulated with chitosan in microcapsules form. In this study aims to determine the best conditions in the encapsulation process using the extrusion method, characterization of the physicochemical properties of the microcapsules, antioxidant activity test using DPPH, in vitro release performance and evaluate the storage stability against temperature. The results of the encapsulation process is obtained: Na-TPP is better than Na-citrate as crosslinker and chitosan content 3% as a coating with ratio of chitosan to phycocyanin ratio 1: 1. Test of antioxidant activity also showed encapsulation with chitosan content 3% has the highest antioxidant activity. Morphological analysis microcapsules were found to have compact spherical shape with diameter range 900-1000 µm. In vitro release testing showed a quick release in an acidic environment (SGF) for 2 hours and slowly release under alkaline conditions (SIF) for 8 hours under mechanical stirring at 37°C. Phycocyanin much more stable against temperature during storage in microcapsules.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

Science.gov (United States)

Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav

2016-12-28

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Influence of Lithium Carbonate on C3A Hydration

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Weiwei Han

2018-01-01

Full Text Available Lithium salts, known to ameliorate the effects of alkali-silica reaction, can make significant effects on cement setting. However, the mechanism of effects on cement hydration, especially the hydration of C3A which is critical for initial setting time of cement, is rarely reported. In this study, the development of pH value of pore solution, conductivity, thermodynamics, and mineralogical composition during hydration of C3A with or without Li2CO3 are investigated. The results demonstrate that Li2CO3 promotes C3A hydration through high alkalinity, due to higher activity of lithium ion than that of calcium ion in the solution and carbonation of C3A hydration products resulted from Li2CO3. Li2CO3 favors the C3A hydration in C3A-CaSO4·2H2O-Ca(OH2-H2O hydration system and affects the mineralogical variation of the ettringite phase(s.

Fractionation of hydrogen and oxygen isotopes between hydrated and free water molecules in aqueous urea solution

International Nuclear Information System (INIS)

Kakiuchi, M.; Matsuo, S.

1985-01-01

Ratios of D/H and 18 O/ 16 O in the vapor phase in equilibrium with aqueous urea solution with different urea molalities were measured at 15 and 25 0 C. Under the assumption that urea solutions consist of two species, i.e., the urea-water cluster and free water, the results are interpreted to give the average hydration number, i.e., the number of water molecules per urea molecule in the urea-water cluster. Good agreement was obtained for the hydration number estimated independently from hydrogen and oxygen isotopic fractions. On the basis of hydrogen isotopic data at 25 0 C, the average hydration number of urea in the cluster is 6.3 +/- 0.8 at 2.1 m and 2.75 +/- 0.08 at saturation (20.15 m). The corresponding average hydration numbers based on oxygen isotopic data were calculated to be 6.7 +/- 2.4 at 2.1 m and 2.75 +/- 0.25 at urea saturation. HD 16 O is enriched in the urea-water cluster and H 2 18 O is enriched in free water. Isotopic partitioning between the cluster and free water is markedly different from those between hydration spheres and free water in aqueous electrolyte solutions. 29 references, 6 figures, 5 tables

The effects of temperature and frequencies in ultrasound assisted extraction of phycocyanin from microalgae Spirulina sp

Energy Technology Data Exchange (ETDEWEB)

Hadiyanto,, E-mail: hadiyanto@live.undip.ac.id; Suttrisnorhadi,; Soetrisnanto, Danny; Azizah, Nur [Department of Chemical Engineering, Diponegoro University, Jl. Prof. Soedarto, SH-Tembalang, Semarang 50239 INDONESIA (Indonesia); Sutanto, Heri [Physic Department, Faculty of Science and Mathematics, Diponegoro University (Indonesia); Suzery, Meiny [Chemistry Department, Faculty of Science and Mathematics, Diponegoro University (Indonesia)

2015-12-29

Microalgae Spirulina sp has been identified as source of protein and other high added value compounds. One of the compounds is phycocyanin as also known for antioxidant use. The extraction of this compound by using conventional method (soxhlet extraction) resulted low yield and longer processing time. This research was aimed to extract phycocyanin by using an extraction assisted by ultrasound irradiation. The extraction was performed by using variable of ultrasound frequency and extraction temperature and ethanol was used as a solvent. The result showed that yield of phycocyanin extracted by conventional method was 11.13% while the ultrasound irradiation could increase the yield up to 15.61% at constant frequency of 42 kHz, while the optimum temperature was obtained at 45°C. The analysis of variable interactions showed that both temperature and time has an interaction and temperature was the highest variable in increasing the yield. The conclusion of this research was the ultrasound could improve significantly the efficiency of extraction as well as activity of phycocyanin extracted from microalgae.

The effects of temperature and frequencies in ultrasound assisted extraction of phycocyanin from microalgae Spirulina sp

Science.gov (United States)

Hadiyanto, Suttrisnorhadi, Sutanto, Heri; Suzery, Meiny; Soetrisnanto, Danny; Azizah, Nur

2015-12-01

Microalgae Spirulina sp has been identified as source of protein and other high added value compounds. One of the compounds is phycocyanin as also known for antioxidant use. The extraction of this compound by using conventional method (soxhlet extraction) resulted low yield and longer processing time. This research was aimed to extract phycocyanin by using an extraction assisted by ultrasound irradiation. The extraction was performed by using variable of ultrasound frequency and extraction temperature and ethanol was used as a solvent. The result showed that yield of phycocyanin extracted by conventional method was 11.13% while the ultrasound irradiation could increase the yield up to 15.61% at constant frequency of 42 kHz, while the optimum temperature was obtained at 45°C. The analysis of variable interactions showed that both temperature and time has an interaction and temperature was the highest variable in increasing the yield. The conclusion of this research was the ultrasound could improve significantly the efficiency of extraction as well as activity of phycocyanin extracted from microalgae.

The effects of temperature and frequencies in ultrasound assisted extraction of phycocyanin from microalgae Spirulina sp

International Nuclear Information System (INIS)

Hadiyanto,; Suttrisnorhadi,; Soetrisnanto, Danny; Azizah, Nur; Sutanto, Heri; Suzery, Meiny

2015-01-01

Microalgae Spirulina sp has been identified as source of protein and other high added value compounds. One of the compounds is phycocyanin as also known for antioxidant use. The extraction of this compound by using conventional method (soxhlet extraction) resulted low yield and longer processing time. This research was aimed to extract phycocyanin by using an extraction assisted by ultrasound irradiation. The extraction was performed by using variable of ultrasound frequency and extraction temperature and ethanol was used as a solvent. The result showed that yield of phycocyanin extracted by conventional method was 11.13% while the ultrasound irradiation could increase the yield up to 15.61% at constant frequency of 42 kHz, while the optimum temperature was obtained at 45°C. The analysis of variable interactions showed that both temperature and time has an interaction and temperature was the highest variable in increasing the yield. The conclusion of this research was the ultrasound could improve significantly the efficiency of extraction as well as activity of phycocyanin extracted from microalgae

Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

Science.gov (United States)

Barlag, Rebecca; Nyasulu, Frazier

2011-01-01

The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

A role for subducted super-hydrated kaolinite in Earth's deep water cycle

Science.gov (United States)

Hwang, Huijeong; Seoung, Donghoon; Lee, Yongjae; Liu, Zhenxian; Liermann, Hanns-Peter; Cynn, Hyunchae; Vogt, Thomas; Kao, Chi-Chang; Mao, Ho-Kwang

2017-12-01

Water is the most abundant volatile component in the Earth. It continuously enters the mantle through subduction zones, where it reduces the melting temperature of rocks to generate magmas. The dehydration process in subduction zones, which determines whether water is released from the slab or transported into the deeper mantle, is an essential component of the deep water cycle. Here we use in situ and time-resolved high-pressure/high-temperature synchrotron X-ray diffraction and infrared spectra to characterize the structural and chemical changes of the clay mineral kaolinite. At conditions corresponding to a depth of about 75 km in a cold subducting slab (2.7 GPa and 200 °C), and in the presence of water, we observe the pressure-induced insertion of water into kaolinite. This super-hydrated phase has a unit cell volume that is about 31% larger, a density that is about 8.4% lower than the original kaolinite and, with 29 wt% H2O, the highest water content of any known aluminosilicate mineral in the Earth. As pressure and temperature approach 19 GPa and about 800 °C, we observe the sequential breakdown of super-hydrated kaolinite. The formation and subsequent breakdown of super-hydrated kaolinite in cold slabs subducted below 200 km leads to the release of water that may affect seismicity and help fuel arc volcanism at the surface.

The In Vitro Anti-Tumor Activity of Phycocyanin against Non-Small Cell Lung Cancer Cells

Directory of Open Access Journals (Sweden)

Shuai Hao

2018-05-01

Full Text Available Phycocyanin, a type of functional food colorant, is shown to have a potent anti-cancer property. Non-small cell lung cancer (NSCLC is one of the most aggressive form of cancers with few effective therapeutic options. Previous studies have demonstrated that phycocyanin exerts a growth inhibitory effect on NSCLC A549 cells. However, its biological function and underlying regulatory mechanism on other cells still remain unknown. Here, we investigated the in vitro function of phycocyanin on three typical NSCLC cell lines, NCI-H1299, NCI-H460, and LTEP-A2, for the first time. The results showed that phycocyanin could significantly induce apoptosis, cell cycle arrest, as well as suppress cell migration, proliferation, and the colony formation ability of NSCLC cells through regulating multiple key genes. Strikingly, phycocyanin was discovered to affect the cell phenotype through regulating the NF-κB signaling of NSCLC cells. Our findings demonstrated the anti-neoplastic function of phycocyanin and provided valuable information for the regulation of phycocyanin in NSCLC cells.

Phycocyanin assemblies onto nanostructured TiO2 for photovoltaic cells

Directory of Open Access Journals (Sweden)

Paula Enciso

2013-01-01

Full Text Available The use of renewable energies is of increasing importance due to depletion of fossil fuel sources and environmental damages caused by their utilization. The energy available from the sun is clean and widely distributed. Solar cells are devices used to convert solar energy into electricity. Among them, dye sensitized solar cells are an interesting alternative to conventional silicon ones, because of their low cost and simple assembly process. They are made of a semiconductor with colored dyes adsorbed onto the surface that work as antennas to catch energy in the visible range of the spectra. In this work, nanostructured TiO2 was synthesized and the protein phycocyanin was used as dye. TiO2 was characterized by electron microscopy, X ray diffraction and infrared spectroscopy (FTIR. Phycocyanin was extracted from commercial Spirulina spp. capsules. The assembly process of the electrode covered with TiO2 and phycocyanin was controlled by cyclic voltammetry and FTIR. Results were in accordance with the assembling of an electrode sensitized with phycocyanin.

Calcium Aluminate Cement Hydration Model

Directory of Open Access Journals (Sweden)

Matusinović, T.

2011-01-01

Full Text Available Calcium aluminate cement (AC is a very versatile special cement used for specific applications. As the hydration of AC is highly temperature dependent, yielding structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. The kinetics of AC hydration is a complex process and the use of single mechanisms models cannot describe the rate of hydration during the whole stage.This paper examines the influence of temperature (ϑ=5–20 °C and water-to-cement mass ratio (mH /mAC = 0.4; 0.5 and 1.0 on hydration of commercial iron-rich AC ISTRA 40 (producer: Istra Cement, Pula, Croatia, which is a part of CALUCEM group, Figs 1–3. The flow rate of heat generation of cement pastes as a result of the hydration reactions was measured with differential microcalorimeter. Chemically bonded water in the hydrated cement samples was determined by thermo-gravimetry.Far less heat is liberated when cement and water come in contact for the first time, Fig. 1, than in the case for portland cement (PC. Higher water-to-cement ratio increases the heat evolved at later ages (Fig. 3 due to higher quantity of water available for hydration. A significant effect of the water-to-cement ratio on the hydration rate and hydration degree showed the importance of water as being the limiting reactant that slows down the reaction early. A simplified stoichiometric model of early age AC hydration (eq. (8 based on reaction schemes of principal minerals, nominally CA, C12A7 and C4AF (Table 1, was employed. Hydration kinetics after the induction period (ϑ < 20 °C had been successfully described (Fig. 4 and Table 2 by a proposed model (eq. (23 which simultaneously comprised three main mechanisms: nucleation and growth, interaction at phase boundary, and mass transfer. In the proposed kinetic model the nucleation and growth is proportional to the amount of reacted minerals (eq

Gas hydrate inhibition by perturbation of liquid water structure

Science.gov (United States)

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

2015-06-01

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

Cement hydration from hours to centuries controlled by diffusion through barrier shells of C-S-H

Science.gov (United States)

Rahimi-Aghdam, Saeed; Bažant, Zdeněk P.; Abdolhosseini Qomi, M. J.

2017-02-01

Although a few good models for cement hydration exist, they have some limitations. Some do not take into account the complete range of variation of pore relative humidity and temperature, and apply over durations limited from up a few months to up to about a year. The ones that are applicable for long durations are either computationally too intensive for use in finite element programs or predict the hydration to terminate after few months. However, recent tests of autogenous shrinkage and swelling in water imply that the hydration may continue, at decaying rate, for decades, provided that a not too low relative pore humidity (above 0.7) persists for a long time, as expected for the cores of thick concrete structural members. Therefore, and because design lifetimes of over hundred years are required for large concrete structures, a new hydration model for a hundred year lifespan and beyond is developed. The new model considers that, after the first day of hydration, the remnants of anhydrous cement grains, gradually consumed by hydration, are enveloped by contiguous, gradually thickening, spherical barrier shells of calcium-silicate hydrate (C-S-H). The hydration progress is controlled by transport of water from capillary pores through the barrier shells toward the interface with anhydrous cement. The transport is driven by a difference of humidity, defined by equivalence with the difference in chemical potential of water. Although, during the period of 4-24 h, the C-S-H forms discontinuous nano-globules around the cement grain, an equivalent barrier shell control was formulated for this period, too, for ease and effectiveness of calculation. The entire model is calibrated and validated by published test data on the evolution of hydration degree for various cement types, particle size distributions, water-cement ratios and temperatures. Computationally, this model is sufficiently effective for calculating the evolution of hydration degree (or aging) at every

Hydrate phase equilibrium and structure for (methane + ethane + tetrahydrofuran + water) system

International Nuclear Information System (INIS)

Sun Changyu; Chen Guangjin; Zhang Lingwei

2010-01-01

The separation of methane and ethane through forming hydrate is a possible choice in natural gas, oil processing, or ethylene producing. The hydrate formation conditions of five groups of (methane + ethane) binary gas mixtures in the presence of 0.06 mole fraction tetrahydrofuran (THF) in water were obtained at temperatures ranging from (277.7 to 288.2) K. In most cases, the presence of THF in water can lower the hydrate formation pressure of (methane + ethane) remarkably. However, when the composition of ethane is as high as 0.832, it is more difficult to form hydrate than without THF system. Phase equilibrium model for hydrates containing THF was developed based on a two-step hydrate formation mechanism. The structure of hydrates formed from (methane + ethane + THF + water) system was also determined by Raman spectroscopy. When THF concentration in initial aqueous solution was only 0.06 mole fraction, the coexistence of structure I hydrate dominated by ethane and structure II hydrate dominated by THF in the hydrate sample was clearly demonstrated by Raman spectroscopic data. On the contrary, only structure II hydrate existed in the hydrate sample formed from (methane + ethane + THF + water) system when THF concentration in initial aqueous solution was increased to 0.10 mole fraction. It indicated that higher THF concentration inhibited the formation of structure I hydrate dominated by ethane and therefore lowered the trapping of ethane in hydrate. It implies a very promising method to increase the separation efficiency of methane and ethane.

Role of histamine in the inhibitory effects of phycocyanin in experimental models of allergic inflammatory response

Directory of Open Access Journals (Sweden)

D. Remirez

2002-01-01

Full Text Available It has recently been reported that phycocyanin, a biliprotein found in the blue-green microalgae Spirulina, exerts anti-inflammatory effects in some animal models of inflammation. Taking into account these findings, we decided to elucidate whether phycocyanin might exert also inhibitory effects in the induced allergic inflammatory response and on histamine release from isolated rat mast cells. In in vivo experiments, phycocyanin (100, 200 and 300 mg/kg post-orally (p.o. was administered 1 h before the challenge with 1 μg of ovalbumin (OA in the ear of mice previously sensitized with OA. One hour later, myeloperoxidase activity and ear edema were assessed. Phycocyanin significantly reduced both parameters. In separate experiments, phycocyanin (100 and 200 mg/kg p.o. also reduced the blue spot area induced by intradermal injections of histamine, and the histamine releaser compound 48/80 in rat skin. In concordance with the former results, phyco-cyanin also significantly reduced histamine release induced by compound 48/80 from isolated peritoneal rat mast cells. The inhibitory effects of phycocyanin were dose dependent. Taken together, our results suggest that inhibition of allergic inflammatory response by phycocyanin is mediated, at least in part, by inhibition of histamine release from mast cells.

A role for subducted super-hydrated kaolinite in Earth’s deep water cycle

Energy Technology Data Exchange (ETDEWEB)

Hwang, Huijeong; Seoung, Donghoon; Lee, Yongjae; Liu, Zhenxian; Liermann, Hanns-Peter; Cynn, Hyunchae; Vogt, Thomas; Kao, Chi-Chang; Mao, Ho-Kwang

2017-11-20

Water is the most abundant volatile component in the Earth. It continuously enters the mantle through subduction zones, where it reduces the melting temperature of rocks to generate magmas. The dehydration process in subduction zones, which determines whether water is released from the slab or transported into the deeper mantle, is an essential component of the deep water cycle. Here we use in situ and time-resolved high-pressure/high-temperature synchrotron X-ray diffraction and infrared spectra to characterize the structural and chemical changes of the clay mineral kaolinite. At conditions corresponding to a depth of about 75 km in a cold subducting slab (2.7 GPa and 200 °C), and in the presence of water, we observe the pressure-induced insertion of water into kaolinite. This super-hydrated phase has a unit cell volume that is about 31% larger, a density that is about 8.4% lower than the original kaolinite and, with 29 wt% H2O, the highest water content of any known aluminosilicate mineral in the Earth. As pressure and temperature approach 19 GPa and about 800 °C, we observe the sequential breakdown of super-hydrated kaolinite. The formation and subsequent breakdown of super-hydrated kaolinite in cold slabs subducted below 200 km leads to the release of water that may affect seismicity and help fuel arc volcanism at the surface.

An in situ synchrotron energy-dispersive diffraction study of the hydration of oilwell cement systems under high temperature/autoclave conditions up to 130 deg. C

International Nuclear Information System (INIS)

Colston, Sally L.; Barnes, Paul; Jupe, Andrew C.; Jacques, Simon D.M.; Hall, Christopher; Livesey, Paul; Dransfield, John; Meller, Nicola; Maitland, Geoffrey C.

2005-01-01

The technique of synchrotron energy dispersive diffraction has been developed for in situ studies of cement hydration under autoclave conditions. This has been applied to oilwell cements hydrating at typical oilwell temperatures up to 130 deg. C. The results show clearly the detailed interplay between 11 detectable phases, from which a phase transformation scheme has been derived; this illustrates the progression of hydration up to 130 deg. C for two extreme cases, with and without conservation of water content and autoclave pressure. The monosulphate hydrate phases are found to exhibit different stability bounds, with a surprising sequence of the 14-water, 10-water then 12-water monosulphate as temperature/time increases; the latter form is particularly associated with conditions of water/pressure loss. The effect of retarders on C 3 S dissolution and CH formation is negligible above 70 deg. C, whereas the effect on the calcium sulphoaluminate hydrates is more complex, and possible reasons for this are discussed

Hydration and nutrition knowledge in adolescent swimmers. Does water intake affect urine hydration markers after swimming?

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Cesare Altavilla

2017-12-01

Full Text Available Little data exists regarding nutritional knowledge and hydration in adolescent swimmers. The aim of this study was to assess the level of nutrition and hydration knowledge and to describe the fluid balance in adolescent swimmers during training. A study was carried out with a cross-sectional descriptive part and a longitudinal part with repeated measurements over five swimming sessions. Eighty-six adolescent swimmers completed a questionnaire to assess their sport nutrition and hydration knowledge. Fluid balance and urine hydration markers were studied during training. Swimmers showed a limited nutrition knowledge (33.26 % ± SD 12.59 and meagre hydration knowledge (28.61 % ± SD 28.59. Females showed lower scores than male swimmers in nutrition and hydration knowledge. Based on urine specific gravity, swimmers started the training close to the euhydrated threshold (1.019 g/mL ± SD 0.008. Although urine specific gravity and urine colour were reduced after the training, there were minimal changes in body mass (-0.12 Kg ± SD 0.31. Sweat loss (2.67 g/min ± SD 3.23 and the net changes in the fluid balance (-0.22 % ± SD 0.59 were low. The poor knowledge in nutrition and hydration encountered in the swimmers can justify the development of a strategy to incorporate nutritional education programmes for this group. Body water deficit from swimming activity seems to be easily replaced with the water intake to maintain hydration. After the training, the urine of swimmers was diluted regardless of their water intake. Dilution of urine did not reflect real hydration state in swimming.

Thermostable phycocyanin from the red microalga Cyanidioschyzon merolae, a new natural blue food colorant

NARCIS (Netherlands)

Rahman, D. Y.; Sarian, F. D.; van Wijk, A.; Martinez-Garcia, M.; van der Maarel, M. J. E. C.

The demand for natural food colorants is growing as consumers question the use of artificial colorants more and more. The phycobiliprotein C-phycocyanin of Arthospira platensis is used as a natural blue colorant in certain food products. The thermoacidophilic red microalga Cyanidioschyzon merolae

Determining the water-cement ratio, cement content, water content and degree of hydration of hardened cement paste: Method development and validation on paste samples

International Nuclear Information System (INIS)

Wong, H.S.; Buenfeld, N.R.

2009-01-01

We propose a new method to estimate the initial cement content, water content and free water/cement ratio (w/c) of hardened cement-based materials made with Portland cements that have unknown mixture proportions and degree of hydration. This method first quantifies the composition of the hardened cement paste, i.e. the volumetric fractions of capillary pores, hydration products and unreacted cement, using high-resolution field emission scanning electron microscopy (FE-SEM) in the backscattered electron (BSE) mode and image analysis. From the obtained data and the volumetric increase of solids during cement hydration, we compute the initial free water content and cement content, hence the free w/c ratio. The same method can also be used to calculate the degree of hydration. The proposed method has the advantage that it is quantitative and does not require comparison with calibration graphs or reference samples made with the same materials and cured to the same degree of hydration as the tested sample. This paper reports the development, assumptions and limitations of the proposed method, and preliminary results from Portland cement pastes with a range of w/c ratios (0.25-0.50) and curing ages (3-90 days). We also discuss the extension of the technique to mortars and concretes, and samples made with blended cements.

Clinker mineral hydration at reduced relative humidities

DEFF Research Database (Denmark)

Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.

1999-01-01

and experimental data are presented showing that C(3)A can hydrate at lower humidities than either C3S or C2S. It is suggested that the initiation of hydration during exposure to water vapour is nucleation controlled. When C(3)A hydrates at low humidity, the characteristic hydration product is C(3)AH(6......Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations...

Fast cleavage of phycocyanobilin from phycocyanin for use in food colouring.

Science.gov (United States)

Roda-Serrat, Maria Cinta; Christensen, Knud Villy; El-Houri, Rime Bahij; Fretté, Xavier; Christensen, Lars Porskjær

2018-02-01

Phycocyanins from cyanobacteria are possible sources for new natural blue colourants. Their chromophore, phycocyanobilin (PCB), was cleaved from the apoprotein by solvolysis in alcohols and alcoholic aqueous solutions. In all cases two PCB isomers were obtained, while different solvent adducts were formed upon the use of different reagents. The reaction is believed to take place via two competing pathways, a concerted E2 elimination and a S N 2 nucleophilic substitution. Three cleavage methods were compared in terms of yield and purity: conventional reflux, sealed vessel heated in an oil bath, and microwave assisted reaction. The sealed vessel method is a new approach for fast cleavage of PCB from phycocyanin and gave at 120°C the same yield within 30min compared to 16h by the conventional reflux method (P<0.05). In addition the sealed vessel method resulted in improved purity compared to the other methods. Microwave irradiation increased product degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of surfactants on gas-hydrate formation' kinetics in water-oil emulsion

Science.gov (United States)

Zemenkov, Yu D.; Shirshova, A. V.; Arinstein, E. A.; Shuvaev, A. N.

2018-05-01

The kinetics of gas hydrate formation of propane in a water-oil emulsion is experimentally studied when three types of surfactants (SAA (surface acting agent)) - anionic type emulsifiers - are added to the aqueous phase. It is shown that all three types of surfactants decelerate the growth of the gas-hydrate in the emulsion and can be considered as anti-agglutinating and kinetic low-dose inhibitors. The most effective inhibitor of hydrate formation in water-oil emulsion of SV-102 surfactant was revealed. For comparison, experimental studies of gas-hydrate formation under the same conditions for bulk water have been carried out. It is shown that in bulk water, all the surfactants investigated act as promoters (accelerators) of hydrate formation. A qualitative explanation of the action mechanisms of emulsifiers in the process of gas-hydrate formation in water-oil emulsion is given.

Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

Science.gov (United States)

Biswas, Biswajit; Singh, Prashant Chandra

2015-11-11

The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes.

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

Science.gov (United States)

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

2018-02-01

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

Macroscopic investigation of water volume effects on interfacial dynamic behaviors between clathrate hydrate and water.

Science.gov (United States)

Cha, Minjun; Couzis, Alexander; Lee, Jae W

2013-05-14

This study investigated the effects of the water volume on the interfacial dynamics between cyclopentane (CP) hydrate and water droplet in a CP/n-decane oil mixture. The adhesion force between CP hydrate and various water droplets was determined using the z-directional microbalance. Through repetition of precise measurements over several cycles from contact to detachment, we observed abnormal wetting behaviors in the capillary bridge during the retraction process when the water drop volume is larger than 100 μL. With the increase in water droplet volumes, the contact force between CP hydrate and water also increases up to 300 μL. However, there is a dramatic reduction of increasing rate in the contact forces over 300 μL of water droplet. With the addition of the surfactants of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) to the water droplet, the contact force between CP hydrate and solution droplet exhibits a lower value and a transition volume of the contact force comes with a smaller solution volume of 200 μL. The water volume effects on the liquid wetting of the probe and the size of capillary bridges provide important insight into hydrate growth and aggregation/agglomeration in the presence of free water phase inside gas/oil pipelines.

Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

International Nuclear Information System (INIS)

Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R.; Miller, Benjamin T.; Brooks, Bernard R.; Ichiye, Toshiko

2015-01-01

The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V E as a function of ethanol mole fraction X E is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water

Ethylene Separation via Hydrate Formation in W/O Emulsions

Directory of Open Access Journals (Sweden)

Yong Pan

2015-05-01

Full Text Available An hybrid absorption-hydration method was adopted to recover C2H4 from C2H4/CH4 binary gas mixtures and the hydrate formation conditions of C2H4/CH4 mixtures was studied experimentally in diesel in water (w/o emulsions. Span 20 at a concentration of 1.0 wt% in the aqueous phase was added to form water in diesel emulsions before hydrate formation and then hydrate in diesel slurry was separated after hydrate formation. The influences of initial gas-liquid volume ratio (53–142, pressure (3.4–5.4 MPa, temperature (274.15–278.15 K, water cuts (10–30 vol%, and the mole fraction of C2H4 in feed gas (13.19–80.44 mol% upon the C2H4 separation efficiency were systematically investigated. The experimental results show that ethylene can be enriched in hydrate slurry phase with high separation factor (S and recovery ratio (R. Most hydrate formation finished in 20 min, after that, the hydrate formation rate became very slow. The conclusion is useful for determining the suitable operation conditions when adopting an absorption-hydration method to separate C2H4/CH4.

Water Transfer Characteristics during Methane Hydrate Formation Processes in Layered Media

Directory of Open Access Journals (Sweden)

Yousheng Deng

2011-08-01

Full Text Available Gas hydrate formation processes in porous media are always accompanied by water transfer. To study the transfer characteristics comprehensively, two kinds of layered media consisting of coarse sand and loess were used to form methane hydrate in them. An apparatus with three PF-meter sensors detecting water content and temperature changes in media during the formation processes was applied to study the water transfer characteristics. It was experimentally observed that the hydrate formation configurations in different layered media were similar; however, the water transfer characteristics and water conversion ratios were different.

Probing the hydration water diffusion of macromolecular surfaces and interfaces

International Nuclear Information System (INIS)

Ortony, Julia H; Cheng, Chi-Yuan; Franck, John M; Pavlova, Anna; Hunt, Jasmine; Han, Songi; Kausik, Ravinath

2011-01-01

We probe the translational dynamics of the hydration water surrounding the macromolecular surfaces of selected polyelectrolytes, lipid vesicles and intrinsically disordered proteins with site specificity in aqueous solutions. These measurements are made possible by the recent development of a new instrumental and methodological approach based on Overhauser dynamic nuclear polarization (DNP)-enhanced nuclear magnetic resonance (NMR) spectroscopy. This technique selectively amplifies 1 H NMR signals of hydration water around a spin label that is attached to a molecular site of interest. The selective 1 H NMR amplification within molecular length scales of a spin label is achieved by utilizing short-distance range (∼r -3 ) magnetic dipolar interactions between the 1 H spin of water and the electron spin of a nitroxide radical-based label. Key features include the fact that only minute quantities (<10 μl) and dilute (≥100 μM) sample concentrations are needed. There is no size limit on the macromolecule or molecular assembly to be analyzed. Hydration water with translational correlation times between 10 and 800 ps is measured within ∼10 A distance of the spin label, encompassing the typical thickness of a hydration layer with three water molecules across. The hydration water moving within this time scale has significant implications, as this is what is modulated whenever macromolecules or molecular assemblies undergo interactions, binding or conformational changes. We demonstrate, with the examples of polymer complexation, protein aggregation and lipid-polymer interaction, that the measurements of interfacial hydration dynamics can sensitively and site specifically probe macromolecular interactions.

NMR Studies of Protein Hydration and Protein-Ligand Interactions

Science.gov (United States)

Chong, Yuan

Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be

Transport of hydrate slurry at high water cut

OpenAIRE

Melchuna , Aline; Cameirão , Ana; Herri , Jean-Michel; Ouabbas , Yamina; Glenat , Philippe

2014-01-01

Poster; International audience; Oil transportation in pipelines at the end of field production life implies to flow high quantities of water which represents the dominant phase. The process of crystallization of gas hydrates in this system needs to be studied and compared to the opposite one widely studied in the literature where water is the dispersed phase. The laboratory is equipped with the Archimede flow loop where the hydrate crystallization and transport are monitored. The flow loop is...

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

Science.gov (United States)

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-01-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature

Suspension hydration of C3S [tricalcium silicate] at constant pH. II. Effect of previously formed hydrates and of additives

NARCIS (Netherlands)

McCurdy, K.G.; Stein, H.N.

1973-01-01

A retardation shown by the hydration of C3S at pH=11.5 can be prevented if before the addition of C3S there are present hydrate particles in the aqueous medium. These hydrate particles probably have the composition CSHn. This indicates a hydrate CSHn, precipitated from solution, as the retarding

Hydration of DNA by tritiated water and isotope distribution: a study by 1H, 2H, and 3H NMR spectroscopy

International Nuclear Information System (INIS)

Mathur-De Vre, R.; Grimee-Declerck, R.; Lejeune, P.; Bertinchamps, A.J.

1982-01-01

The hydration layer of DNA (0.75%) in tritiated water represents 3.5% of solvent 3 HHO. The combined effects of temperature (-6 to -40 0 C) and H 2 O/ 2 H 2 O solvent composition on the spin-lattice relaxation times of water protons and deuterons suggest selective distribution of isotopes in the hydration layer. The ''hydration isotope'' effect and the localization of tritiated water molecules in the hydration layer of DNA have important implications in describing the radiobiological effects of tritiated water because the initial molecular damage caused by 3 HHO (internal radiation source) localizes close to 3 H due to the short range and low energy of 3 H β rays

Water Intake and Hydration Indices in Healthy European Adults: The European Hydration Research Study (EHRS).

Science.gov (United States)

Malisova, Olga; Athanasatou, Adelais; Pepa, Alex; Husemann, Marlien; Domnik, Kirsten; Braun, Hans; Mora-Rodriguez, Ricardo; Ortega, Juan F; Fernandez-Elias, Valentin E; Kapsokefalou, Maria

2016-04-06

Hydration status is linked with health, wellness, and performance. We evaluated hydration status, water intake, and urine output for seven consecutive days in healthy adults. Volunteers living in Spain, Germany, or Greece (n = 573, 39 ± 12 years (51.1% males), 25.0 ± 4.6 kg/m² BMI) participated in an eight-day study protocol. Total water intake was estimated from seven-day food and drink diaries. Hydration status was measured in urine samples collected over 24 h for seven days and in blood samples collected in fasting state on the mornings of days 1 and 8. Total daily water intake was 2.75 ± 1.01 L, water from beverages 2.10 ± 0.91 L, water from foods 0.66 ± 0.29 L. Urine parameters were: 24 h volume 1.65 ± 0.70 L, 24 h osmolality 631 ± 221 mOsmol/kg Η2Ο, 24 h specific gravity 1.017 ± 0.005, 24 h excretion of sodium 166.9 ± 54.7 mEq, 24 h excretion of potassium 72.4 ± 24.6 mEq, color chart 4.2 ± 1.4. Predictors for urine osmolality were age, country, gender, and BMI. Blood indices were: haemoglobin concentration 14.7 ± 1.7 g/dL, hematocrit 43% ± 4% and serum osmolality 294 ± 9 mOsmol/kg Η2Ο. Daily water intake was higher in summer (2.8 ± 1.02 L) than in winter (2.6 ± 0.98 L) (p = 0.019). Water intake was associated negatively with urine specific gravity, urine color, and urine sodium and potassium concentrations (p < 0.01). Applying urine osmolality cut-offs, approximately 60% of participants were euhydrated and 20% hyperhydrated or dehydrated. Most participants were euhydrated, but a substantial number of people (40%) deviated from a normal hydration level.

Effects of C3H8 on hydrate formation and dissociation for integrated CO2 capture and desalination technology

International Nuclear Information System (INIS)

Yang, Mingjun; Zheng, Jianan; Liu, Weiguo; Liu, Yu; Song, Yongchen

2015-01-01

Hydrate-based technology has been developing for decades to meet the demands in industrial applications. With the global demands for reduced carbon dioxide (CO 2 ) emissions and more fresh water, CHBD (CO 2 hydrate-based desalination) was proposed and has developed rapidly. In this study, to provide basic data for the improvement of CHBD, the thermodynamic and kinetic characteristics of CO 2 and propane (C 3 H 8 ) mixed-gas hydrates in salt solution were experimentally investigated in which C 3 H 8 was chosen as the hydrate formation promoter. We studied nine experimental cases (54 cycles) with different C 3 H 8 proportions (ranging from 0 to 13%) and different initial solution saturations (30%, 40% and 50%). The hydrate phase equilibrium data were generated using the isochoric method, and the hydrate formation saturations were calculated using the relative gas uptake equation. The results indicated that the increase in the C 3 H 8 proportion significantly decreases the gas mixture hydrate equilibrium pressure. Additionally, the relative gas uptake was reduced as the C 3 H 8 proportion increased. A lower relative gas uptake was obtained at a lower gas pressure for the same gas mixture. The initial solution saturation exhibited an insignificant effect on the hydrate phase equilibrium conditions. When the initial solution saturations increased from 30% to 50%, the relative gas uptake decreased. - Highlights: • C 3 H 8 improves the thermodynamics and kinetics of CO 2 hydrates formation. • Hydrates equilibrium pressure decreases with the increase of C 3 H 8 proportion. • Higher C 3 H 8 proportion and/or solution saturation decrease relative gas uptake. • Initial pressure and solution saturation has interactive effect on gas uptake.

The composition of cement hydrating at 60 deg C from synchrotron radiation

International Nuclear Information System (INIS)

Auld, J.; Turner, K.; Thorogood, G.J.; Ball, C.J.; Aldridge, L.P.; Taylor, J.C.

2002-01-01

Full text: Cement consists of 5 phases C3S, C2S, C3A, C4AF (where C denotes CaO, S denotes SiO 2 , A denotes AI 2 O 3 and F denotes Fe 2 O 3 ) and gypsum. When cement hydrates it forms an amorphous calcium silicate hydrate (C-S-H) as well as the crystalline ettringite and calcium hydroxide. The x-ray diffraction pattern of the hydrated cement is difficult to interpret because of its complexity. In addition, the overlapping lines from the remaining cement compounds make it difficult to quantify the amount of the crystalline components present. Using Rietveld analysis we have been able to interpret the patterns obtained from synchrotron x-ray diffraction patterns obtained at the Photon Factory at the Australian National Beamline Facility using BIGDIF. The changes in the composition of the hydrated cement paste were determined as a function of time during hydration at 60 deg C. Copyright (2002) Australian X-ray Analytical Association Inc

Modelling membrane hydration and water balance of a pem fuel cell

DEFF Research Database (Denmark)

Liso, Vincenzo; Nielsen, Mads Pagh

2015-01-01

Polymer electrolyte membrane (PEM) fuel cells requires an appropriate hydration in order to ensure high efficiency and long durability. As water is essential for promoting proton conductivity in the membrane, it is important to control membrane water hydration to avoid flooding. In this study we...

Calculation of amorphous silica solubilities at 25° to 300°C and apparent cation hydration numbers in aqueous salt solutions using the concept of effective density of water

Science.gov (United States)

Fournier, Robert O.; Williams, Marshall L.

1983-01-01

The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. pe, of “free” water in that solution. At temperatures of 100°C and above, pe closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to pe that incorporates a term called the apparent cation hydration number, h. Because of the many assumptions and other uncertainties involved in determining values of h, by the model used here, the reported numbers are not necessarily real hydration numbers even though they do agree with some published values determined by activity and diffusion methods. Whether or not h is a real hydration number, it would appear to be useful in its inclusion within a more extensive activity coefficient term that describes the departure of silica solubilities in concentrated salt solutions from expected behavior according to the model presented here. Values of h can be calculated from measured amorphous silica solubilities in salt solutions at 25°C provided there is no complexing of dissolved silica with the dissolved salt, or if the degree of complexing is known. The previously postulated aqueous silica-sulfate complexing in aqueous Na2SO4 solutions is supported by results of the present effective density of water model

Water around fullerene shape amphiphiles: A molecular dynamics simulation study of hydrophobic hydration

Energy Technology Data Exchange (ETDEWEB)

Varanasi, S. R., E-mail: s.raovaranasi@uq.edu.au, E-mail: guskova@ipfdd.de; John, A. [Institut Theorie der Polymere, Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, Dresden D-01069 (Germany); Guskova, O. A., E-mail: s.raovaranasi@uq.edu.au, E-mail: guskova@ipfdd.de [Institut Theorie der Polymere, Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, Dresden D-01069 (Germany); Dresden Center for Computational Materials Science (DCMS), Technische Universität Dresden, Dresden D-01069 (Germany); Sommer, J.-U. [Institut Theorie der Polymere, Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, Dresden D-01069 (Germany); Dresden Center for Computational Materials Science (DCMS), Technische Universität Dresden, Dresden D-01069 (Germany); Institut für Theoretische Physik, Technische Universität Dresden, Zellescher Weg 17, Dresden D-01069 (Germany)

2015-06-14

Fullerene C{sub 60} sub-colloidal particle with diameter ∼1 nm represents a boundary case between small and large hydrophobic solutes on the length scale of hydrophobic hydration. In the present paper, a molecular dynamics simulation is performed to investigate this complex phenomenon for bare C{sub 60} fullerene and its amphiphilic/charged derivatives, so called shape amphiphiles. Since most of the unique properties of water originate from the pattern of hydrogen bond network and its dynamics, spatial, and orientational aspects of water in solvation shells around the solute surface having hydrophilic and hydrophobic regions are analyzed. Dynamical properties such as translational-rotational mobility, reorientational correlation and occupation time correlation functions of water molecules, and diffusion coefficients are also calculated. Slower dynamics of solvent molecules—water retardation—in the vicinity of the solutes is observed. Both the topological properties of hydrogen bond pattern and the “dangling” –OH groups that represent surface defects in water network are monitored. The fraction of such defect structures is increased near the hydrophobic cap of fullerenes. Some “dry” regions of C{sub 60} are observed which can be considered as signatures of surface dewetting. In an effort to provide molecular level insight into the thermodynamics of hydration, the free energy of solvation is determined for a family of fullerene particles using thermodynamic integration technique.

Water around fullerene shape amphiphiles: A molecular dynamics simulation study of hydrophobic hydration

International Nuclear Information System (INIS)

Varanasi, S. R.; John, A.; Guskova, O. A.; Sommer, J.-U.

2015-01-01

Fullerene C 60 sub-colloidal particle with diameter ∼1 nm represents a boundary case between small and large hydrophobic solutes on the length scale of hydrophobic hydration. In the present paper, a molecular dynamics simulation is performed to investigate this complex phenomenon for bare C 60 fullerene and its amphiphilic/charged derivatives, so called shape amphiphiles. Since most of the unique properties of water originate from the pattern of hydrogen bond network and its dynamics, spatial, and orientational aspects of water in solvation shells around the solute surface having hydrophilic and hydrophobic regions are analyzed. Dynamical properties such as translational-rotational mobility, reorientational correlation and occupation time correlation functions of water molecules, and diffusion coefficients are also calculated. Slower dynamics of solvent molecules—water retardation—in the vicinity of the solutes is observed. Both the topological properties of hydrogen bond pattern and the “dangling” –OH groups that represent surface defects in water network are monitored. The fraction of such defect structures is increased near the hydrophobic cap of fullerenes. Some “dry” regions of C 60 are observed which can be considered as signatures of surface dewetting. In an effort to provide molecular level insight into the thermodynamics of hydration, the free energy of solvation is determined for a family of fullerene particles using thermodynamic integration technique

Thermodynamic properties of hydrated cement phases: C-S-H, C-A-S-H and M-S-H

International Nuclear Information System (INIS)

Roosz, Cedric

2016-01-01

representative phases of the studied chemical system, and (ii) a precise knowledge of the structure and chemical formulas of these phases. Three types of hydrates were therefore synthesized and characterized: C-S-H, C-A-S-H and M-S-H. Analytical methods such as XRD, TGA and solid state NMR ( 29 Si, 27 Al) are used to ascertain similarities between the structure of C-(A-)S-H and that of tobermorite, and between the structure of M-S-H and that of Mg-Si phyllosilicates 2:1. Hydrates, however, have a lower crystallinity, with defects in the polymerization of silica chains, and random stacking faults (turbostratism). A multi-technique approach is also used, combining adsorption isotherm(water and nitrogen) and 1 HNMR with XRD and TGA, and allows characterization of different types of water more or less bound to the structure of C-(A-)S-H. This study allowed to highlight and quantify the different types of water in the C-(A-)S-H structure. The impact of the drying process was also highlighted on the quantification of different types of water, including interlayer water. The acquisition of thermodynamic parameters of the synthesized phases is carried out from the analysis of equilibrium solutions for the calculation of log K and Δ f G 0 , while calorimetric acquisitions permit obtaining heat capacities and the calculation of S 0 . Finally, enthalpy of formation of these phases is calculated from the Gibbs free energy of formation and entropies. The predictive model is developed from the acquired thermodynamic properties. The Gibbs free energy of formation Δ f G 0 is predicted from an electronegativity model, while Cp and S 0 are predicted through polyhedral decomposition model. Finally, a comparison of data obtained with those published in the literature, and the realization of predominance diagrams generalized to the whole CaO-MgO-Al 2 O 3 -SiO 2 -H 2 O system assess the reliability of the proposed model. (author) [fr

Optimization of linear and branched alkane interactions with water to simulate hydrophobic hydration

Science.gov (United States)

Ashbaugh, Henry S.; Liu, Lixin; Surampudi, Lalitanand N.

2011-08-01

Previous studies of simple gas hydration have demonstrated that the accuracy of molecular simulations at capturing the thermodynamic signatures of hydrophobic hydration is linked both to the fidelity of the water model at replicating the experimental liquid density at ambient pressure and an accounting of polarization interactions between the solute and water. We extend those studies to examine alkane hydration using the transferable potentials for phase equilibria united-atom model for linear and branched alkanes, developed to reproduce alkane phase behavior, and the TIP4P/2005 model for water, which provides one of the best descriptions of liquid water for the available fixed-point charge models. Alkane site/water oxygen Lennard-Jones cross interactions were optimized to reproduce the experimental alkane hydration free energies over a range of temperatures. The optimized model reproduces the hydration free energies of the fitted alkanes with a root mean square difference between simulation and experiment of 0.06 kcal/mol over a wide temperature range, compared to 0.44 kcal/mol for the parent model. The optimized model accurately reproduces the temperature dependence of hydrophobic hydration, as characterized by the hydration enthalpies, entropies, and heat capacities, as well as the pressure response, as characterized by partial molar volumes.

Hydration of ammonia, methylamine, and methanol in amorphous solid water

Science.gov (United States)

Souda, Ryutaro

2016-02-01

Interactions of polar protic molecules with amorphous solid water (ASW) have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. The ammonia and methylamine are incorporated into the interior of porous ASW films. They are caged by water molecules and are released during water crystallization. In contrast, the methanol-water interaction is not influenced by pores of ASW. The methanol additives tend to survive water crystallization and are released during ASW film evaporation. The hydration of n-hexane in ASW is influenced significantly by methanol additives because n-hexane is accommodated in a methanol-induced hydration shell.

Differential scanning calorimetric study of the binding between native DNA and its primary water of hydration.

Science.gov (United States)

Marlowe, R. L.; Lukan, A. M.; Lee, S. A.; Anthony, L.; Rupprecht, A.

1996-03-01

Differential scanning calorimetry was used to measure the binding strength between calf-thymus DNA and its primary water of hydration. The specific heat of wet-spun films was found to have a broad endothermic transition near 80 ^oC and a sharp exothermic transition near 250 ^oC. The broad transition is believed to be mainly due to the breaking of the bonds of the strongly bound water of hydration. This transition was found to be reversible, as expected. Kissinger analysis indicates that the activation barrier for breaking the bonds of these water molecules is about 0.6 eV. The sharp transition appeared to be an indication of a thermal decomposition of the DNA. Samples taken above this transition lost mass, showed evidence of having melted, and had turned black in color. This transition is irreversible.

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

Science.gov (United States)

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

2014-10-01

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

Nonlinear fluid dynamics of nanoscale hydration water layer

Science.gov (United States)

Jhe, Wonho; Kim, Bongsu; Kim, Qhwan; An, Sangmin

In nature, the hydration water layer (HWL) ubiquitously exists in ambient conditions or aqueous solutions, where water molecules are tightly bound to ions or hydrophilic surfaces. It plays an important role in various mechanisms such as biological processes, abiotic materials, colloidal interaction, and friction. The HWL, for example, can be easily formed between biomaterials since most biomaterials are covered by hydrophilic molecules such as lipid bilayers, and this HWL is expected to be significant to biological and physiological functions. Here (1) we present the general stress tensor of the hydration water layer. The hydration stress tensor provided the platform form for holistic understanding of the dynamic behaviors of the confined HWL including tapping and shear dynamics which are until now individually studied. And, (2) through fast shear velocity ( 1mm/s) experiments, the elastic turbulence caused by elastic property of the HWL is indirectly observed. Our results may contribute to a deeper study of systems where the HWL plays an important role such as biomolecules, colloidal particles, and the MEMS. This work was supported by the National Research Foundation of Korea(NRF) Grant funded by the Korea government(MSIP) (2016R1A3B1908660).

Multilayer perceptron neural network-based approach for modeling phycocyanin pigment concentrations: case study from lower Charles River buoy, USA.

Science.gov (United States)

Heddam, Salim

2016-09-01

This paper proposes multilayer perceptron neural network (MLPNN) to predict phycocyanin (PC) pigment using water quality variables as predictor. In the proposed model, four water quality variables that are water temperature, dissolved oxygen, pH, and specific conductance were selected as the inputs for the MLPNN model, and the PC as the output. To demonstrate the capability and the usefulness of the MLPNN model, a total of 15,849 data measured at 15-min (15 min) intervals of time are used for the development of the model. The data are collected at the lower Charles River buoy, and available from the US Environmental Protection Agency (USEPA). For comparison purposes, a multiple linear regression (MLR) model that was frequently used for predicting water quality variables in previous studies is also built. The performances of the models are evaluated using a set of widely used statistical indices. The performance of the MLPNN and MLR models is compared with the measured data. The obtained results show that (i) the all proposed MLPNN models are more accurate than the MLR models and (ii) the results obtained are very promising and encouraging for the development of phycocyanin-predictive models.

Dietary controlled carcinogenicity study of chloral hydrate in male B6C3F1 mice

International Nuclear Information System (INIS)

Leakey, Julian E.A.; Seng, John E.; Latendresse, John R.; Hussain, Nursreen; Allen, Laura J.; Allaben, William T.

2003-01-01

Chloral hydrate, which is used as a sedative in pediatric medicine and is a by-product of water chlorination, is hepatocarcinogenic in B6C3F 1 mice, a strain that can exhibit high rates of background liver tumor incidence, which are associated with increased body weight. In this study, dietary control was used to manipulate body growth in male B6C3F 1 mice in a 2-year bioassay of chloral hydrate. Male B6C3F 1 mice were treated with water or 25, 50, or 100 mg/kg chloral hydrate by gavage. The study compared ad libitum-fed mice with dietary controlled mice. The latter received variably restricted feed allocations to maintain their body weights on a predetermined 'idealized' weight curve predictive of a terminal background liver tumor incidence of 15-20%. These mice exhibited less individual body weight variation than did their ad libitum-fed counterparts. This was associated with a decreased variation in liver to body weight ratios, which allowed the demonstration of a statistically significant dose response to chloral hydrate in the dietary controlled, but not the ad libitum-fed, test groups. Chloral hydrate increased terminally adjusted liver tumor incidence in both dietary controlled (23.4, 23.9, 29.7, and 38.6% for the four dose groups, respectively) and ad libitum-fed mice (33.4, 52.6, 50.6, and 46.2%), but a statistically significant dose response was observed only in the dietary controlled mice. This dose response positively correlated with markers of peroxisomal proliferation in the dietary controlled mice only. The study suggests that dietary control not only improves terminal survival and decreases interassay variation, but also can increase assay sensitivity by decreasing intra-assay variation

Adsorption of water and carbon dioxide on hematite and consequences for possible hydrate formation.

Science.gov (United States)

Kvamme, Bjørn; Kuznetsova, Tatiana; Kivelae, Pilvi-Helina

2012-04-07

The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decline in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide into the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures, conditions which may lead to formation of hydrates from residual water dissolved in carbon dioxide and carbon dioxide. The critical question is whether the water at certain temperatures and pressures will drop out as liquid droplets first, and then form hydrates, or alternatively, adsorb on the pipeline surfaces, and subsequently form hydrates heterogeneously. In this work, we used several different basis sets of density functional theory in ab initio calculations to estimate the charge distribution of hematite (the dominating component of rust) crystals. These rust particles were embedded in water and chemical potential for adsorbed water molecules was estimated through thermodynamic integration and compared to similar estimates for water clusters of the same size. While the generated charges were not unique, the use of high order approximations and different basis sets provides a range of likely charge distributions. Values obtained for the chemical potential of water in different surroundings indicated that it would be thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based on this formation mechanism. Depending on the basis set and approximations, the estimated gain for water to adsorb on the hematite surface rather than condense as droplets varied between -1.7 kJ mole(-1) and -3.4 kJ mole(-1). The partial charge distribution on the hematite surface is incompatible with the hydrate structure, and thus hydrates will be unable to attach to the surface. The behavior of water outside the immediate vicinity of hematite (beyond 3

Scavenging of peroxynitrite by phycocyanin and phycocyanobilin from Spirulina platensis: protection against oxidative damage to DNA.

Science.gov (United States)

Bhat, V B; Madyastha, K M

2001-07-13

Peroxynitrite (ONOO(-)) is known to inactivate important cellular targets and also mediate oxidative damage in DNA. The present study has demonstrated that phycocyanin, a biliprotein from spirulina platensis and its chromophore, phycocyanobilin (PCB), efficiently scavenge ONOO(-), a potent physiological inorganic toxin. Scavenging of ONOO(-) by phycocyanin and PCB was established by studying their interaction with ONOO(-) and quantified by using competition kinetics of pyrogallol red bleaching assay. The relative antioxidant ratio and IC(50) value clearly indicate that phycocyanin is a more efficient ONOO(-) scavenger than PCB. The present study has also shown that PCB significantly inhibits the ONOO(-)-mediated single-strand breaks in supercoiled plasmid DNA in a dose-dependent manner with an IC(50) value of 2.9 +/- 0.6 microM. These results suggest that phycocyanin, has the ability to inhibit the ONOO(-)-mediated deleterious biological effects and hence has the potential to be used as a therapeutic agent. Copyright 2001 Academic Press.

Squirt flow due to interfacial water films in hydrate bearing sediments

Directory of Open Access Journals (Sweden)

K. Sell

2018-05-01

Full Text Available Sediments containing gas hydrate dispersed in the pore space are known to show a characteristic seismic anomaly which is a high attenuation along with increasing seismic velocities. Currently, this observation cannot be fully explained albeit squirt-flow type mechanisms on the microscale have been speculated to be the cause. Recent major findings from in situ experiments, using the gas in excess and water in excess formation method, and coupled with high-resolution synchrotron-based X-ray micro-tomography, have revealed the systematic presence of thin water films between the quartz grains and the encrusting hydrate. The data obtained from these experiments underwent an image processing procedure to quantify the thicknesses and geometries of the aforementioned interfacial water films. Overall, the water films vary from sub-micrometer to a few micrometers in thickness. In addition, some of the water films interconnect through water bridges. This geometrical analysis is used to propose a new conceptual squirt flow model for hydrate bearing sediments. A series of numerical simulations is performed considering variations of the proposed model to study seismic attenuation caused by such thin water films. Our results support previous speculation that squirt flow can explain high attenuation at seismic frequencies in hydrate bearing sediments, but based on a conceptual squirt flow model which is geometrically different than those previously considered.

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4)

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Toft, A.; Nielsen, O.J.

2006-01-01

. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source...

Water Dynamics in Protein Hydration Shells: The Molecular Origins of the Dynamical Perturbation

Science.gov (United States)

2014-01-01

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra. PMID:24479585

Antioxidant activity of hydrated carboxylated nanodiamonds and its influence on water γ-radiolysis

Science.gov (United States)

Santacruz-Gomez, Karla; Sarabia-Sainz, A.; Acosta-Elias, M.; Sarabia-Sainz, M.; Janetanakit, Woraphong; Khosla, Nathan; Melendrez, R.; Pedroza Montero, Martin; Lal, Ratnesh

2018-03-01

Water radiolysis involves chemical decomposition of the water molecule into free radicals after exposure to ionizing radiation. These free radicals have deleterious effects on normal cell physiology. Carboxylated nanodiamonds (cNDs) appear to modulate the deleterious effects of γ-irradiation on the pathophysiology of red blood cells (RBCs). In the present work, the antioxidant activity of hydrated cNDs (h-cNDs) on limiting oxidative damage (the water radiolysis effect) by γ-irradiation was confirmed. Our results show that h-cNDs have remarkable free radical scavenging ability and preserve the enzymatic activity of catalase after γ-irradiation. The underlying mechanism through which nanodiamonds exhibit antioxidant activity appears to depend on their colloidal stability. This property of detonation synthesized nanodiamonds is improved after carboxylation, which in turn influences changes in the hydrogen bond strength in water. The observed stability of h-cNDs in water and their antioxidant activity correlates with their protective effect on RBCs against γ-irradiation.

The influence of Na2O on the hydration of C3A II. Suspension hydration

NARCIS (Netherlands)

Spierings, G.A.C.M.; Stein, H.N.

1976-01-01

The influence of Na2O on the hydration of C3A was studied in suspensions from the start of the reaction onwards. The heat evolution rate in very early stages of the hydration, measured at varying NaOH concentrations, and SEM, indicate that at NaOH concentrations larger then 0.1 M the reaction

Hydrophobic hydration and anomalous excess partial molar volume of tert-butyl alcohol-water mixture studied by quasielastic neutron scattering

International Nuclear Information System (INIS)

Nakada, Masaru; Maruyama, Kenji; Misawa, Masakatsu; Yamamuro, Osamu

2007-01-01

Quasielastic neutron scattering has been used to investigate the hydration of alcohol clusters in tert-butyl alcohol-water mixture. The measurements were made in a range of alcohol concentration, x TBA , from 0.0 to 0.17 in mole fraction at 25degC. Fraction, α, of water molecules hydrated to fractal-surface of alcohol clusters in tert-butyl alcohol-water mixture was obtained as a function of alcohol concentration. Average hydration number N WS of tert-butyl alcohol molecule was derived from the value of α as a function of alcohol concentration. The value of N WS for an isolated alcohol molecule in water was 19-21. The anomalous excess partial molar volume of tert-butyl alcohol-water mixture was interpreted successfully by applying the same model with the same values of volume parameter as used for 1-propanol-water mixture, δ 1 (=-0.36 cm 3 ·mol -1 ) and δ 2 (=0.60 cm 3 ·mol -1 ). (author)

Solubility data for cement hydrate phases (25oC)

International Nuclear Information System (INIS)

Atkins, M.; Glasser, F.P.; Kindness, A.; Macphee, D.E.

1991-05-01

Solubility measurements were performed on most of the more thermodynamically-stable cement hydrate phases, at 25 o C. The results for each hydrate phase are summarised in the form of datasheets. Solubility properties are discussed, and where possible a K sp value is calculated. The data are compared with the data in the literature. (author)

Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

Energy Technology Data Exchange (ETDEWEB)

Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin, E-mail: gaoyq@pku.edu.cn [Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering and Biodynamic Optical Imaging Center, Peking University, Beijing 100871 (China)

2015-12-14

In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics.

Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

International Nuclear Information System (INIS)

Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin

2015-01-01

In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics

In silico studies of the properties of water hydrating a small protein

International Nuclear Information System (INIS)

Sinha, Sudipta Kumar; Chakraborty, Kausik; Bandyopadhyay, Sanjoy; Jana, Madhurima

2014-01-01

Atomistic molecular dynamics simulation of an aqueous solution of the small protein HP-36 has been carried out with explicit solvent at room temperature. Efforts have been made to explore the influence of the protein on the relative packing and ordering of water molecules around its secondary structures, namely, three α-helices. The calculations reveal that the inhomogeneous water ordering and density distributions around the helices are correlated with their relative hydrophobicity. Importantly, we have identified the existence of a narrow relatively dehydrated region containing randomly organized “quasi-free” water molecules beyond the first layer of “bound” waters at the protein surface. These water molecules with relatively weaker binding energies form the transition state separating the “bound” and “free” water molecules at the interface. Further, increased contribution of solid-like caging motions of water molecules around the protein is found to be responsible for reduced fluidity of the hydration layer. Interestingly, we notice that the hydration layer of helix-3 is more fluidic with relatively higher entropy as compared to the hydration layers of the other two helical segments. Such characteristics of helix-3 hydration layer correlate well with the activity of HP-36, as helix-3 contains the active site of the protein

In silico studies of the properties of water hydrating a small protein

Energy Technology Data Exchange (ETDEWEB)

Sinha, Sudipta Kumar; Chakraborty, Kausik; Bandyopadhyay, Sanjoy, E-mail: sanjoy@chem.iitkgp.ernet.in [Molecular Modeling Laboratory, Department of Chemistry, Indian Institute of Technology, Kharagpur - 721302 (India); Jana, Madhurima [Molecular Simulation Laboratory, Department of Chemistry, National Institute of Technology, Rourkela - 769008 (India)

2014-12-14

Atomistic molecular dynamics simulation of an aqueous solution of the small protein HP-36 has been carried out with explicit solvent at room temperature. Efforts have been made to explore the influence of the protein on the relative packing and ordering of water molecules around its secondary structures, namely, three α-helices. The calculations reveal that the inhomogeneous water ordering and density distributions around the helices are correlated with their relative hydrophobicity. Importantly, we have identified the existence of a narrow relatively dehydrated region containing randomly organized “quasi-free” water molecules beyond the first layer of “bound” waters at the protein surface. These water molecules with relatively weaker binding energies form the transition state separating the “bound” and “free” water molecules at the interface. Further, increased contribution of solid-like caging motions of water molecules around the protein is found to be responsible for reduced fluidity of the hydration layer. Interestingly, we notice that the hydration layer of helix-3 is more fluidic with relatively higher entropy as compared to the hydration layers of the other two helical segments. Such characteristics of helix-3 hydration layer correlate well with the activity of HP-36, as helix-3 contains the active site of the protein.

Remote quantification of phycocyanin in potable water sources through an adaptive model

Science.gov (United States)

Song, Kaishan; Li, Lin; Tedesco, Lenore P.; Li, Shuai; Hall, Bob E.; Du, Jia

2014-09-01

Cyanobacterial blooms in water supply sources in both central Indiana USA (CIN) and South Australia (SA) are a cause of great concerns for toxin production and water quality deterioration. Remote sensing provides an effective approach for quick assessment of cyanobacteria through quantification of phycocyanin (PC) concentration. In total, 363 samples spanning a large variation of optically active constituents (OACs) in CIN and SA waters were collected during 24 field surveys. Concurrently, remote sensing reflectance spectra (Rrs) were measured. A partial least squares-artificial neural network (PLS-ANN) model, artificial neural network (ANN) and three-band model (TBM) were developed or tuned by relating the Rrs with PC concentration. Our results indicate that the PLS-ANN model outperformed the ANN and TBM with both the original spectra and simulated ESA/Sentinel-3/Ocean and Land Color Instrument (OLCI) and EO-1/Hyperion spectra. The PLS-ANN model resulted in a high coefficient of determination (R2) for CIN dataset (R2 = 0.92, R: 0.3-220.7 μg/L) and SA (R2 = 0.98, R: 0.2-13.2 μg/L). In comparison, the TBM model yielded an R2 = 0.77 and 0.94 for the CIN and SA datasets, respectively; while the ANN obtained an intermediate modeling accuracy (CIN: R2 = 0.86; SA: R2 = 0.95). Applying the simulated OLCI and Hyperion aggregated datasets, the PLS-ANN model still achieved good performance (OLCI: R2 = 0.84; Hyperion: R2 = 0.90); the TBM also presented acceptable performance for PC estimations (OLCI: R2 = 0.65, Hyperion: R2 = 0.70). Based on the results, the PLS-ANN is an effective modeling approach for the quantification of PC in productive water supplies based on its effectiveness in solving the non-linearity of PC with other OACs. Furthermore, our investigation indicates that the ratio of inorganic suspended matter (ISM) to PC concentration has close relationship to modeling relative errors (CIN: R2 = 0.81; SA: R2 = 0.92), indicating that ISM concentration exert

De novo quence analysis and intact mass measurements for characterization of phycocyanin subunit isoforms from the blue-green alga Aphanizomenon flos-aquae

DEFF Research Database (Denmark)

Rinalducci, Sara; Roepstorff, Peter; Zolla, Lello

2009-01-01

isothiocyanate (SPITC) and MALDI-TOF/TOF analyses, facilitated the acquisition of sequence information for AFA phycocyanin subunits. In fact, SPITC-derivatized peptides underwent facile fragmentation, predominantly resulting in y-series ions in the MS/MS spectra and often exhibiting uninterrupted sequences of 20...... of phycocyanin subunits was also revealed; subsequently Intact Mass Measurements (IMMs) by both MALDI- and ESI-MS supported the detection of these protein isoforms. Finally, we discuss the evolutionary importance of phycocyanin isoforms in cyanobacteria, suggesting the possible use of the phycocyanin operon...

Theoretical description of biomolecular hydration - Application to A-DNA

International Nuclear Information System (INIS)

Garcia, A.E.; Hummer, G.; Soumpasis, D.M.

1994-01-01

The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG) 5 ] 2 and [d(C 5 G 5 )] 2 . We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers

Influence of pozzolana on C4AF hydratio n and the effects of chloride and sulfate io ns on the hydrates formed

Directory of Open Access Journals (Sweden)

RIMVYDAS KAMINSKAS

2011-09-01

Full Text Available This study investigated the influence of natural pozzolana additive on the hydration of C4AF (aluminoferrite and the effects of chloride and sulfate ions on the hydrates formed. In the samples, 25% (by weight of the C4AF was replaced with pozzolana. The mixture was then hardened for 28 days in water, soaked in a saturated NaCl solution for 3 months, and then soaked in a 5% Na2SO4 solution for 3 months at 20°C. It is estimated that under normal conditions, pozzolana additive accelerates the formation of CO32-–AFm (monocarboaluminate and gibbsite, however, impede the formation of cubic aluminum hydrates. Also, part of the amorphous SiO2 penetrates into the structure of hydrates of C4AF and initiates the formation of hydrated alumino-silicate (gismondine. Monocarboaluminate affected by NaCl becomes unstable and takes part in reactions producing Ca2Al(OH6Cl·2H2O (hydrocalumite-M. After samples were transferred from a saturated NaCl solution to a 5% Na2SO4 solution, hydrocalumite-M was the source of aluminates for the formation of ettringite. In samples with pozzolana additive, the hydrated alumino-silicate and gibbsite compounds that were formed remained stable in an environment containing chloride and sulfate ions and retarded the corrosion reaction of C4AF hydrates.

Statistical evaluation of nutritional components impacting phycocyanin production in Synechocystis SP

Directory of Open Access Journals (Sweden)

Devendra V. Deshmukh

2012-03-01

Full Text Available Alkaliphilic cyanobacterial cultures were isolated from Lonar lake (MS, India. Among the set of cultures, Synechocystis sp, was studied for phycocyanin production. A maximum yield was obtained in BG-11 medium at optimized conditions (pH 10 and 16 h light. In order to increase the phycocyanin yield media optimization based on the eight media components a Plackett-Burman design of the 12 experimental trials was used. As per the analysis CaCl2.2H2O and Na2CO3 have been found to be the most influencing media components at 95% significance. Further the optimum concentrations of these components were estimated following a Box Wilson Central Composite Design (CCD with four star points and five replicates at the center points for each of two factors was adopted for optimization of these two media components. The results indicated that there was an interlinked influence of CaCl2.2H2O and Na2CO3 on 98% significance. The maximum yield of phycocyanin (12% of dry wt could be obtained at 0.058 g/l and 0.115 g/l of CaCl2.2H2O and Na2CO3, respectively.

Hydration measured by doubly labeled water in ALS and its effects on survival.

Science.gov (United States)

Scagnelli, Connor N; Howard, Diantha B; Bromberg, Mark B; Kasarskis, Edward J; Matthews, Dwight E; Mitsumoto, Hiroshi M; Simmons, Zachary; Tandan, Rup

2018-05-01

We present a study of hydration in ALS patients and its effects on survival. This was a multicenter study over 48 weeks in 80 ALS patients who underwent 250 individual measurements using doubly labeled water (DLW). Total body water (TBW) and water turnover (a surrogate for water intake) were 3.4% and 8.6% lower, respectively, in patients compared to age- and gender-matched healthy controls, and both significantly decreased over study duration. In 20% of patients, water turnover measured over 10 d was 2 standard deviations below the mean value in healthy controls. In a separate clinic cohort of 208 patients, water intake estimated from a de novo equation created from common clinical endpoints was a prognostic indicator of survival. Regardless of nutritional state assessed by BMI, survival was two-fold longer in the group above the median for estimated water intake, suggesting that hydration may be a more important predictor of survival than malnutrition. Risk factors for poor hydration were identified. Water intake equations recommended by US Centers for Medicare and Medicaid Services in healthy elderly were inaccurate for use in ALS patients. We developed equations to estimate TBW and water intake in ALS patients for use in clinics to accurately estimate hydration and improve clinical care.

Dietary water affects human skin hydration and biomechanics

Directory of Open Access Journals (Sweden)

Palma L

2015-08-01

Full Text Available Lídia Palma,1 Liliana Tavares Marques,1 Julia Bujan,2,3 Luís Monteiro Rodrigues1,4 1CBIOS – Research Center for Health Science and Technologies, Universidade Lusófona, Campo Grande, Lisboa, Portugal; 2Department of Medicine and Medical Specialities, Universidad de Alcalá de Henares, Madrid, Spain; 3CIBER-BBN, Madrid, España, Spain; 4Department of Pharmacological Sciences, School of Pharmacy, Universidade de Lisboa, Lisboa, Portugal Abstract: It is generally assumed that dietary water might be beneficial for the health, especially in dermatological (age preventing terms. The present study was designed to quantify the impact of dietary water on major indicators of skin physiology. A total of 49 healthy females (mean 24.5±4.3 years were selected and characterized in terms of their dietary daily habits, especially focused in water consumption, by a Food Frequency Questionnaire. This allowed two groups to be set – Group 1 consuming less than 3,200 mL/day (n=38, and Group 2 consuming more than 3,200 mL/day (n=11. Approximately 2 L of water were added to the daily diet of Group 2 individuals for 1 month to quantify the impact of this surplus in their skin physiology. Measurements involving epidermal superficial and deep hydration, transepidermal water loss, and several biomechanical descriptors were taken at day 0 (T0, 15 (T1, and 30 (T2 in several anatomical sites (face, upper limb, and leg. This stress test (2 L/day for 30 days significantly modified superficial and deep skin hydration, especially in Group 1. The same impact was registered with the most relevant biomechanical descriptors. Thus, in this study, it is clear that higher water inputs in regular diet might positively impact normal skin physiology, in particular in those individuals with lower daily water consumptions. Keywords: dietary water, water consume, skin hydration, TEWL, skin biomechanics

Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

Science.gov (United States)

Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

2009-04-23

In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

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

Science.gov (United States)

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

2017-12-01

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

Theoretical description of biomolecular hydration - Application to A-DNA

Energy Technology Data Exchange (ETDEWEB)

Garcia, A.E.; Hummer, G. [Los Alamos National Laboratory, NM (United States); Soumpasis, D.M. [Max Planck Inst. for Biophysical Chemistry, Goettingen (Germany)

1994-12-31

The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG){sub 5}]{sub 2} and [d(C{sub 5}G{sub 5})]{sub 2}. We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers.

Tritium-exchange method for obsidian hydration shell measurement

Energy Technology Data Exchange (ETDEWEB)

Lowe, J P; Wilson, A T; Lowe, D J; Hodder, A P.W. [Waikato Univ., Hamilton (New Zealand)

1984-12-01

A new radiochemical method for measuring the amount of water in the hydrated layer on the surface of obsidians exchanges tritiated water with the water in the layer (20 ..mu..l of 5 Ci ml/sup -1/ at 90/sup 0/C for 10 days) and then back-exchanges it (in 150 ml of water at 35/sup 0/C for approx. 200 hr.). The activity of the back-exchange water (F) is monitored by liquid scintillation counting of aliquots extracted at known time intervals (t). The activity so measured is then related to the thickness of the hydration rim. A sheet diffusion model shows that the thickness of the hydration shell (l) is inversely proportional to the slope of the F vs. tsup(1/2) plot. Comparison of l-values so obtained between obsidians, whose age (x) is inferred from archaeological occupation layers containing radiocarbon-dated wood and charcoal, suggests a relationship between l and x. Implications for New Zealand prehistory are briefly considered. The technique, which is non-destructive, appears particularly applicable to young glasses where the development of hydrated layers may be inadequate for accurate optical measurement.

Shifting Focus: From Hydration for Performance to Hydration for Health.

Science.gov (United States)

Perrier, Erica T

2017-01-01

Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

Higher production of C-phycocyanin by nitrogen-free (diazotrophic) cultivation of Nostoc sp. NK and simplified extraction by dark-cold shock.

Science.gov (United States)

Lee, Na Kyeong; Oh, Hee-Mock; Kim, Hee-Sik; Ahn, Chi-Yong

2017-03-01

Nostoc sp. NK (KCTC 12772BP) was isolated and cultivated in a BG11 medium and a nitrate-free BG11 medium (BG11 0 ). To enhance C-phycocyanin (C-PC) content in the cells, different fluorescent lamps (white, plant, and red) were used as light sources for complementary chromatic adaptation (CCA). The maximum biomass productivity was 0.42g/L/d and 0.32g/L/d under BG11 and BG11 0 conditions, respectively. The maximum C-PC contents were 8.4% (w/w) under white lamps, 13.6% (w/w) under plant lamps, and 18% (w/w) under BG11 0 and the red light condition. The maximum C-PC productivity was 57.4mg/L/d in BG11 0 under the red lamp condition. These results indicate that a higher C-PC content could be obtained under a diazotrophic condition and a CCA reaction. The C-PC could be released naturally from cells without any extraction processes, when Nostoc sp. NK was cultivated in the BG11 0 medium with CO 2 aeration and put in dark conditions at 5°C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Differential Scanning Calorimetric Study and Potential Model of the Binding of the Primary Water of Hydration to K-Hyaluronate

Science.gov (United States)

Whitson, K. B.; Marlowe, R. L.; Lukan, A. M.; Lee, S. A.; Anthony, L.; Rupprecht, A.

1997-11-01

DSC was performed on samples of K-hyaluronate (KHA) through a temperature range of 25-180^oC. A transition peak was observed which is due to the desorption of the primary water of hydration. The maximum position of the peak was observed to change with different scan rates. The average energy of activation, E_A, and enthalpy for desorption of the primary water of hydration was determined to be 0.62 and 0.17 eV per water molecule, respectively. Analysis of Mossbauer data(G. Albanese et al., Hyperfine Int.,) 95, 97 (1995) allowed us to determine the effective force constant, k_eff, of the water bound to KHA to be approximately 19.4 eV/nm^2. The parameters E_A, ΔH,and k_eff allow us to construct a potential model for the primary water of hydration of KHA. Comparison of these parameters with the same parameters for HA and DNA with different counterions reveal that the energy of activation is similar, as well as the enthalpy change.

Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

International Nuclear Information System (INIS)

Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

2011-01-01

The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C 3 S, β-C 2 S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of β-C 2 S and the 30-70 (T1-C 3 S and β-C 2 S mixture) are higher than those from hydration of T1-C 3 S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C 2 S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 2 9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

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

Science.gov (United States)

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

2008-08-28

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

A Scanning Transmission X-ray Microscopy Study of Cubic and Orthorhombic C3A and Their Hydration Products in the Presence of Gypsum

Directory of Open Access Journals (Sweden)

Vanessa Rheinheimer

2016-08-01

Full Text Available This paper shows the microstructural differences and phase characterization of pure phases and hydrated products of the cubic and orthorhombic (Na-doped polymorphs of tricalcium aluminate (C3A, which are commonly found in traditional Portland cements. Pure, anhydrous samples were characterized using scanning transmission X-ray microscopy (STXM, X-ray photoelectron spectroscopy (XPS and X-ray diffraction (XRD and demonstrated differences in the chemical and mineralogical composition as well as the morphology on a micro/nano-scale. C3A/gypsum blends with mass ratios of 0.2 and 1.9 were hydrated using a water/C3A ratio of 1.2, and the products obtained after three days were assessed using STXM. The hydration process and subsequent formation of calcium sulfate in the C3A/gypsum systems were identified through the changes in the LIII edge fine structure for Calcium. The results also show greater Ca LII binding energies between hydrated samples with different gypsum contents. Conversely, the hydrated samples from the cubic and orthorhombic C3A at the same amount of gypsum exhibited strong morphological differences but similar chemical environments.

Dietary water affects human skin hydration and biomechanics.

Science.gov (United States)

Palma, Lídia; Marques, Liliana Tavares; Bujan, Julia; Rodrigues, Luís Monteiro

2015-01-01

It is generally assumed that dietary water might be beneficial for the health, especially in dermatological (age preventing) terms. The present study was designed to quantify the impact of dietary water on major indicators of skin physiology. A total of 49 healthy females (mean 24.5±4.3 years) were selected and characterized in terms of their dietary daily habits, especially focused in water consumption, by a Food Frequency Questionnaire. This allowed two groups to be set - Group 1 consuming less than 3,200 mL/day (n=38), and Group 2 consuming more than 3,200 mL/day (n=11). Approximately 2 L of water were added to the daily diet of Group 2 individuals for 1 month to quantify the impact of this surplus in their skin physiology. Measurements involving epidermal superficial and deep hydration, transepidermal water loss, and several biomechanical descriptors were taken at day 0 (T0), 15 (T1), and 30 (T2) in several anatomical sites (face, upper limb, and leg). This stress test (2 L/day for 30 days) significantly modified superficial and deep skin hydration, especially in Group 1. The same impact was registered with the most relevant biomechanical descriptors. Thus, in this study, it is clear that higher water inputs in regular diet might positively impact normal skin physiology, in particular in those individuals with lower daily water consumptions.

Dynamic lifetimes of cagelike water clusters immersed in liquid water and their implications for hydrate nucleation studies

Energy Technology Data Exchange (ETDEWEB)

Guo, G.J.; Zhang, Y.G.; Li, M.; Wu, C.H. [Chinese Academy of Sciences, Inst. of Geology and Geophysics, Beijing (China). Key Laboratory of the Study of Earth' s Deep Interior

2008-07-01

In hydrate research fields, the hydrate nucleation mechanism still remains as an unsolved question. The static lifetimes of cagelike water clusters (CLWC) immersed in bulk liquid water have recently been measured by performing molecular dynamics simulations in the methane-water system, during which the member-water molecules of CLWCs are not allowed to exchange with their surrounding water molecules. This paper presented a study that measured the dynamic lifetimes of CLWCs permitting such water exchanges. The study involved re-analysis of previous simulation data that were used to study the effect of methane adsorption on the static lifetimes of a dodecahedral water cluster (DWC). The dynamic lifetimes of the DWC were calculated. The results of lifetime measurements of DWC in different systems were provided. The implications of this study for hydrate nucleation were also discussed. It was found that the dynamic lifetimes of CLWCs were not less than the static lifetimes previously obtained, and their ratio increased with the lifetime values. The results strengthened that CLWCs are metastable structures in liquid water and the occurrence probability of long-lived CLWCs will increase if one uses the dynamic lifetimes instead of the static lifetimes. 13 refs., 1 tab., 3 figs.

Thermal Stability and Proton Conductivity of Rare Earth Orthophosphate Hydrates

DEFF Research Database (Denmark)

Anfimova, Tatiana; Li, Qingfeng; Jensen, Jens Oluf

2014-01-01

as the rhabdophane structure is preserved. The bound hydrate water is accommodated in the rhabdophane structure and is stable at temperatures of up to 650 oC. The thermal stability of the hydrate water and the phosphate structure are of significance for the proton conductivity. The LaPO4·0.6H2O and NdPO4•0.5H2O......Hydrated orthophosphate powders of three rare earth metals, lanthanum, neodymium and gadolinium, were prepared and studied as potential proton conducting materials for intermediate temperature electrochemical applications. The phosphates undergo a transformation from the rhabdophane structure...... to the monazite structure upon dehydration. The thermal stability of the hydrate is studied and found to contain water of two types, physically adsorbed and structurally bound hydrate water. The adsorbed water is correlated to the specific surface area and can be reversibly recovered when dehydrated as long...

Properties of cyclodextrins. II. Preparation of a stable β-cyclodextrin hydrate and determination of its water content and enthalpy of solution in water from 15 to 30.deg

NARCIS (Netherlands)

Wiedenhof, N.; Lammers, J.N.J.J.

1968-01-01

The solubility of ß-cyclodextrin (ß-CD) in water has been measured by a refractive-index method at 15–30°. Evidence was obtained that the same, solid ß-CD hydrate phase is present in this temperature range. The formula of the hydrate was shown to be C42H70O35(12.0 ± 0.5)H20. A method for preparation

Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

International Nuclear Information System (INIS)

Sedaira, H.; Idriss, K.A.; Hashem, E.Y.

1996-01-01

The solvation number and hydration constant of Th 4+ in ethanol-water medium were determined at 25 degrees C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H 2 O to form ThS 3 (H 2 O) 3 4+ . Formation of thorium monochelate with lawsone (2-hydroxy-1.4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agent s K a and the formation contant of the monochelated metal ion s K f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochlate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant, s K f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by log x K f * =vpK a + log s K h - log [LH] - vpH + 3 log v where vpK a is the dissociation constant of the chelating agent LH in the solvent system of v volume fraction of water and s K h is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constants s K h , s K f * and s K z * are found to be 7.8 ±0.02, 11.38±0.04 and -0.753, respectively

Clathrate Hydrates for Thermal Energy Storage in Buildings: Overview of Proper Hydrate-Forming Compounds

Directory of Open Access Journals (Sweden)

Beatrice Castellani

2014-09-01

Full Text Available Increasing energy costs are at the origin of the great progress in the field of phase change materials (PCMs. The present work aims at studying the application of clathrate hydrates as PCMs in buildings. Clathrate hydrates are crystalline structures in which guest molecules are enclosed in the crystal lattice of water molecules. Clathrate hydrates can form also at ambient pressure and present a high latent heat, and for this reason, they are good candidates for being used as PCMs. The parameter that makes a PCM suitable to be used in buildings is, first of all, a melting temperature at about 25 °C. The paper provides an overview of groups of clathrate hydrates, whose physical and chemical characteristics could meet the requirements needed for their application in buildings. Simulations with a dynamic building simulation tool are carried out to evaluate the performance of clathrate hydrates in enhancing thermal comfort through the moderation of summer temperature swings and, therefore, in reducing energy consumption. Simulations suggest that clathrate hydrates have a potential in terms of improvement of indoor thermal comfort and a reduction of energy consumption for cooling. Cooling effects of 0.5 °C and reduced overheating hours of up to 1.1% are predicted.

High protein flexibility and reduced hydration water dynamics are key pressure adaptive strategies in prokaryotes

KAUST Repository

Martinez, N.

2016-09-06

Water and protein dynamics on a nanometer scale were measured by quasi-elastic neutron scattering in the piezophile archaeon Thermococcus barophilus and the closely related pressure-sensitive Thermococcus kodakarensis, at 0.1 and 40 MPa. We show that cells of the pressure sensitive organism exhibit higher intrinsic stability. Both the hydration water dynamics and the fast protein and lipid dynamics are reduced under pressure. In contrast, the proteome of T. barophilus is more pressure sensitive than that of T. kodakarensis. The diffusion coefficient of hydration water is reduced, while the fast protein and lipid dynamics are slightly enhanced with increasing pressure. These findings show that the coupling between hydration water and cellular constituents might not be simply a master-slave relationship. We propose that the high flexibility of the T. barophilus proteome associated with reduced hydration water may be the keys to the molecular adaptation of the cells to high hydrostatic pressure.

High protein flexibility and reduced hydration water dynamics are key pressure adaptive strategies in prokaryotes

KAUST Repository

Martinez, N.; Michoud, Gregoire; Cario, A.; Ollivier, J.; Franzetti, B.; Jebbar, M.; Oger, P.; Peters, J.

2016-01-01

Water and protein dynamics on a nanometer scale were measured by quasi-elastic neutron scattering in the piezophile archaeon Thermococcus barophilus and the closely related pressure-sensitive Thermococcus kodakarensis, at 0.1 and 40 MPa. We show that cells of the pressure sensitive organism exhibit higher intrinsic stability. Both the hydration water dynamics and the fast protein and lipid dynamics are reduced under pressure. In contrast, the proteome of T. barophilus is more pressure sensitive than that of T. kodakarensis. The diffusion coefficient of hydration water is reduced, while the fast protein and lipid dynamics are slightly enhanced with increasing pressure. These findings show that the coupling between hydration water and cellular constituents might not be simply a master-slave relationship. We propose that the high flexibility of the T. barophilus proteome associated with reduced hydration water may be the keys to the molecular adaptation of the cells to high hydrostatic pressure.

Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

Directory of Open Access Journals (Sweden)

Carles Calero

2016-04-01

Full Text Available Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs. We calculate the rotational and translational slowdown of the dynamics of water confined in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii to the higher probability of water–lipid HBs as the hydration decreases. Our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.

Hydration rate of obsidian.

Science.gov (United States)

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.

Heat of hydration measurements on cemented radioactive wastes. Part 1: cement-water pastes

International Nuclear Information System (INIS)

Lee, D.J.

1983-12-01

This report describes the hydration of cement pastes in terms of chemical and kinetic models. A calorimetric technique was used to measure the heat of hydration to develop these models. The effects of temperature, water/cement ratio and cement replacements, ground granulated blast furnace slag (BFS) and pulverised fuel ash (PFA) on the hydration of ordinary Portland cement (OPC) is reported. The incorporation of BFS or PFA has a marked effect on the hydration reaction. The effect of temperature is also important but changing the water/cement ratio has little effect. Results from cement pastes containing only water and cement yield total heats of reaction of 400, 200 and 100 kJ/kg for OPC, BFS and PFA respectively. Using the results from the models which have been developed, the effect of major salts present in radioactive waste streams can be assessed. Values of the total heat of reaction, the time to complete 50 percent reaction, and the energy of activation, can be compared for different waste systems. (U.K.)

Topological modeling of methane hydrate crystallization from low to high water cut emulsion systems

OpenAIRE

Melchuna , Aline; Cameirão , Ana; Herri , Jean-Michel; Glénat , Philippe

2016-01-01

International audience; Hydrate formation and remediation in oil flowlines facilities represent a major concern for oil industry in respect of capital and operational costs. It is necessary to have a better understanding on the hydrate formation process to be more efficient in hydrate prevention, especially in respect to additive dosage. This work is a contribution to enhance the knowledge of hydrate formation at high water cuts, by introducing new techniques of analysis in the Archimede flow...

Types and characteristics of drinking water for hydration in the elderly.

Science.gov (United States)

Casado, Ángela; Ramos, Primitivo; Rodríguez, Jaime; Moreno, Norberto; Gil, Pedro

2015-01-01

The role of hydration in the maintenance of health is increasingly recognized. Hydration requirements vary for each person, depending on physical activity, environmental conditions, dietary patterns, alcohol intake, health problems, and age. Elderly individuals have higher risk of developing dehydration than adults. Diminution of liquid intake and increase in liquid losses are both involved in causing dehydration in the elderly. The water used for drinking is provided through regular public water supply and the official sanitary controls ensure their quality and hygiene, granting a range of variation for most of its physical and chemical characteristics, being sometimes these differences, though apparently small, responsible for some disorders in sensitive individuals. Hence, the advantages of using bottled water, either natural mineral water or spring water, are required by law to specify their composition, their major components, and other specific parameters. It is essential to take this into account to understand the diversity of indications and favorable effects on health that certain waters can offer.

Hydration of alcohol clusters in 1-propanol-water mixture studied by quasielastic neutron scattering and an interpretation of anomalous excess partial molar volume.

Science.gov (United States)

Misawa, M; Inamura, Y; Hosaka, D; Yamamuro, O

2006-08-21

Quasielastic neutron scattering measurements have been made for 1-propanol-water mixtures in a range of alcohol concentration from 0.0 to 0.167 in mole fraction at 25 degrees C. Fraction alpha of water molecules hydrated to fractal surface of alcohol clusters in 1-propanol-water mixture was obtained as a function of alcohol concentration. Average hydration number N(ws) of 1-propanol molecule is derived from the value of alpha as a function of alcohol concentration. By extrapolating N(ws) to infinite dilution, we obtain values of 12-13 as hydration number of isolated 1-propanol molecule. A simple interpretation of structural origin of anomalous excess partial molar volume of water is proposed and as a result a simple equation for the excess partial molar volume is deduced in terms of alpha. Calculated values of the excess partial molar volumes of water and 1-propanol and the excess molar volume of the mixture are in good agreement with experimental values.

Effect of hydration of sugar groups on adsorption of Quillaja bark saponin at air/water and Si/water interfaces.

Science.gov (United States)

Wojciechowski, Kamil; Orczyk, Marta; Marcinkowski, Kuba; Kobiela, Tomasz; Trapp, Marcus; Gutberlet, Thomas; Geue, Thomas

2014-05-01

Adsorption of a natural glycoside surfactant Quillaja bark saponin ("QBS", Sigma Aldrich 84510) was studied at the air/water and Si/water interfaces using a combination of surface pressure (SP), surface dilatational rheology, neutron reflectivity (NR), Infra-Red Attenuated Total Reflection Spectroscopy (IR ATR) and Quartz Crystal Microbalance (QCM). The adsorbed layers formed at the air/water interface are predominantly elastic, with the dilatational surface storage modulus reaching the maximum value of E'=184 mN/m. The NR results point to a strong hydration of the adsorbed layers (about 65% hydration, corresponding to about 60 molecules of water per one QBS molecule), most likely related to the presence of multiple sugar groups constituting the glycone part of the QBS molecules. With a layer thickness of 19 Å, the adsorbed amount obtained from NR seems largely underestimated in comparison to the value obtained from the surface tension isotherm. While this high extent of hydration does not prevent formation of dense and highly elastic layers at the air-water surface, QBS adsorption at the Si/water interface is much weaker. The adsorption isotherm of QBS on Si obtained from the QCM study reflects much lower affinity of highly hydrated and negatively charged saponin molecules to the Si/water interface. We postulate that at the air/water interface, QBS adsorbs through the triterpene aglycone moiety. In contrast, weak hydrogen bonding between the glycone part and the surface silanol groups of Si is responsible for QBS adsorption on more polar Si/water interface. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-01

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

Skin hydration: interplay between molecular dynamics, structure and water uptake in the stratum corneum.

Science.gov (United States)

Mojumdar, Enamul Haque; Pham, Quoc Dat; Topgaard, Daniel; Sparr, Emma

2017-11-16

Hydration is a key aspect of the skin that influences its physical and mechanical properties. Here, we investigate the interplay between molecular and macroscopic properties of the outer skin layer - the stratum corneum (SC) and how this varies with hydration. It is shown that hydration leads to changes in the molecular arrangement of the peptides in the keratin filaments as well as dynamics of C-H bond reorientation of amino acids in the protruding terminals of keratin protein within the SC. The changes in molecular structure and dynamics occur at a threshold hydration corresponding to ca. 85% relative humidity (RH). The abrupt changes in SC molecular properties coincide with changes in SC macroscopic swelling properties as well as mechanical properties in the SC. The flexible terminals at the solid keratin filaments can be compared to flexible polymer brushes in colloidal systems, creating long-range repulsion and extensive swelling in water. We further show that the addition of urea to the SC at reduced RH leads to similar molecular and macroscopic responses as the increase in RH for SC without urea. The findings provide new molecular insights to deepen the understanding of how intermediate filament organization responds to changes in the surrounding environment.

Hydrogen speciation in hydrated layers on nuclear waste glass

International Nuclear Information System (INIS)

Aines, R.D.; Weed, H.C.; Bates, J.K.

1987-01-01

The hydration of an outer layer on nuclear waste glasses is 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 and 165, and PNL 76-68), which were leached at 90 0 C (all glasses) or hydrated in a vapor-saturated atmosphere at 202 0 C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water 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. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 μm layer on SRL-131 glass formed by leaching at 90 0 C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H + interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups

Computational phase diagrams of noble gas hydrates under pressure

Energy Technology Data Exchange (ETDEWEB)

Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk [Centre for Science at Extreme Conditions and SUPA, School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3FD (United Kingdom)

2015-10-21

We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

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Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

2017-10-13

Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

[Skin hydration and hydrating products].

Science.gov (United States)

Duplan, H; Nocera, T

2018-05-01

One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

Influence of Hydration on Proton Transfer in the Guanine-Cytosine Radical Cation (G•+-C) Base Pair: A Density Functional Theory Study

Science.gov (United States)

Kumar, Anil; Sevilla, Michael D.

2009-01-01

On one-electron oxidation all molecules including DNA bases become more acidic in nature. For the GC base pair experiments suggest that a facile proton transfer takes place in the G•+-C base pair from N1 of G•+ to N3 of cytosine. This intra-base pair proton transfer reaction has been extensively considered using theoretical methods for the gas phase and it is predicted that the proton transfer is slightly unfavorable in disagreement with experiment. In the present study, we consider the effect of the first hydration layer on the proton transfer reaction in G•+-C by the use of density functional theory (DFT), B3LYP/6-31+G** calculations of the G•+-C base pair in the presence of 6 and 11 water molecules. Under the influence of hydration of 11 waters, a facile proton transfer from N1 of G•+ to N3 of C is predicted. The zero point energy (ZPE) corrected forward and backward energy barriers, for the proton transfer from N1 of G•+ to N3 of C, was found to be 1.4 and 2.6 kcal/mol, respectively. The proton transferred G•-(H+)C + 11H2O was found to be 1.2 kcal/mol more stable than G•+-C + 11H2O in agreement with experiment. The present calculation demonstrates that the inclusion of the first hydration shell around G•+-C base pair has an important effect on the internal proton transfer energetics. PMID:19485319

Barley seed radiosensitivity following post-hydration in oxygen-, nitrogen- and nitrous oxide-saturated water, 1

International Nuclear Information System (INIS)

Singh, S.P.; Kesavan, P.C.

1990-01-01

Dry (∼3.5 and 4.0 per cent moisture content) barley seeds were exposed to 350 Gy of 60 Co-γ-rays in vacuo and post-hydrated at 4degC for 8 h in O 2 -, N 2 -, or N 2 O-saturated water. The effect of caffeine and t-butyl alcohol (t-BuOH) dissolved in the post-hydration medium on the magnitude of damage developing under these three different gaseous circumstances was studied. The post-irradiation damage and its modification by caffeine and t-BuOH was assessed in terms of 8-day-old seedling injury, peroxidase activity and total peroxides in the 8-day-old seedlings. Post-irradiation O 2 -saturated hydration caused maximal 8-day-old seedling injury, and increased peroxidase activity with concomitant reduction in total peroxides. Both caffeine and t-BuOH afforded significant radioprotection against post-irradiation O 2 -dependent damage. Post-irradiation N 2 O-saturated hydration was even more significantly radioprotective than the N 2 -saturated post-hydration. Under these circumstances, t-BuOH exerted no effect whatsoever on the N 2 - and N 2 O-mediated post-irradiation damage. Caffeine, on the other hand, significantly potentiated these two components of damage. A brief consideration of the physicochemical events which possibly account for the observed effects is presented. (author)

The Temperature Dependence of the Partition of CH4 and C2H6 in Structure I Hydrates

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Cheng, H.; Lu, W.

2017-12-01

At present, we mainly use hydrocarbon gas and carbon isotope composition to determine the gas source of natural gas hydrate. Judging the type of gas source plays a key role in the evaluation of hydrate reservoirs, but there is still controversy over this approach. Considering the crystal properties of hydrate, the process of aggregation and decomposition of natural gas hydrates may have an important effect on the gas composition. We used CH4 (C1), C2H6 (C2) and their mixture as gas sources to synthesize hydrates from aqueous solution in high-pressure capillary tubes. Gas concentration in hydrates grew at different temperatures was measured with quantitative Raman spectroscopy. The results show that concentrations of gas in pure methane and pure ethane hydrates increase with temperature. The results of the mixture are similar to pure gas below 288.15 K, the concentration of C1 in small cages (SC, 512) slowly increased, but the competitive relationship between methane and ethane in large cages (LC, 51262) become obvious after 288.15 K. From 278.15 K to 294.15 K, the value of C1/C2 decreased from 26.38 to 6.61, gradually closing to the original gas composition of 4. We find that gas hydrates are more likely to gather C1 when they accumulate. The lower the temperature is, the more obvious it will be, and the closer the value of C1/C2 is to the microbial gases.

Coordination variation of hydrated Cu2+/Br1− ions traversing the interfacial water in mesopores

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Q. Wang

2012-06-01

Full Text Available Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ∼35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

Measurements of gas permeability and non-Darcy flow in gas-water-hydrate systems

Energy Technology Data Exchange (ETDEWEB)

Ersland, G.; Husebo, J.; Graue, A.; Kvamme, B. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology; Baldwin, B. [Green Country Petrophysics LLC, Dewey, OK (United States); Stevens, J.; Howard, J. [ConocoPhillips, OK (United States)

2008-07-01

Storage of carbon dioxide (CO{sub 2}) in natural gas hydrate reservoirs may offer stable long-term storage of a greenhouse gas while benefiting from methane production, without requiring heat. By exposing hydrate to a thermodynamically preferred hydrate former, CO{sub 2}, the hydrate may be maintained macroscopically in the solid state and retain the stability of the formation. However, there is concern over the flow capacity in such reservoirs. This depends on several factors, notably thermodynamic destabilization of hydrate in small pores due to capillary effects; the presence of liquid channels separating the hydrate from the mineral surfaces; and, the connectivity of gas or liquid filled pores and channels. This paper described a technique for measuring gas permeability in gas-water-hydrate systems. It reported on several experiments that measured gas permeability during stages of hydrate growth in sandstone core plugs. Interactions between minerals and surrounding molecules were also discussed. The formation of methane hydrate in porous media was monitored and quantified with magnetic resonance imaging (MRI). MRI images of hydrate growth within the porous rock were provided along with measurements of gas permeability and non-Darcy flow effects at various hydrate saturations. Gas permeability was measured at steady state flow of methane through the hydrate-bearing core sample. Significant gas permeability was recorded for porous sandstone even when hydrates occupied up to 60 per cent of the pore space. It was concluded that MRI imaging can be used effectively to map and quantify hydrate saturation in sandstone core plugs. 27 refs., 2 tabs., 10 figs.

Gas hydrate in nature

Science.gov (United States)

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.

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

Science.gov (United States)

Dai, S.; Seol, Y.

2015-12-01

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

The impact of kosmotropes and chaotropes on bulk and hydration shell water dynamics in a model peptide solution

International Nuclear Information System (INIS)

Russo, Daniela

2008-01-01

Kosmotropic (order-making) and chaotropic (order-breaking) co-solvents influence stability and biochemical equilibrium in aqueous solutions of proteins, acting indirectly through the structure and dynamics of the hydration water that surrounds the protein molecules. We have investigated the influence of kosmotropic and chaotropic co-solvents on the hydrogen bonding network dynamics of both bulk water and hydration water. To this end the evolution of bulk water and hydration water dynamics of a prototypical hydrophobic amino acid with polar backbone, N-acetyl-leucine-methylamide (NALMA), has been studied by quasielastic neutron scattering as a function of solvent composition. The results show that bulk water and hydration water dynamics, apart from a dynamical suppression that depends on the NALMA solute, exhibit the same dependence on addition of co-solvent for all of the co-solvents studied (urea, glycerol, MgSO 4 , and dimethyl sulfoxide). The hydrophobic solute and the high concentration water-structuring additive have the same effect on the water hydrogen bonding network. Water remains the preferential hydration of the hydrophobic side chain and backbone. We also find that the reorganization of the bulk water hydrogen bond network, upon addition of kosmotrope and chaotrope additives, is not dynamically perturbed, and that the hydrogen bond lifetime is maintained at 1 ps as in pure bulk water. On the other hand the addition of NALMA to the water/co-solvent binary system causes reorganization of the hydrogen bonds, resulting in an increased hydrogen bond lifetime. Furthermore, the solute's side chain dynamics is not affected by high concentrations of co-solvent. We shall discuss the hydration dynamics results in the context of protein folding and protein-solvent interactions

Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

International Nuclear Information System (INIS)

Matsuoka, Daisuke; Nakasako, Masayoshi

2013-01-01

Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

Late Glacial temperature and precipitation changes in the lowland Neotropics by tandem measurement of δ 18O in biogenic carbonate and gypsum hydration water

Science.gov (United States)

Hodell, David A.; Turchyn, Alexandra V.; Wiseman, Camilla J.; Escobar, Jaime; Curtis, Jason H.; Brenner, Mark; Gilli, Adrian; Mueller, Andreas D.; Anselmetti, Flavio; Ariztegui, Daniel; Brown, Erik T.

2012-01-01

We applied a new method to reconstruct paleotemperature in the tropics during the last deglaciation by measuring oxygen isotopes of co-occurring gypsum hydration water and biogenic carbonate in sediment cores from two lakes on the Yucatan Peninsula. Oxygen and hydrogen isotope values of interstitial and gypsum hydration water indicate that the crystallization water preserves the isotopic signal of the lake water, and has not undergone post-depositional isotopic exchange with sediment pore water. The estimated lake water δ18O is combined with carbonate δ18O to calculate paleotemperature. Three paired measurements of 1200-yr-old gypsum and gastropod aragonite from Lake Chichancanab, Mexico, yielded a mean temperature of 26 °C (range 23-29.5 °C), which is consistent with the mean and range of mean annual temperatures (MAT) in the region today. Paired measurements of ostracods, gastropods, and gypsum hydration water samples were measured in cores from Lake Petén Itzá, Guatemala, spanning the Late Glacial and early Holocene period (18.5-10.4 ka). The lowest recorded temperatures occurred at the start of Heinrich Stadial (HS) 1 at 18.5 ka. Inferred temperatures from benthic ostracods ranged from 16 to 20 °C during HS 1, which is 6-10 °C cooler than MAT in the region today, whereas temperatures derived from shallow-water gastropods were generally warmer (20-25 °C), reflecting epilimnetic temperatures. The derived temperatures support previous findings of greater tropical cooling on land in Central America during the Late Glacial than indicated by nearby marine records. Temperature increased in two steps during the last deglaciation. The first occurred during the Bolling-Allerod (B-A; from 14.7 to 13 ka) when temperature rose to 20-24 °C towards the end of this period. The second step occurred at 10.4 ka near the beginning of the Holocene when ostracod-inferred temperature rose to 26 °C, reflecting modern hypolimnetic temperature set during winter, whereas

Revealing the influence of water-cement ratio on the pore size distribution in hydrated cement paste by using cyclohexane

Science.gov (United States)

Bede, Andrea; Ardelean, Ioan

2017-12-01

Varying the amount of water in a concrete mix will influence its final properties considerably due to the changes in the capillary porosity. That is why a non-destructive technique is necessary for revealing the capillary pore distribution inside hydrated cement based materials and linking the capillary porosity with the macroscopic properties of these materials. In the present work, we demonstrate a simple approach for revealing the differences in capillary pore size distributions introduced by the preparation of cement paste with different water-to-cement ratios. The approach relies on monitoring the nuclear magnetic resonance transverse relaxation distribution of cyclohexane molecules confined inside the cement paste pores. The technique reveals the whole spectrum of pores inside the hydrated cement pastes, allowing a qualitative and quantitative analysis of different pore sizes. The cement pastes with higher water-to-cement ratios show an increase in capillary porosity, while for all the samples the intra-C-S-H and inter-C-S-H pores (also known as gel pores) remain unchanged. The technique can be applied to various porous materials with internal mineral surfaces.

Description of gas hydrates equilibria in sediments using experimental data of soil water potential

Energy Technology Data Exchange (ETDEWEB)

Istomin, V. [NOVATEK, Moscow (Russian Federation); Chuvilin, E. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology; Makhonina, N.; Kvon, V. [VNIIGAZ, Moscow (Russian Federation); Safonov, S. [Schlumberger Moscow Research, Moscow (Russian Federation)

2008-07-01

Analytical relationships have been developed between hydrate dissociation pressure and vapor pressure above the pore water surface. In addition, experiments have been discussed in numerous publications on the effect of narrow interconnected throats between pores on clathrate dissociation conditions in porous media. This paper presented an approach that improved upon the available thermodynamic methods for calculation of hydrate phase equilibria. The approach took into account the properties of pore water in natural sediments including three-phase equilibrium of gas-pore water-gas hydrate in a similar way as for unfrozen water in geocryology science. The purpose of the paper was to apply and adapt geocryology and soil physics method to the thermodynamic calculation of non-clathrated water content in sediments. It answered the question of how to estimate the non-clathrated water content if pore water potential was known. The paper explained the thermodynamics of water phase in porous media including the thermodynamic properties of supercooled water, the thermodynamic properties of pore water and pore ice in sediments, and the phase equilibria of pore water. The paper also discussed the quantitative techniques that were utilized for determination of unfrozen water content in sediments and its dependence on temperature variation. These included contact-saturation, calorimetric, dielectric, nuclear magnetic resonance, and others. The thermodynamic calculations of pore water phase equilibria were also presented. 30 refs., 5 tabs., 8 figs.

Portlandite content and ionic transport properties of hydrated C3S pastes

International Nuclear Information System (INIS)

Henocq, P.; Samson, E.; Marchand, J.

2012-01-01

This paper presents the results of a C 3 S paste characterization study. The objective was to determine the parameters needed to model the process of degradation. The experimental study focused on determining the portlandite content and the ionic diffusion coefficients of C 3 S paste. The molar C/S ratio of C–S–H in hydrated C 3 S pastes was also investigated. The portlandite content was determined with an experimental method based on an electron microprobe analysis. This method leads to a portlandite mass content of 24.4 ± 2.3%. The diffusion coefficient of each ionic species was determined by inverse analysis of diffusion test data performed on hydrated C 3 S samples using a multiionic transport model.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

Science.gov (United States)

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) water water in the hydration shell of anions.

Isolation, purification and properties of an R-phycocyanin from the phycobilisomes of a marine red macroalga Polysiphonia urceolata.

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Lu Wang

Full Text Available Phycobilisomes were prepared from a marine red macroalga Polysiphonia urceolata (P. urceolata by sucrose step-gradient ultracentrifugation. From the prepared phycobilisomes, an R-phycocyanin was isolated by gel filtration on Sephadex G-150 and then purified by ion exchange chromatography on DEAE-Sepharose Fast Flow and native polyacrylamide gel electrophoresis (PAGE performed in neutral buffer systems. The purified R-phycocyanins showed not only a homogeneous trimer of 136 kDa in gel filtration and a single band in native PAGE, but also exhibited one band at about pH 5.7 in native isoelectric focusing (IEF. By a gradient SDS-PAGE the purified R-phycocyanin was determined to contain one a subunit of 17.5 kDa (α17.5 and two b subunits of 21.3 kDa and 22.6 kDa (β21.3 and β22.6. The analysis from denaturing isoelectric focusing and two-dimension PAGE demonstrated that α17.5, β21.3 and β22.6 had their pIs of 6.4, 5.3 and 5.4, respectively. Furthermore, mass spectroscopy analysis of β21.3 and β22.6 by MALDI-TOF mass spectrometry demonstrated the two b subunits had differences in peptide mass fingerprinting. These results revealed that the prepared R-phycocyanins were composed of one a and two b subunits. (α17:53 β21:32 β22:61 and (α17:53 β21:31 β22:62, which have a structural foundation to show their pIs too close for them to be definitely resolved by native IEF, are postulated to be the most possible trimeric forms of the R-phycocyanins prepared from the phycobilisomes of P. urceolata.

Effect of MXene (Nano-Ti3C2 on Early-Age Hydration of Cement Paste

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Haibin Yin

2015-01-01

Full Text Available As a new two-dimensional material, MXene (nano-Ti3C2 has been widely applied in many fields, especially for reinforced composite materials. In this paper, mechanical testing, X-ray diffraction (XRD, hydration heat, scanning electron microscope (SEM, and EDS analysis were used to analyze the impact of MXene on cement hydration properties. The obtained results revealed that (a MXene could greatly improve the early compressive strength of cement paste with 0.04 wt% concentration, (b the phase type of early-age hydration products has not been changed after the addition of MXene, (c hydration exothermic rate within 72 h has small difference at different amount of MXene, and (d morphologies of hydration products were varied with the dosage of MXene, a lot of tufted ettringites appeared in 3 d hydration products when the content of MXene was 0.04 wt%, which will have a positive effect on improving the early mechanical properties of cement paste. MXene has inhibited the Portland cement hydration process; the main role of MXene in the cement hydration process is to promote the messy ettringite becoming regular distribution at a node and form network connection structure in the crystals growth process, making the mechanics performance of cement paste significantly improved.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

International Nuclear Information System (INIS)

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan

2016-01-01

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO_2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Sensitivity of hydrogen bonds of DNA and RNA to hydration, as gauged by 1JNH measurements in ethanol-water mixtures

International Nuclear Information System (INIS)

Manalo, Marlon N.; Kong Xiangming; LiWang, Andy

2007-01-01

Hydrogen-bond lengths of nucleic acids are (1) longer in DNA than in RNA, and (2) sequence dependent. The physicochemical basis for these variations in hydrogen-bond lengths is unknown, however. Here, the notion that hydration plays a significant role in nucleic acid hydrogen-bond lengths is tested. Watson-Crick N1...N3 hydrogen-bond lengths of several DNA and RNA duplexes are gauged using imino 1 J NH measurements, and ethanol is used as a cosolvent to lower water activity. We find that 1 J NH values of DNA and RNA become less negative with added ethanol, which suggests that mild dehydration reduces hydrogen-bond lengths even as the overall thermal stabilities of these duplexes decrease. The 1 J NH of DNA are increased in 8 mol% ethanol to those of RNA in water, which suggests that the greater hydration of DNA plays a significant role in its longer hydrogen bonds. The data also suggest that ethanol-induced dehydration is greater for the more hydrated G:C base pairs and thereby results in greater hydrogen-bond shortening than for the less hydrated A:T/U base pairs of DNA and RNA

Novel understanding of calcium silicate hydrate from dilute hydration

KAUST Repository

Zhang, Lina

2017-05-13

The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10 was conducted for tricalcium silicate (C3S) to interpret long-term hydration process and investigate the formation, structure and properties of C-S-H. Based on results from XRD, IR, SEM, NMR and so forth, loose and dense clusters of C-S-H with analogous C/S ratio were obtained along with the corresponding chemical formulae proposed as Ca5Si4O13∙6.2H2O. Crystalline structure inside C-S-H was observed by TEM, which was allocated at the foil-like proportion as well as the edge of wrinkles of the product. The long-term hydration process of C3S in dilute suspension could be sketchily described as migration of calcium hydroxide and in-situ growth of C-S-H with equilibrium silicon in aqueous solution relatively constant and calcium varied.

Class H cement hydration at 180 deg. C and high pressure in the presence of added silica

International Nuclear Information System (INIS)

Jupe, Andrew C.; Wilkinson, Angus P.; Luke, Karen; Funkhouser, Gary P.

2008-01-01

Under deep oil-well conditions of elevated temperature and pressure, crystalline calcium silicate hydrates are formed during Portland cement hydration. The use of silica rich mineral additives leads to the formation of crystalline hydrates with better mechanical properties than those formed without the additive. The effects of silica flour, silica fume (amorphous silica), and a natural zeolite mixture on the hydration of Class H cement slurries at 180 deg. C under externally applied pressures of 7 and 52 MPa are examined in real time using in-situ synchrotron X-ray diffraction. For some compositions examined, but not all, pressure was found to have a large effect on the kinetics of crystalline hydrate formation. The use of silica fume delayed both C 3 S hydration and the formation of crystalline silicate hydrates compared to what was seen with other silica sources

Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample.

Science.gov (United States)

Muraoka, Michihiro; Susuki, Naoko; Yamaguchi, Hiroko; Tsuji, Tomoya; Yamamoto, Yoshitaka

2016-03-21

Methane hydrates (MHs) are present in large amounts in the ocean floor and permafrost regions. Methane and hydrogen hydrates are being studied as future energy resources and energy storage media. To develop a method for gas production from natural MH-bearing sediments and hydrate-based technologies, it is imperative to understand the thermal properties of gas hydrates. The thermal properties' measurements of samples comprising sand, water, methane, and MH are difficult because the melting heat of MH may affect the measurements. To solve this problem, we performed thermal properties' measurements at supercooled conditions during MH formation. The measurement protocol, calculation method of the saturation change, and tips for thermal constants' analysis of the sample using transient plane source techniques are described here. The effect of the formation heat of MH on measurement is very small because the gas hydrate formation rate is very slow. This measurement method can be applied to the thermal properties of the gas hydrate-water-guest gas system, which contains hydrogen, CO2, and ozone hydrates, because the characteristic low formation rate of gas hydrate is not unique to MH. The key point of this method is the low rate of phase transition of the target material. Hence, this method may be applied to other materials having low phase-transition rates.

Calcium aluminates hydration in presence of amorphous SiO2 at temperatures below 90 deg. C

International Nuclear Information System (INIS)

Rivas Mercury, J.M.; Turrillas, X.; Aza, A.H. de; Pena, P.

2006-01-01

The hydration behaviour of Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 with added amorphous silica at 40, 65 and 90 deg. C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x ) and gibbsite, Al(OH) 3 , were identified, likewise amorphous phases like Al(OH) x , calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), which was the main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy. - Graphical abstract: Katoite, Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), was identified besides gibbsite, Al(OH) 3 , as a crystalline stable hydration products in Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 hydrated with added amorphous silica between 40 and 90 deg. C

The binding of the primary water of hydration to nucleosides, CsDNA and potassium hyaluronate

Science.gov (United States)

Lukan, A. M.; Cavanaugh, D.; Whitson, K. B.; Marlowe, R. L.; Lee, S. A.; Anthony, L.; Rupprecht, A.; Mohan, V.

1998-03-01

Differential scanning calorimetry (DSC) has been used to study the eight nucleosides, CsDNA and KHA hydrated at 59% relative humidity. Thermograms were measured between 25 and 180 ^oC for scan rates of 1, 2, 5, 10 and 20 K/min. A broad endothermic transition (due to the desorption of the water) near 80 ^oC was observed for all runs. The average enthalpy of desorption per water molecule was evaluated from the area under the peak. A Kissinger analysis of these data yielded the net activation energy for desorption. Both parameters were very similar for the two biopolymers. Rayleigh scattering of Mossbauer radiation (RSMR) data(G. Albanese et al. ) Hyperfine Int. 95, 97 (1995) were analyzed via a simple harmonic oscillator model to evaluate the effective force constant of the water bound to the biopolymer. This analysis suggests that the effective force constant of water bound to HA is much larger (about 5 times) than for water bound to DNA.

Gravimetric analysis and differential scanning calorimetric studies on glycerin-induced skin hydration.

Science.gov (United States)

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).

Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

Energy Technology Data Exchange (ETDEWEB)

Gallucci, E., E-mail: gallucci.emmanuel@ch.sika.com; Zhang, X.; Scrivener, K.L.

2013-11-15

Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures. -- Highlights: •C-S-H structure studied at the atomic level •Multiple analytical techniques used •Studies conducted at temperatures above and below normal temperatures.

Beaufort Sea deep-water gas hydrate recovery from a seafloor mound in a region of widespread BSR occurrence

Science.gov (United States)

Hart, Patrick E.; Pohlman, John W.; Lorenson, T.D.; Edwards, Brian D.

2011-01-01

Gas hydrate was recovered from the Alaskan Beaufort Sea slope north of Camden Bay in August 2010 during a U.S. Coast Guard Cutter Healy expedition (USCG cruise ID HLY1002) under the direction of the U.S. Geological Survey (USGS). Interpretation of multichannel seismic (MCS) reflection data collected in 1977 by the USGS across the Beaufort Sea continental margin identified a regional bottom simulating reflection (BSR), indicating that a large segment of the Beaufort Sea slope is underlain by gas hydrate. During HLY1002, gas hydrate was sampled by serendipity with a piston core targeting a steep-sided bathymetric high originally thought to be an outcrop of older, exposed strata. The feature cored is an approximately 1100m diameter, 130 m high conical mound, referred to here as the Canning Seafloor Mound (CSM), which overlies the crest of a buried anticline in a region of sub-parallel compressional folds beneath the eastern Beaufort outer slope. An MCS profile shows a prominent BSR upslope and downslope from the mound. The absence of a BSR beneath the CSM and occurrence of gas hydrate near the summit indicates that free gas has migrated via deep-rooted thrust faults or by structural focusing up the flanks of the anticline to the seafloor. Gas hydrate recovered from near the CSM summit at a subbottom depth of about 5.7 meters in a water depth of 2538 m was of nodular and vein-filling morphology. Although the hydrate was not preserved, residual gas from the core liner contained >95% methane by volume when corrected for atmospheric contamination. The presence of trace C4+hydrocarbons (extrusion contributing to the development of the mound. Blister-like inflation of the seafloor caused by formation and accumulation of shallow hydrate lenses is also a likely factor in CSM growth. Pore water analysis shows the sulfate-methane transition to be very shallow (0-1 mbsf), also supporting an active high-flux interpretation. Pore water with chloride concentrations as low as 160 m

A positron annihilation study of hydrated DNA

DEFF Research Database (Denmark)

Warman, J. M.; Eldrup, Morten Mostgaard

1986-01-01

Positron annihilation measurements are reported for hydrated DNA as a function of water content and as a function of temperature (20 to -180.degree. C) for samples containing 10 and 50% wt of water. The ortho-positronium mean lifetime and its intensity show distinct variations with the degree...

Hydration process for calcium-aluminate cement within EVA emulsion by SPring-8 synchrotron radiation x-ray diffraction method

International Nuclear Information System (INIS)

Kotera, Masaru; Matsuda, Ikuyo; Miyashita, Keiko; Adachi, Nobuyuki; Tamura, Hisayuki

2005-01-01

Polymer-modified mortars which consist of a polymer emulsion and cement materials have been widely developed in the construction materials fields. Forming process of the polymer-modified cement membrane simultaneously involves evaporation of water within the polymer emulsion and hydration of cement. It is important for the polymer-modified cement paste that the hydrate crystal of cement is generating by the hydration during the setting process under existence of the polymer emulsion. In this study, hydration process for calcium-aluminate cement under existence of poly (ethylene-vinyl acetate) (EVA) emulsion (polymer-cement ratio=100%) was investigated by X-ray diffraction method using synchrotron radiation (SPring-8). The diffraction peaks of calcium aluminate (CA) disappeared after the hardening, on the other hand, the peaks of hydrate crystals of calcium-aluminate cement (C 2 AH 8 and C 3 AH 6 ) could be observed. This polymer-modified cement paste hydrated using the water within the polymer emulsion. The hydration of C 2 AH 8 from CA started at around 300 min, and then C 3 AH 6 hydrate crystal increased after 700 min at ambient temperature. This implies that the conversion from C 2 AH 8 to C 3 AH 6 occurred to be more stable phase. The setting temperature affected the reaction rate. In case of hydration at 35degC, the start time of the hydration for calcium-aluminate cement was quicker than that in the ambient temperature four or more times. (author)

Methane recovery from coal mine gas using hydrate formation in water-in-oil emulsions

International Nuclear Information System (INIS)

Zhong, Dong-Liang; Ding, Kun; Lu, Yi-Yu; Yan, Jin; Zhao, Wei-Long

2016-01-01

Highlights: • A water-in-oil emulsion was developed for CH_4 separation from coal mine methane gas. • Stable W/O emulsions were obtained with water cut in the range of (10–70%). • Gas hydrates nucleated faster with the reduction of water–oil volume ratio. • Gas uptake increased with the decrease of water–oil volume ratio. • CH_4 recovery was greatly enhanced by hydrate formation in W/O emulsions. - Abstract: In this work, a water-in-oil (W/O) emulsion was developed using liquid water, mineral oil, Sorbitan monooleate (Span 80), and cyclopentane. It was employed to enhance gas hydrate formation for CH_4 separation from a simulated coal mine methane (CMM) gas (30 mol% CH_4, 60 mol% N_2, and 10 mol% O_2). The stability test at atmospheric pressure and at a high pressure of 3.5 MPa showed that stable W/O emulsions were obtained when the water–oil volume ratio (WOR) was below 80%. The emulsified droplets size was measured with WOR ranging from 10% to 70%. Then kinetic experiments of CH_4 separation by hydrate formation in W/O emulsions were carried out at 273.6 K and (3.5–5.0) MPa in batch operation. The results indicated that water–oil volume ratio is a key factor that affects the kinetics of gas hydrate formation from the CMM gas mixture. Hydrate nucleation was observed to occur faster while WOR was decreased, and gas uptake increased significantly with the decrease of WOR. CH_4 concentration in the recovered gas mixture was increased to 52 mol% as compared to 30 mol% in the original gas mixture through one-stage hydrate formation in the W/O emulsions. It was found that the experimental conditions of 273.6 K, 3.5 MPa and WOR = 30% were favorable for CH_4 recovery from the CMM gas. The CH_4 recovery obtained under these conditions was 43%. It was higher than those obtained at WOR = 10% and 70%, and was greatly increased as compared with those obtained in the same reactor with the presence of TBAB (26%) and CP (33%).

Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

International Nuclear Information System (INIS)

Anderson, Graydon K.

2004-01-01

The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

Modeling the hydration process of bean grains coated with carnauba wax

Directory of Open Access Journals (Sweden)

Aline Almeida da Paixão

2017-08-01

Full Text Available Edible waxes are widely used to maintain foodstuff until they are consumed. However, some products may be subjected to industrial procedures, such as hydration, prior to their consumption. Hydration of a material is a complex process, which aims to reconstitute the original characteristics of a product when in contact with a liquid phase. An important agricultural product that requires this procedure is beans. Thus, the purpose of this work is to study the hydration process of beans (cultivar BRSMG Majestoso in different temperatures and concentrations of carnauba wax, which is applied on the product surface. Beans with initial moisture content of 0.2015, 0.1972 and 0.1745 (d.b. corresponding to treatments 0 (witness, 1 (wax diluted in water in the ratio 1:1, and 2 (carnauba wax, without dilution were used. Later, these samples were imbibed in distilled water at temperatures of 20, 30 and 40 ºC, for 15 h. The temperature and the carnauba wax influenced the water absorption rate. The Peleg model described satisfactory experimental data and the Mitscherlich model presented biased residual distribution. The constants C1 and C2 of the Peleg model exhibited opposite behaviors with increasing temperatures in the hydration process.

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

Science.gov (United States)

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

2018-02-01

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

Analysis of the hydration water around bovine serum albumin using terahertz coherent synchrotron radiation.

Science.gov (United States)

Bye, Jordan W; Meliga, Stefano; Ferachou, Denis; Cinque, Gianfelice; Zeitler, J Axel; Falconer, Robert J

2014-01-09

Terahertz spectroscopy was used to study the absorption of bovine serum albumin (BSA) in water. The Diamond Light Source operating in a low alpha mode generated coherent synchrotron radiation that covered a useable spectral bandwidth of 0.3-3.3 THz (10-110 cm(-1)). As the BSA concentration was raised, there was a nonlinear change in absorption inconsistent with Beer's law. At low BSA concentrations (0-1 mM), the absorption remained constant or rose slightly. Above a concentration of 1 mM BSA, a steady decrease in absorption was observed, which was followed by a plateau that started at 2.5 mM. Using a overlapping hydration layer model, the hydration layer was estimated to extend 15 Å from the protein. Calculation of the corrected absorption coefficient (αcorr) for the water around BSA by subtracting the excluded volume of the protein provides an alternative approach to studying the hydration layer that provides evidence for complexity in the population of water around BSA.

Studies on the fixation of tritiated water using the cement hydration, 2

International Nuclear Information System (INIS)

Nishimaki, Kenzo; Tsutsui, Tenson; Miake, Chiaki.

1989-01-01

In the previous paper, we have reported the results of basic experiments to fix tritiated water using the hydration of cement, and found that most tritiated water transfers to surrounding water, even if it is incorporated using the hydration of cement. In this report, we tried to apply a simple compartment model to the tritium transfer curves reported in the previous paper, which represent the phenomena that most water containing tritium is exchanging with a surrounding water, regardless of its forms, i.e., a crystalline water, free water and so on. We divided a solidified cement into three groupes with respect to the exchangeability of water, i.e., a compartment of fixed water, of compositions expect water, and of exchanging water. We developed a simple compartment model under the assumption that the water in the third compartment is exchangeable with the sorrounding water with a certain exchanging volume rate E, not altering by time. The transfer curves calculated with the model contains unknown parameter, E. By the method of least squares, varying the values of E, we could obtain most approximated transfer curves of tritium to those obtained by the previous experiments. In the result, we knew that the simple compartment model is applied to the tritium transfer curves reported in the previous paper. (author)

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

Science.gov (United States)

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

Crystal water as the mol-ecular glue for obtaining different co-crystal ratios: the case of gallic acid tris-caffeine hexa-hydrate.

Science.gov (United States)

Vella-Zarb, L; Baisch, U

2018-04-01

The crystal structure of the hexa-hydrate co-crystal of gallic acid and caffeine, C 7 H 6 O 5 ·3C 8 H 10 N 4 O 2 ·6H 2 O or GAL3CAF·6H 2 O , is a remarkable example of the importance of hydrate water acting as structural glue to facilitate the crystallization of two components of different stoichiometries and thus to compensate an imbalance of hydrogen-bond donors and acceptors. The water mol-ecules provide the additional hydrogen bonds required to form a crystalline solid. Whereas the majority of hydrogen bonds forming the inter-molecular network between gallic acid and caffeine are formed by crystal water, only one direct classical hydrogen bond between two mol-ecules is formed between the carb-oxy-lic oxygen of gallic acid and the carbonyl oxygen of caffeine with d ( D ⋯ A ) = 2.672 (2) Å. All other hydrogen bonds either involve crystal water or utilize protonated carbon atoms as donors.

Final Scientific/Technical Report: Characterizing the Response of the Cascadia Margin Gas Hydrate Reservoir to Bottom Water Warming Along the Upper Continental Slope

Energy Technology Data Exchange (ETDEWEB)

Solomon, Evan A. [Univ. of Washington, Seattle, WA (United States); Johnson, H. Paul [Univ. of Washington, Seattle, WA (United States); Salmi, Marie [Univ. of Washington, Seattle, WA (United States); Whorley, Theresa [Univ. of Washington, Seattle, WA (United States)

2017-11-10

samples were extracted from the gravity cores, and the pore water was analyzed for a comprehensive suite of solutes, gases, and stable isotope ratios. This comprehensive geochemical dataset was used to characterize the fluid and gas source(s) at each of the seep sites surveyed. The primary results of this project are: 1) Bottom simulating reflector-derived heat flow values decrease from 95 mW/m2 10 km east of the deformation front to ~60 mW/m2 60 km landward of the deformation front, with anomalously low values of ~25 mW/m2 on a prominent mid-margin terrace off central Washington. 2) The temperature of the incoming sediment/ocean crust interface at the deformation front ranges between 164-179 oC off central Washington, and the 350 oC isotherm at the top of the subducting ocean crust occurs 95 km landward of the deformation front. Differences between BSR-derived heat flow and modeled conductive heat flow suggest mean upward fluid flow rates of 0.4 cm/yr across the margin, with local regions (e.g. fault zones) exhibiting fluid flow rates up to 3.5 cm/yr. 3) A compilation of 2122 high-resolution CTD, glider, and Argo float temperature profiles spanning the upper continental slope of the Washington margin from the years 1968 to 2013 show a long-term warming trend that ranges from 0.006-0.008 oC/yr. Based on this long-term bottom water warming, we developed a 2-D thermal model to simulate the change in sediment temperature distribution over this period, along with the downslope retreat of the methane hydrate stability field. Over the 43 years of the simulation, the thermal disturbance propagated 30 m into the sediment column, causing the base of the methane hydrate stability field to shoal ~13 m and to move ~1 km downslope. 4) A preliminary analysis of seafloor observations and mid-water column acoustic data to detect bubble plumes was used to characterize the depth distribution of seeps along the Cascadia margin. These results indicate high bubble plume densities along the

Controls on Gas Hydrate Formation and Dissociation

Energy Technology Data Exchange (ETDEWEB)

Miriam Kastner; Ian MacDonald

2006-03-03

The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

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

Science.gov (United States)

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

Hydrophobic hydration of poly-N-isopropyl acrylamide: a matter of the mean energetic state of water

Science.gov (United States)

Bischofberger, I.; Calzolari, D. C. E.; de Los Rios, P.; Jelezarov, I.; Trappe, V.

2014-03-01

The enthalpically favoured hydration of hydrophobic entities, termed hydrophobic hydration, impacts the phase behaviour of numerous amphiphiles in water. Here, we show experimental evidence that hydrophobic hydration is strongly determined by the mean energetics of the aqueous medium. We investigate the aggregation and collapse of an amphiphilic polymer, poly-N-isopropyl acrylamide (PNiPAM), in aqueous solutions containing small amounts of alcohol and find that the thermodynamic characteristics defining the phase transitions of PNiPAM evolve relative to the solvent composition at which the excess mixing enthalpy of the water/alcohol mixtures becomes minimal. Such correlation between solvent energetics and solution thermodynamics extends to other mixtures containing neutral organic solutes that are considered as kosmotropes to induce a strengthening of the hydrogen bonded water network. This denotes the energetics of water as a key parameter controlling the phase behaviour of PNiPAM and identifies the excess mixing enthalpy of water/kosmotrope mixtures as a gauge of the kosmotropic effect on hydrophobic assemblies.

Pf1 bacteriophage hydration by magic angle spinning solid-state NMR

Energy Technology Data Exchange (ETDEWEB)

Sergeyev, Ivan V.; Bahri, Salima; McDermott, Ann E., E-mail: aem5@columbia.edu [Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027 (United States); Day, Loren A. [Public Health Research Institute, Rutgers University, 225 Warren St., Newark, New Jersey 07103 (United States)

2014-12-14

High resolution two- and three-dimensional heteronuclear correlation spectroscopy ({sup 1}H–{sup 13}C, {sup 1}H–{sup 15}N, and {sup 1}H–{sup 13}C–{sup 13}C HETCOR) has provided a detailed characterization of the internal and external hydration water of the Pf1 virion. This long and slender virion (2000 nm × 7 nm) contains highly stretched DNA within a capsid of small protein subunits, each only 46 amino acid residues. HETCOR cross-peaks have been unambiguously assigned to 25 amino acids, including most external residues 1–21 as well as residues 39–40 and 43–46 deep inside the virion. In addition, the deoxyribose rings of the DNA near the virion axis are in contact with water. The sets of cross-peaks to the DNA and to all 25 amino acid residues were from the same hydration water {sup 1}H resonance; some of the assigned residues do not have exchangeable side-chain protons. A mapping of the contacts onto structural models indicates the presence of water “tunnels” through a highly hydrophobic region of the capsid. The present results significantly extend and modify results from a lower resolution study, and yield a comprehensive hydration surface map of Pf1. In addition, the internal water could be distinguished from external hydration water by means of paramagnetic relaxation enhancement. The internal water population may serve as a conveniently localized magnetization reservoir for structural studies.

Mineralogy of C-S-H belite hydrates incorporating Zn-Al-Ti layered double hydroxides

Directory of Open Access Journals (Sweden)

Amor F.

2018-01-01

Full Text Available Recently, the belitic cements with low alite content were the subject of several research works which aimed to replace the Ordinary Portland Clinker (OPC for ecological reasons (reduction of CO2 emissions, so to understand the reactivity of this cement, the hydration study of the C2S “dicalcium silicate” phase is primordial research step. As well for a clean environment, the TiO2 photocatalyst has been extensively applied in the science of building materials because of its ability to degrade the cement surface pollutants. New photocatalyst based layered double hydroxides (LDH associated with zinc, aluminium and TiO2 was introduced to increase the compatibility with mortars. The present work is subjected to investigate the effect of the layered double hydroxides on the hydration of C2S in following the evolution of hydration by X-ray diffraction at 2, 7, 28 and 90 days and analyzing the calcium/silicon ratio of different formed hydrates.

Comparison of the rate constants for energy transfer in the light-harvesting protein, C-phycocyanin, calculated from Foerster`s theory and experimentally measured by time-resolved fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Debreczeny, Martin Paul [Univ. of California, Berkeley, CA (United States)

1994-05-01

We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.

Can hydrate dissolution experiments predict the fate of a natural hydrate system?

Energy Technology Data Exchange (ETDEWEB)

Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

2008-07-01

Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

Major factors influencing the generation of natural gas hydrate in porous media

Directory of Open Access Journals (Sweden)

V.N. Khlebnikov

2017-11-01

Full Text Available Current researches related to natural gas hydrate mainly focus on its physical and chemical properties, as well as the approaches to the production (decomposition of hydrate. Physical modeling of the flow process in hydrate deposits is critical to the study on the exploitation or decomposition of hydrate. However, investigation of the dynamic hydrate process by virtue of porous media like sand-packed tubes which are widely used in petroleum production research is rarely reported in literature. In this paper, physical simulation of methane hydrate generation process was conducted using river sand-packed tubes in the core displacement apparatus. During the simulation, the influences of parameters such as reservoir temperature, methane pressure and reservoir model properties on the process of hydrate generation were investigated. The following results are revealed. First, the use of ice-melted water as the immobile water in the reservoir model can significantly enhance the rate of methane hydrate generation. Second, the process driving force in porous media (i.e., extents to which the experimental pressure or temperature deviating those corresponding to the hydrate phase equilibrium plays a key role in the generation of methane hydrate. Third, the induction period of methane hydrate generation almost does not change with temperature or pressure when the methane pressure is above 1.4 folds of the hydrate phase equilibrium pressure or the laboratory temperature is lower than the phase equilibrium temperature by 3 °C or more. Fourth, the parameters such as permeability, water saturation and wettability don't have much influence on the generation of methane hydrate.

Evaluation of Hydrate Inhibition Performance of Water-soluble Polymers using Torque Measurement and Differential Scanning Calorimeter

International Nuclear Information System (INIS)

Shin, Kyuchul; Park, Juwoon; Kim, Jakyung; Kim, Hyunho; Seo, Yutaek; Lee, Yohan; Seo, Yongwon

2014-01-01

In this work, hydrate inhibition performance of water-soluble polymers including pyrrolidone, caprolactam, acrylamide types were evaluated using torque measurement and high pressure differential scanning calorimeter (HP µ-DSC). The obtained experimental results suggest that the studied polymers represent the kinetic hydrate inhibition (KHI) performance. 0.5 wt% polyvinylcaprolactam (PVCap) solution shows the hydrate onset time of 34.4 min and subcooling temperature of 15.9 K, which is better KHI performance than that of pure water - hydrate onset time of 12.3 min and subcooling temperature of 6.0 K. 0.5 wt% polyvinylpyrrolidone (PVP) solution shows the hydrate onset time of 27.6 min and the subcooling temperature of 13.2 K while polyacrylamide-co-acrylic acid partial sodium salt (PAM-co-AA) solution shows less KHI performance than PVP solution at both 0.5 and 5.0 wt%. However, PAM-co-AA solution shows slow growth rate and low hydrate amount than PVCap. In addition to hydrate onset and growth condition, torque change with time was investigated as one of KHI evaluation methods. 0.5 wt% PVCap solution shows the lowest average torque of 6.4 N cm and 0.5 wt% PAM-co-AA solution shows the average torque of 7.2 N cm. For 0.5 wt% PVP solution, it increases 11.5 N cm and 5.0 wt% PAM-co-AA solution shows the maximum average torque of 13.4 N cm, which is similar to the average torque of pure water, 15.2 N cm. Judging from the experimental results obtained by both an autoclave and a HP µ-DSC, the PVCap solution shows the best performance among the KHIs in terms of delaying hydrate nucleation. From these results, it can be concluded that the torque change with time is useful to identify the flow ability of tested solution, and the further research on the inhibition of hydrate formation can be approached in various aspects using a HP µ-DSC

Halting of the calcium aluminate cement hydration process

International Nuclear Information System (INIS)

Luz, A.P.; Borba, N.Z; Pandolfelli, V.C.

2011-01-01

The calcium aluminate cement reactions with water lead to the anhydrous phases dissolution resulting a saturated solution, followed by nucleation and crystal growth of the hydrate compounds. This is a dynamic process, therefore, it is necessary to use suitable methods to halt the hydration in order to study the phase transformations kinetics of such materials. In this work two methods are evaluated: use of acetone and microwave drying, aiming to withdraw the free water and inhibit further reactions. X ray diffraction and thermogravimetric tests were used to quantify the phases generated in the cement samples which were kept at 37 deg C for 1 to 15 days. The advantages and disadvantages of those procedures are presented and discussed. The use of microwave to halt the hydration process seems to be effective to withdraw the cement free water, and it can further be used in researches of the refractory castables area, endodontic cements, etc. (author)

In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Science.gov (United States)

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

2011-01-01

In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

Thermodynamic description of the solubility of C-S-H gels in hydrated Portland cement. Literature review

International Nuclear Information System (INIS)

Soler, J.M.

2007-11-01

The objective of this study is to compile the available information published in the scientific literature regarding the solubility of C-S-H (calcium silica hydrate) gels, which are the main components of hydrated Portland cement. Modeling the thermodynamic properties of C-S-H, including its incongruent dissolution behavior, is an important requirement to understand the evolution and degradation of hydrated cement and concrete. The thermodynamic modeling of C-S-H started with the use of empirical or semi-empirical models and evolved to the application of solid solution models. Most of the experimental work has been performed at or near 25 deg C and the models are in principle applicable to temperatures near 25 deg C. One of the models provides an explicit dependence on temperature. (orig.)

In vitro antioxidant and antiproliferative activities of selenium-containing phycocyanin from selenium-enriched Spirulina platensis.

Science.gov (United States)

Chen, Tianfeng; Wong, Yum-Shing

2008-06-25

Both selenium and phycocyanin have been reported to show potent cancer chemopreventive activities. In this study, we investigated the in vitro antioxidant and antiproliferative activities of selenium-containing phycocyanin (Se-PC) purified from selenium-enriched Spirulina platensis. The antioxidant activity of Se-PC was evaluated by using four different free radical scavenging assays, namely, the 2,2'-azinobis-3-ethylbenzothiazolin-6-sulfonic acid (ABTS) assay, 1,1-diphenyl-2-picryhydrazyl (DPPH) assay, superoxide anion scavenging assay, and erythrocyte hemolysis assay. The results indicated that Se-PC exhibited stronger antioxidant activity than phycocyanin by scavenging ABTS, DPPH, superoxide anion, and 2,2'-azobis-(2-amidinopropane)dihydrochloride free radicals. Se-PC also showed dose-dependent protective effects on erythrocytes against H 2O 2-induced oxidative DNA damage as evaluated by the Comet assay. Moreover, Se-PC was identified as a potent antiproliferative agent against human melanoma A375 cells and human breast adenocarcinoma MCF-7 cells. Induction of apoptosis in both A375 and MCF-7 cells by Se-PC was evidenced by accumulation of sub-G1 cell populations, DNA fragmentation, and nuclear condensation. Further investigation on intracellular mechanisms indicated that depletion of mitochondrial membrane potential (DeltaPsi m) was involved in Se-PC-induced cell apoptosis. Our findings suggest that Se-PC is a promising organic Se species with potential applications in cancer chemoprevention.

Combining Multicomponent Seismic Attributes, New Rock Physics Models, and In Situ Data to Estimate Gas-Hydrate Concentrations in Deep-Water, Near-Seafloor Strata of the Gulf of Mexico

Energy Technology Data Exchange (ETDEWEB)

Bureau of Economic Geology

2009-04-30

The Bureau of Economic Geology was contracted to develop technologies that demonstrate the value of multicomponent seismic technology for evaluating deep-water hydrates across the Green Canyon area of the Gulf of Mexico. This report describes the methodologies that were developed to create compressional (P-P) and converted-shear (P-SV) images of near-seafloor geology from four-component ocean-bottom-cable (4C OBC) seismic data and the procedures used to integrate P-P and P-SV seismic attributes with borehole calibration data to estimate hydrate concentration across two study areas spanning 16 and 25 lease blocks (or 144 and 225 square miles), respectively. Approximately 200 km of two-dimensional 4C OBC profiles were processed and analyzed over the course of the 3-year project. The strategies we developed to image near-seafloor geology with 4C OBC data are unique, and the paper describing our methodology was peer-recognized with a Best Paper Award by the Society of Exploration Geophysicists in the first year of the project (2006). Among the valuable research findings demonstrated in this report, the demonstrated ability to image deep-water near-seafloor geology with sub-meter resolution using a standard-frequency (10-200 Hz) air gun array on the sea surface and 4C sensors on the seafloor has been the accomplishment that has received the most accolades from professional peers. Our study found that hydrate is pervasive across the two study areas that were analyzed but exists at low concentrations. Although our joint inversion technique showed that in some limited areas, and in some geologic units across those small areas, hydrates occupied up to 40-percent of the sediment pore space, we found that when hydrate was present, hydrate concentration tended to occupy only 10-percent to 20-percent of the pore volume. We also found that hydrate concentration tended to be greater near the base of the hydrate stability zone than it was within the central part of the stability

The role of pH in the vapor hydration at 175 °C of the French SON68 glass

International Nuclear Information System (INIS)

Ait Chaou, Abdelouahed; Abdelouas, Abdesselam; El Mendili, Yassine; Martin, Christelle

2017-01-01

The French simulated nuclear waste SON68 glass was altered in the presence of water vapor at 175 °C and 98% of relative humidity under several atmospheres (NH_3, H_2S, CO_2 and argon). The objectives were to study the role of pH on hydration kinetics and secondary phases formation. The hydration was followed by infrared spectroscopy and the nature and extent of alteration products were determined by characterizing the reacted glass surface with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), μ-Raman spectroscopy and X-ray diffraction (XRD). The glass hydration/alteration rate clearly increased with increasing pH, that is controlled by the gas atmosphere, as the following: NH_3 > Ar > CO_2 > H_2S. This can directly be linked to the secondary phases precipitated on the glass surface. Hence, the major alteration products observed at high pH (under NH_3 and Ar) are analcime and Ca-silicates hydrates (CSH) while at low pH (under CO_2 and H_2S) only a hydrated gel layer was identified. - Highlights: • The vapor hydration study of the SON68 glass under geological conditions. • The secondary phases formation in the alteration of SON68 glass. • The pH effect on the alteration kinetics of glass.

Characterizing Natural Gas Hydrates in the Deep Water Gulf of Mexico: Applications for Safe Exploration and Production Activities

Energy Technology Data Exchange (ETDEWEB)

Bent, Jimmy

2014-05-31

In 2000 Chevron began a project to learn how to characterize the natural gas hydrate deposits in the deep water portion of the Gulf of Mexico (GOM). Chevron is an active explorer and operator in the Gulf of Mexico and is aware that natural gas hydrates need to be understood to operate safely in deep water. In August 2000 Chevron worked closely with the National Energy Technology Laboratory (NETL) of the United States Department of Energy (DOE) and held a workshop in Houston, Texas to define issues concerning the characterization of natural gas hydrate deposits. Specifically, the workshop was meant to clearly show where research, the development of new technologies, and new information sources would be of benefit to the DOE and to the oil and gas industry in defining issues and solving gas hydrate problems in deep water.

Basin-Wide Temperature Constraints On Gas Hydrate Stability In The Gulf Of Mexico

Science.gov (United States)

MacDonald, I. R.; Reagan, M. T.; Guinasso, N. L.; Garcia-Pineda, O. G.

2012-12-01

Gas hydrate deposits commonly occur at the seafloor-water interface on marine margins. They are especially prevalent in the Gulf of Mexico where they are associated with natural oil seeps. The stability of these deposits is potentially challenged by fluctuations in bottom water temperature, on an annual time-scale, and under the long-term influence of climate change. We mapped the locations of natural oil seeps where shallow gas hydrate deposits are known to occur across the entire Gulf of Mexico basin based on a comprehensive review of synthetic aperture radar (SAR) data (~200 images). We prepared a bottom water temperature map based on the archive of CTD casts from the Gulf (~6000 records). Comparing the distribution of gas hydrate deposits with predicted bottom water temperature, we find that a broad area of the upper slope lies above the theoretical stability horizon for structure 1 gas hydrate, while all sites where gas hydrate deposits occur are within the stability horizon for structure 2 gas hydrate. This is consistent with analytical results that structure 2 gas hydrates predominate on the upper slope (Klapp et al., 2010), where bottom water temperatures fluctuate over a 7 to 10 C range (approx. 600 m depth), while pure structure 1 hydrates are found at greater depths (approx. 3000 m). Where higher hydrocarbon gases are available, formation of structure 2 gas hydrate should significantly increase the resistance of shallow gas hydrate deposits to destabilizing effects variable or increasing bottom water temperature. Klapp, S.A., Bohrmann, G., Kuhs, W.F., Murshed, M.M., Pape, T., Klein, H., Techmer, K.S., Heeschen, K.U., and Abegg, F., 2010, Microstructures of structure I and II gas hydrates from the Gulf of Mexico: Marine and Petroleum Geology, v. 27, p. 116-125.Bottom temperature and pressure for Gulf of Mexico gas hydrate outcrops and stability horizons for sI and sII hydrate.

Neutron emission during lithium deuteride hydration in heavy water

International Nuclear Information System (INIS)

Arzhannikov, A.V.; Kezerashvili, G.Ya.; Muratov, V.V.; Sinitskij, S.L.

1989-01-01

An experiment on neutron detection during lithium deuteride hydration in heavy water using a system of SNM-17 or SNM-18 gas counters was set up. Signals were simultaneously detected by 6 counters and the data were stored in a computer. At the same time the temperature of the reaction ampule external surface was measured. It was found that the neutron number per 1 gram of lithium deuteride reacted with water in the ampule was equal to several dozens if their initial energy was about 2.5 MeV. 4 refs.; 2 figs

Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

Directory of Open Access Journals (Sweden)

Dolado, J. S.

2011-06-01

Full Text Available The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C3S, β-C2S and their blends are studied by Nitrogen sorption and nanoindentation experiments. The surface area and nanoporosity of C-S-H gels formed from the hydration of β-C2S and the 30-70 (T1-C3S and β-C2S mixture are higher than those from hydration of T1-C3S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nanoindentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C2S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 29Si magic-angle-spinning (MAS NMR, of the C-S-H gels.La caracterización textural y mecánica de geles C-S-H formados a partir de la hidratación de muestras puras de T1-C3S, ß-C2S y sus mezclas ha sido estudiada por medio de adsorción de nitrógeno y nanoindentación. El área superficial y la nano-porosidad de los geles formados durante la hidratación del ß-C2S y la mezcla 30-70 (T1-C3S- ß-C2S son mayores que los correspondientes a los geles del T1-C3S, y la mezcla 70-30; esta diferencia disminuye con el tiempo de hidratación. Estos cambios coinciden con los resultados de nanoindentación que indican un aumento de volumen relativo de las fases C-S-H con una densidad menor en el caso del ß-C2S y la mezcla 30-70. Al aumentar el tiempo de hidratación, el volumen relativo de fases C-S-H de mayor densidad aumenta a expensas de aquellas de menor densidad. Importantes correlaciones cuantitativas se establecen entre las características texturales y la longitud de cadena media del gel C-S-H, determinada mediante RMN-MAS de 29Si.

Changes in the solid state of anhydrous and hydrated forms of sodium naproxen under different grinding and environmental conditions: Evidence of the formation of new hydrated forms.

Science.gov (United States)

Censi, Roberta; Rascioni, Riccardo; Di Martino, Piera

2015-05-01

The aim of the present work was to investigate the solid state change of the anhydrous and hydrate solid forms of sodium naproxen under different grinding and environmental conditions. Grinding was carried out manually in a mortar under the following conditions: at room temperature under air atmosphere (Method A), in the presence of liquid nitrogen under air atmosphere (Method B), at room temperature under nitrogen atmosphere (Method C), and in the presence of liquid nitrogen under nitrogen atmosphere (Method D). Among the hydrates, the following forms were used: a dihydrate form (DSN) obtained by exposing the anhydrous form at 55% RH; a dihydrate form (CSN) obtained by crystallizing sodium naproxen from water; the tetrahydrate form (TSN) obtained by exposing the anhydrous form at 75% RH. The metastable monohydrate form (MSN), previously described in the literature, was not used because of its high physical instability. The chemical stability during grinding was firstly assessed and proven by HPLC. Modification of the particle size and shape, and changes in the solid state under different grinding methods were evaluated by scanning electron microscopy, and X-ray powder diffractometry and thermogravimetry, respectively. The study demonstrated the strong influence of starting form, grinding and environmental conditions on particle size, shape and solid state of recovered sodium naproxen forms. In particular, it was demonstrated that in the absence of liquid nitrogen (Methods A and C), either at air or at nitrogen atmosphere, the monohydrate form (MSN) was obtained from any hydrates, meaning that these grinding conditions favored the dehydration of superior hydrates. The grinding process carried out in the presence of liquid nitrogen (Method B) led to further hydration of the starting materials: new hydrate forms were identified as one pentahydrate form and one hexahydrate form. The hydration was caused by the condensation of the atmospheric water on sodium naproxen

Geochemical evidences of methane hydrate dissociation in Alaskan Beaufort Margin during Holocene

Science.gov (United States)

Uchida, M.; Rella, S.; Kubota, Y.; Kumata, H.; Mantoku, K.; Nishino, S.; Itoh, M.

2017-12-01

Alaskan Beaufort margin bear large abundances of sub-sea and permafrost methane hydrate[Ruppel, 2016]. During the Last Glacial, previous reported direct and indirect evidences accumulated from geochemical data from marginal sea sediment suggests that methane episodically released from hydrate trapped in the seafloor sediments[Kennett et al., 2000; Uchida et al., 2006, 2008; Cook et al, 2011]. Here we analyzed stable isotopes of foraminifera and molecular marker derived from the activity of methanotrophic bacteria from piston cores collected by the 2010 R/V Mirai cruise in Alaskan Beaufort Margin. Our data showed highly depleted 13C compositions of benthic foraminifera, suggesting indirect records of enhanced incorporation of 13C-depleted CO2 formed by methanotrophic process that use 12C-enriched methane as their main source of carbon. This is the first evidence of methane hydrate dissociation in Alaskan margin. Here we discussed timing of signals of methane dissociation with variability of sea ice and intermediate Atlantic water temperature. The dissociation of methane hydrate in the Alaskan Margin may be modulated by Atlantic warm intermediate water warming. Our results suggest that Arctic marginal regions bearing large amount methane hydrate may be a profound effect on future warming climate changes.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

Science.gov (United States)

Braun, Doris E.; Griesser, Ulrich J.

2018-01-01

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

Study of the Effects of Betaine and/or C-Phycocyanin on the Growth of Lung Cancer A549 Cells In Vitro and In Vivo

Directory of Open Access Journals (Sweden)

Rea Bingula

2016-01-01

Full Text Available We investigated the effects of betaine, C-phycocyanin (C-PC, and their combined use on the growth of A549 lung cancer both in vitro and in vivo. When cells were coincubated with betaine and C-PC, an up to 60% decrease in viability was observed which is significant compared to betaine (50% or C-PC treatment alone (no decrease. Combined treatment reduced the stimulation of NF-κB expression by TNF-α and increased the amount of the proapoptotic p38 MAPK. Interestingly, combined treatment induced a cell cycle arrest in G2/M phase for ~60% of cells. In vivo studies were performed in pathogen-free male nude rats injected with A549 cells in their right flank. Their daily food was supplemented with either betaine, C-PC, both, or neither. Compared to the control group, tumour weights and volumes were significantly reduced in either betaine- or C-PC-treated groups and no additional decrease was obtained with the combined treatment. This data indicates that C-PC and betaine alone may efficiently inhibit tumour growth in rats. The synergistic activity of betaine and C-PC on A549 cells growth observed in vitro remains to be further confirmed in vivo. The reason behind the nature of their interaction is yet to be sought.

Raman studies of methane-ethane hydrate metastability.

Science.gov (United States)

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

2009-03-05

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

1H NMR relaxometry as an indicator of setting and water depletion during cement hydration

International Nuclear Information System (INIS)

Wang, Biyun; Faure, Paméla; Thiéry, Mickaël; Baroghel-Bouny, Véronique

2013-01-01

Proton nuclear magnetic resonance relaxometry has been used to detect setting and microstructure evolution during cement hydration. NMR measurements were performed since casting, during setting and until hardening (from 0 to 3 days). The mobility of water molecules was assessed by an analysis focused on the diagram of longitudinal relaxation time T 1 generated by an Inversion Recovery sequence. The initial stiffening of the solid network was identified by an analysis of the relaxation rate 1/T 1 . The kinetics of water depletion was investigated by using a simple one-pulse acquisition sequence. In parallel, conventional techniques (Vicat needle and temperature monitoring), as well as numerical simulations of hydration, were used to complement and validate these NMR results. Cement pastes and mortars with different water-to-cement ratios made of grey or white OPCs were tested. Furthermore, the effects of the addition of sand, super-plasticizer and silica fume on the hydration kinetics were investigated

Selective and reactive hydration of nitriles to amides in water using silver nanoparticles stabilized by organic ligands

International Nuclear Information System (INIS)

Kawai, Koji; Kawakami, Hayato; Narushima, Takashi; Yonezawa, Tetsu

2015-01-01

Water-dispersible silver nanoparticles stabilized by silver–carbon covalent bonds were prepared. They exhibited high catalytic activities for the selective hydration of nitriles to amides in water. The activation of a nitrile group by the functional groups of the substrates and the hydrophobic layer on the nanoparticles influenced the catalyzed reaction were confirmed. Alkyl nitriles could also be selectively hydrated

Transparent hydrogel with enhanced water retention capacity by introducing highly hydratable salt

OpenAIRE

Bai, Yuanyuan; Chen, Baohong; Xiang, Feng; Zhou, Jinxiong; Wang, Hong; Suo, Zhigang

2014-01-01

Polyacrylamide hydrogels containing salt as electrolyte have been used as highly stretchable transparent electrodes in flexible electronics, but those hydrogels are easy to dry out due to water evaporation. Targeted, we try to enhance water retention capacity of polyacrylamide hydrogel by introducing highly hydratable salts into the hydrogel. These hydrogels show enhanced water retention capacity in different level. Specially, polyacrylamide hydrogel containing high content of lithium chlorid...

Electrical Conductive Mechanism of Gas Hydrate-Bearing Reservoirs in the Permafrost Region of Qilian Mountain

Science.gov (United States)

Peng, C.; Zou, C.; Tang, Y.; Liu, A.; Hu, X.

2017-12-01

In the Qilian Mountain, gas hydrates not only occur in pore spaces of sandstones, but also fill in fractures of mudstones. This leads to the difficulty in identification and evaluation of gas hydrate reservoir from resistivity and velocity logs. Understanding electrical conductive mechanism is the basis for log interpretation. However, the research is insufficient in this area. We have collected well logs from 30 wells in this area. Well logs and rock samples from DK-9, DK-11 and DK-12 wells were used in this study. The experiments including SEM, thin section, NMR, XRD, synthesis of gas hydrate in consolidated rock cores under low temperature and measurement of their resistivity and others were performed for understanding the effects of pore structure, rock composition, temperature and gas hydrate on conductivity. The results show that the porosity of reservoir of pore filling type is less than 10% and its clay mineral content is high. As good conductive passages, fractures can reduce resistivity of water-saturated rock. If fractures in the mudstone are filled by calcite, resistivity increases significantly. The resistivity of water-saturated rock at 2°C is twice of that at 18°C. The gas hydrate formation process in the sandstone was studied by resistivity recorded in real time. In the early stage of gas hydrate formation, the increase of residual water salinity may lead to the decrease of resistivity. In the late stage of gas hydrate formation, the continuity decrease of water leads to continuity increase of resistivity. In summary, fractures, rock composition, temperature and gas hydrate are important factors influencing resistivity of formation. This study is helpful for more accurate evaluation of gas hydrate from resistivity log. Acknowledgment: We acknowledge the financial support of the National Special Program for Gas Hydrate Exploration and Test-production (GZH201400302).

Gas Hydrate Occurrence Inferred from Dissolved Cl− Concentrations and δ18O Values of Pore Water and Dissolved Sulfate in the Shallow Sediments of the Pockmark Field in Southwestern Xisha Uplift, Northern South China Sea

Directory of Open Access Journals (Sweden)

Min Luo

2014-06-01

Full Text Available Deep-water pockmarks are frequently accompanied by the occurrence of massive gas hydrates in shallow sediments. A decline in pore-water Cl− concentration and rise in δ18O value provide compelling evidence for the gas hydrate dissociation. Mega-pockmarks are widely scattered in the southwestern Xisha Uplift, northern South China Sea (SCS. Pore water collected from a gravity-core inside of a mega-pockmark exhibits a downward Cl− concentration decrease concomitant with an increase in δ18O value at the interval of 5.7–6.7 mbsf. Concentrations of Cl−, Na+, and K+ mainly cluster along the seawater freshening line without distinct Na+ enrichment and K+ depletion. Thus, we infer that the pore water anomalies of Cl− concentrations and δ18O values are attributed to gas hydrate dissociation instead of clay mineral dehydration. Moreover, the lower δ18O values of sulfate in the target core (C14 than those in the reference core (C9 may be associated with the equilibrium oxygen fractionation during sulfate reduction between sulfate and the relatively 18O-depleted ambient water resulting from gas hydrate formation. The gas hydrate contents are estimated to be 6%–10% and 7%–15%, respectively, according to the offset of Cl− concentrations and δ18O values from the baselines. This pockmark field in southwestern Xisha Uplift is likely to be a good prospective area for the occurrence of gas hydrate in shallow sediments.

Stability conditions and guest distribution of the methane + ethane + propane hydrates or semiclathrates in the presence of tetrahydrofuran or quaternary ammonium salts

International Nuclear Information System (INIS)

Lee, Seungmin; Lee, Youngjun; Park, Sungwon; Kim, Yunju; Cha, Inuk; Seo, Yongwon

2013-01-01

Highlights: • We examined the stability conditions and guest distributions of natural gas hydrates. • THF, TBAB, and TBAF could remarkably stabilize the hydrate dissociation conditions. • Preferential occupation of CH 4 molecules was observed at the stoichiometric concentrations. -- Abstract: In this study, the stability conditions and guest distributions of methane (CH 4 ) + ethane (C 2 H 6 ) + propane (C 3 H 8 ) hydrates or semiclathrates are examined in the presence of tetrahydrofuran (THF) and quaternary ammonium salts such as tetra-n-butylammonium bromide (TBAB) and tetra-n-butylammonium fluoride (TBAF) through thermodynamic and spectroscopic analyses. The three-phase equilibria of hydrate or semiclathrate (H), liquid water (L W ), and vapor (V) for the quinary CH 4 + C 2 H 6 + C 3 H 8 + THF + water, CH 4 + C 2 H 6 + C 3 H 8 + TBAB + water, and CH 4 + C 2 H 6 + C 3 H 8 + TBAF + water mixtures with various concentrations were experimentally measured in order to determine the hydrate or semiclathrate stability conditions. The experimental results demonstrated that all thermodynamic promoters such as THF, TBAB, and TBAF used in this study could remarkably stabilize the hydrate dissociation conditions even though the degree of stabilization was dependent on the type of promoters and on the concentrations of each promoter used. From the 13 C NMR analysis, preferential occupation of CH 4 molecules in the hydrate or semiclathrate lattices was observed at the stoichiometric concentrations of each hydrate or semiclathrate structure. However, at the THF mole fraction lower than 0.056, the large cages of structure II were shared by CH 4 , C 2 H 6 , C 3 H 8 , and THF molecules, whereas the small cages were occupied by only CH 4 molecules. The results given in this study are very useful in understanding the thermodynamic stability, structural characteristics, and guest distribution of the hydrates or semiclathrates with multi-components in the presence of

Methods to determine hydration states of minerals and cement hydrates

Energy Technology Data Exchange (ETDEWEB)

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

2014-11-15

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

Methods to determine hydration states of minerals and cement hydrates

International Nuclear Information System (INIS)

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

2014-01-01

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

Quantitative nanoscale water mapping in frozen-hydrated skin by low-loss electron energy-loss spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yakovlev, Sergey [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Misra, Manoj; Shi, Shanling [Unilever Research and Development, Trumbull, CT 06611 (United States); Firlar, Emre [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Libera, Matthew, E-mail: mlibera@stevens.edu [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States)

2010-06-15

Spatially resolved low-loss electron energy-loss spectroscopy (EELS) is a powerful method to quantitatively determine the water distribution in frozen-hydrated biological materials at high spatial resolution. However, hydrated tissue, particularly its hydrophilic protein-rich component, is very sensitive to electron radiation. This sensitivity has traditionally limited the achievable spatial resolution because of the relatively high noise associated with low-dose data acquisition. We show that the damage caused by high-dose data acquisition affects the accuracy of a multiple-least-squares (MLS) compositional analysis because of inaccuracies in the reference spectrum used to represent the protein. Higher spatial resolution combined with more accurate compositional analysis can be achieved if a reference spectrum is used that better represents the electron-beam-damaged protein component under frozen-hydrated conditions rather than one separately collected from dry protein under low-dose conditions. We thus introduce a method to extract the best-fitting protein reference spectrum from an experimental spectrum dataset. This method can be used when the MLS-fitting problem is sufficiently constrained so that the only unknown is the reference spectrum for the protein component. We apply this approach to map the distribution of water in cryo-sections obtained from frozen-hydrated tissue of porcine skin. The raw spectral data were collected at doses up to 10{sup 5} e/nm{sup 2} despite the fact that observable damage begins at doses as low as 10{sup 3} e/nm{sup 2}. The resulting spatial resolution of 10 nm is 5-10 times better than that in previous studies of frozen-hydrated tissue and is sufficient to resolve sub-cellular water fluctuations as well as the inter-cellular lipid-rich regions of skin where water-mediated processes are believed to play a significant role in the phenotype of keratinocytes in the stratum corneum.

Quantitative nanoscale water mapping in frozen-hydrated skin by low-loss electron energy-loss spectroscopy

International Nuclear Information System (INIS)

Yakovlev, Sergey; Misra, Manoj; Shi, Shanling; Firlar, Emre; Libera, Matthew

2010-01-01

Spatially resolved low-loss electron energy-loss spectroscopy (EELS) is a powerful method to quantitatively determine the water distribution in frozen-hydrated biological materials at high spatial resolution. However, hydrated tissue, particularly its hydrophilic protein-rich component, is very sensitive to electron radiation. This sensitivity has traditionally limited the achievable spatial resolution because of the relatively high noise associated with low-dose data acquisition. We show that the damage caused by high-dose data acquisition affects the accuracy of a multiple-least-squares (MLS) compositional analysis because of inaccuracies in the reference spectrum used to represent the protein. Higher spatial resolution combined with more accurate compositional analysis can be achieved if a reference spectrum is used that better represents the electron-beam-damaged protein component under frozen-hydrated conditions rather than one separately collected from dry protein under low-dose conditions. We thus introduce a method to extract the best-fitting protein reference spectrum from an experimental spectrum dataset. This method can be used when the MLS-fitting problem is sufficiently constrained so that the only unknown is the reference spectrum for the protein component. We apply this approach to map the distribution of water in cryo-sections obtained from frozen-hydrated tissue of porcine skin. The raw spectral data were collected at doses up to 10 5 e/nm 2 despite the fact that observable damage begins at doses as low as 10 3 e/nm 2 . The resulting spatial resolution of 10 nm is 5-10 times better than that in previous studies of frozen-hydrated tissue and is sufficient to resolve sub-cellular water fluctuations as well as the inter-cellular lipid-rich regions of skin where water-mediated processes are believed to play a significant role in the phenotype of keratinocytes in the stratum corneum.

The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering

International Nuclear Information System (INIS)

Sjoestroem, J; Kargl, F; Fernandez-Alonso, F; Swenson, J

2007-01-01

The dynamics of water in fresh and in rehydrated white bread is studied using quasielastic neutron scattering (QENS). A diffusion constant for water in fresh bread, without temperature gradients and with the use of a non-destructive technique, is presented here for the first time. The self-diffusion constant for fresh bread is estimated to be D s = 3.8 x 10 -10 m 2 s -1 and the result agrees well with previous findings for similar systems. It is also suggested that water exhibits a faster dynamics than previously reported in the literature using equilibration of a hydration-level gradient monitored by vibrational spectroscopy. The temperature dependence of the dynamics of low hydration bread is also investigated for T = 280-350 K. The average relaxation time at constant momentum transfer (Q) shows an Arrhenius behavior in the temperature range investigated

Cage occupancies of natural gas hydrates encaging methane and ethane

Energy Technology Data Exchange (ETDEWEB)

Kida, M.; Hachikubo, A.; Sakagami, H.; Minami, H.; Krylov, A.; Yamashita, S.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan); Khlystov, O. [Limnological Inst., Irkutsk (Russian Federation). Siberian Branch of the Russian Academy of Sciences; Poort, J. [Ghent Univ., Ghent (Belgium). Renard Centre of Marine Geology; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan)

2008-07-01

Natural gas hydrates are crystalline compounds that contain large amounts of natural gas in its structure and are expected to provide natural gas resources in the future. The gas species are trapped in different types of polyhedral cages which consist of hydrogen bonded water molecules. Three main types of crystallographic structures exist, notably structure 1, structure 2 and structure H (sH). The crystallographic structure of natural gas hydrates depends on the encaged gas components. The cage occupancy is the ratio of the number of cages occupied by guest molecules to the number of total cages. It is also important to estimate the amount of natural gas, since it depends on the condition of the hydrate formation such as gas composition. The cages of natural gas hydrates mainly contain methane. However, other heavier hydrocarbons such as ethane (C{sub 2}H{sub 6}), propane (C{sub 3}H{sub 8}), and isobutane (i-C{sub 4}H{sub 1}0) may be encaged together with CH{sub 4}. Little is known about cage occupancies of natural gas hydrates including CH{sub 4} and heavier hydrocarbons. This paper discussed a study that developed cage occupancy estimations of natural gas hydrates encaging heavier hydrocarbons. 13C nuclear magnetic resonance (NMR) measurements were conducted. The assignments of resonance lines were based on 13C chemical shifts obtained by artificial sample measurements. The paper presented the experimental data and discussed the results of the study. The large cages were almost fully occupied with CH{sub 4} and C{sub 2}H{sub 6} molecules, whereas the small cage occupancies of CH{sub 4} were below 0.8. The distribution of CH{sub 4} and C{sub 2}H{sub 6} in each cage were similar to that of synthetic CH{sub 4} + C{sub 2}H{sub 6} hydrate. It was concluded that these results should be useful for optimal estimation of the amount of natural gas in gas hydrates. 18 refs., 1 tab., 3 figs.

Experimental Study on Hydrate Induction Time of Gas-Saturated Water-in-Oil Emulsion using a High-Pressure Flow Loop

Directory of Open Access Journals (Sweden)

Lv X.F.

2015-11-01

Full Text Available Hydrate is one of the critical precipitates which have to be controlled for subsea flow assurance. The induction time of hydrate is therefore a significant parameter. However, there have been few studies on the induction time of the natural gas hydrate formation in a flow loop system. Consequently, a series of experiments were firstly performed, including water, natural gas and Diesel oil, on the hydrate induction time under various conditions such as the supercooling and supersaturation degree, water cut, anti-agglomerant dosage, etc. The experiments were conducted in a high-pressure hydrate flow loop newly constructed in the China University of Petroleum (Beijing, and dedicated to flow assurance studies. Then, based on previous research, this study puts forward a method for induction time, which is characterized by clear definition, convenient measurement and good generality. Furthermore, we investigated the influences of the experimental parameters and analyzed the experimental phenomena for the hydrate induction time in a flowing system.

Manufacture of Methane Hydrate using Carbon Nano Tubes

International Nuclear Information System (INIS)

Park, Sung Seek

2010-02-01

Methane hydrate is formed by physical binding between water molecule and gas such as methane, ethane, propane, or carbon dioxide, etc., which is captured in the cavities of water molecule under the specific temperature and pressure. More than 99% of naturally produced methane hydrate consists of methane, and is widely dispersed in the continental slope and continental Shelf of the Pacific and the Atlantic, the Antarctica etc. The reserve of fossil fuel is 500 billion carbon ton and the reserve of methane is 360 million carbon ton. The reserve of gas hydrate is more than 1 trillion carbon ton, which is twice the fossil fuel. Therefore, natural gas hydrate as a kind of gas hydrate is expected to replace fossil fuel as new energy source of 21st century. Also 1 m 3 hydrate of pure methane can be decomposed to the maximum of 216 m 3 methane at standard condition. If these characteristics of hydrate are reversely utilized, natural gas is fixed into water in the form of hydrate solid. Therefore, the hydrate is considered to be a great way to transport and store natural gas in large quantity. Especially the transportation cost is known to be 18∼25% less than the liquefied transportation. However, when natural gas hydrate is artificially formed, its reaction time may be too long and the gas consumption in water becomes relatively low, because the reaction rate between water and gas is low. Therefore, for the practical purpose in the application, the present investigation focuses on the rapid production of hydrates and increases gas consumption by adding MWCNT and NaCl into pure water. The results show that the equilibrium pressure in seawater is more higher than that in pure water, and methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 9K or above in seawater and 8K or above in pure water, respectively. Also, amount of consumed gas volume in pure water is more higher that in seawater at the same experimental conditions

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

Directory of Open Access Journals (Sweden)

Doris E. Braun

2018-02-01

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

Novel understanding of calcium silicate hydrate from dilute hydration

KAUST Repository

Zhang, Lina; Yamauchi, Kazuo; Li, Zongjin; Zhang, Xixiang; Ma, Hongyan; Ge, Shenguang

2017-01-01

The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10

Formation rate of natural gas hydrate

Energy Technology Data Exchange (ETDEWEB)

Mork, Marit

2002-07-01

The rate of methane hydrate and natural gas hydrate formation was measured in a 9.5 litre stirred tank reactor of standard design. The experiments were performed to better understand the performance and scale-up of a reactor for continuous production of natural gas hydrates. The hydrate formation rate was measured at steady-state conditions at pressures between 70 and 90 bar and temperatures between 7 and 15 deg C. Between 44 and 56 % of the gas continuously supplied to the reactor was converted to hydrate. The experimental results show that the rate of hydrate formation is strongly influenced by gas injection rate and pressure. The effect of stirring rate is less significant and subcooling has no observable effect on the formation rate. Hydrate crystal concentration and gas composition do not influence the hydrate formation rate. Observations of produced hydrate crystals indicate that the crystals are elongated, about 5 micron in diameter and 10 micron long. Analysis of the results shows that the rate of hydrate formation is dominated by gas-liquid mass transfer. A mass transfer model, the bubble-to-crystal model, was developed for the hydrate formation rate in a continuous stirred tank reactor, given in terms of concentration driving force and an overall mass transfer coefficient. The driving force is the difference between the gas concentration at the gas-liquid interface and at the hydrate crystal surface. These concentrations correspond to the solubility of gas in water at experimental temperature and pressure and the solubility of gas at hydrate equilibrium temperature and experimental pressure, respectively. The overall mass transfer coefficient is expressed in terms of superficial gas velocity and impeller power consumption, parameters commonly used in study of stirred tank reactors. Experiments and modeling show that the stirred tank reactor has a considerable potential for increased production capacity. However, at higher hydrate production rates the

Effects of Water Provision and Hydration on Cognitive Function among Primary-School Pupils in Zambia: A Randomized Trial.

Directory of Open Access Journals (Sweden)

Victoria Trinies

Full Text Available There is a well-established link between hydration and improved cognitive performance among adults, with evidence of similar findings among children. No trials have investigated the impact of water provision on cognitive performance among schoolchildren in hot and arid low-resource settings. We conducted a randomized-controlled trial in five schools with limited water access in Chipata district in Eastern province, Zambia, to assess the efficacy of water provision on cognition. Pupils in grades 3-6 were randomly assigned to either receive a bottle of drinking water that they could refill throughout the day (water group, n = 149 or only have access to drinking water that was normally available at the school (control group, n = 143. Hydration was assessed in the morning before provision of water and in the afternoon through urine specific gravity (Usg measured with a portable refractometer. In the afternoon we administered six cognitive tests to assess short-term memory, concentration, visual attention, and visual motor skills. Morning prevalence of dehydration, defined as Usg≥1.020, was 42%. Afternoon dehydration increased to 67% among the control arm and dropped to 10% among the intervention arm. We did not find that provision of water or hydration impacted cognitive test scores, although there were suggestive relationships between both water provision and hydration and increased scores on tests measuring visual attention. We identified key improvements to the study design that are warranted to further investigate this relationship.ClinicalTrials.gov NCT01924546.

Growth and phycocyanin synthesis in the heterotrophic microalga Galdieria sulphuraria on substrates made of food waste from restaurants and bakeries

DEFF Research Database (Denmark)

Sloth, Jenni K; Jensen, Henriette Casper; Pleissner, Daniel

2017-01-01

Galdieria sulphuraria 074G (Rhodophyta) was grown heterotrophically in defined medium and on amylolytic and proteolytic hydrolysed food waste from restaurants and bakeries. Substrate uptake, growth, and phycocyanin content were quantified in the cultures. The alga utilised carbohydrates and amino...... in quantities resulting in glucose concentrations of 10 and 50 g L−1 for bakery and restaurant waste, respectively. Still, G. sulphuraria 074G grew and produced phycocyanin efficiently on food waste under adequate conditions and may potentially be utilised for synthesise of high-valuable products from food...

Effect of humidity on the hydration behaviour of prazosin hydrochloride polyhydrate: Thermal, sorption and crystallographic study

International Nuclear Information System (INIS)

Kumar, Lokesh; Bansal, Arvind K.

2011-01-01

Highlights: → Utility of TGA to differentiate between unbound and bound water was demonstrated. → Nature of the lattice arrangement in prazosin hydrochloride polyhydrate was confirmed to be expanded (non-stoichiometric) type hydrate. → Correlation of the DSC, TGA, PXRD and DVS for dehydration of prazosin hydrochloride polyhydrate was delineated. - Abstract: In this study, hydration behaviour of prazosin hydrochloride polyhydrate was assessed using differential scanning calorimetry, thermogravimetric analysis, powder X-ray diffraction and dynamic vapour sorption techniques. Differential scanning calorimetry and thermogravimetric analysis at faster heating rate (20 o C/min) showed single step water loss, attributed to both dihydrate and unbound water. In contrast, thermogravimetric analysis at slower heating rate (1 o C/min) showed unbound and dihydrate lattice water separately, with unbound water being lost initially, followed by loss of dihydrate water. Variable vacuum and variable humidity PXRD study revealed shift in diffraction peaks to higher values on removal of unbound water. Initial PXRD patterns were regained when kept again at ambient conditions. Dynamic vapour sorption depicted type I sorption isotherm with interstitial water, indicating that polyhydrate form show reversible behaviour with change in humidity. Correlation between thermal, sorption and crystallographic data established hydration behaviour to be characteristic of expanded channel type (non-stoichiometric) hydrate.

A novel remote sensing algorithm to quantify phycocyanin in cyanobacterial algal blooms

International Nuclear Information System (INIS)

Mishra, S; Mishra, D R

2014-01-01

We present a novel three-band algorithm (PC 3 ) to retrieve phycocyanin (PC) pigment concentration in cyanobacteria laden inland waters. The water sample and remote sensing reflectance data used for PC 3 calibration and validation were acquired from highly turbid productive catfish aquaculture ponds. Since the characteristic PC absorption feature at 620 nm is contaminated with residual chlorophyll-a (Chl-a) absorption, we propose a coefficient (ψ) for isolating the PC absorption component at 620 nm. Results show that inclusion of the model coefficient relating Chl-a absorption at 620 nm–665 nm enables PC 3 to compensate for the confounding effect of Chl-a at the PC absorption band and considerably increases the accuracy of the PC prediction algorithm. In the current dataset, PC 3 produced the lowest mean relative error of prediction among all PC algorithms considered in this research. Moreover, PC 3 eliminates the nonlinear sensitivity issue of PC algorithms particularly at high PC range (>100 μg L −1 ). Therefore, introduction of PC 3 will have an immediate positive impact on studies monitoring inland and coastal cyanobacterial harmful algal blooms. (letter)

Electron spin resonance study on γ-ray-induced radical species in ethylene hydrate

International Nuclear Information System (INIS)

Takeya, Kei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

2007-01-01

Electron spin resonance (ESR) study on γ-irradiated synthetic ethylene hydrate was performed to investigate induced radicals and their thermal stability. ESR spectra of induced 3-butenyl radical (.CH 2 C 2 H 3 =CH 2 ,g=2.0039±0.0005,A α =2.2±0.1mTandA β =3.0±0.1mT) and induced ethyl radical (.C 2 H 5 , g=2.0044±0.0005, A α =2.2±0.1mT and A β =2.7±0.1mT) were observed in irradiated ethylene hydrate. The decay of the 3-butenyl radicals was observed above 200 K with the activation energy of 51.9±4.4kJ/mol. The obvious decay of ethyl radicals starts above 240 K that is close to the dissociation temperature of ethylene hydrate at atmospheric pressure. The activation energy of the ethyl radical decay is estimated as 63.4±8.2kJ/mol and nearly equal to the enthalpy change of ethylene hydrate into liquid water and gaseous ethylene. It is suggested that the decay of ethyl radicals would be caused by the hydrate dissociation and that ethylene hydrate dissociates into water (supercooled) and ethylene at 240-265 K.

Relationship between diffusivity of water molecules inside hydrating tablets and their drug release behavior elucidated by magnetic resonance imaging.

Science.gov (United States)

Kikuchi, Shingo; Onuki, Yoshinori; Kuribayashi, Hideto; Takayama, Kozo

2012-01-01

We reported previously that sustained release matrix tablets showed zero-order drug release without being affected by pH change. To understand drug release mechanisms more fully, we monitored the swelling and erosion of hydrating tablets using magnetic resonance imaging (MRI). Three different types of tablets comprised of polyion complex-forming materials and a hydroxypropyl methylcellulose (HPMC) were used. Proton density- and diffusion-weighted images of the hydrating tablets were acquired at intervals. Furthermore, apparent self-diffusion coefficient maps were generated from diffusion-weighted imaging to evaluate the state of hydrating tablets. Our findings indicated that water penetration into polyion complex tablets was faster than that into HPMC matrix tablets. In polyion complex tablets, water molecules were dispersed homogeneously and their diffusivity was relatively high, whereas in HPMC matrix tablets, water molecule movement was tightly restricted within the gel. An optimal tablet formulation determined in a previous study had water molecule penetration and diffusivity properties that appeared intermediate to those of polyion complex and HPMC matrix tablets; water molecules were capable of penetrating throughout the tablets and relatively high diffusivity was similar to that in the polyion complex tablet, whereas like the HPMC matrix tablet, it was well swollen. This study succeeded in characterizing the tablet hydration process. MRI provides profound insight into the state of water molecules in hydrating tablets; thus, it is a useful tool for understanding drug release mechanisms at a molecular level.

Processes of hydration aging of superconducting ceramics and problem of regeneration of properties

International Nuclear Information System (INIS)

Komarov, A.V.; Popov, V.P.; Tikhonov, P.A.

1989-01-01

The process of hydration aging (distilled water, saturated water vapors) of YBa 2 Cu 3 O 6.5+x specimens with T s of about 95 K was studied at 55 deg C and water vapors pressure of 119 mmHg. It is established that depending on exposure time and saturated vapors pressure, water affects electric properties of yttrium-barium ceramics with different degree of the effect reversibility. Valuable regeneration of the characteristics can occur only when the hydration process has not led to changes in the phase composition of the material. The mechanism of interaction between cermaics and water is given

Molecular Dynamics Simulation of a Membrane/Water Interface : The Ordering of Water and Its Relation to the Hydration Force

NARCIS (Netherlands)

Marrink, Siewert-Jan; Berkowitz, Max; Berendsen, Herman J.C.

1993-01-01

In order to obtain a better understanding of the origin of the hydration force, three molecular dynamic simulations of phospholipid/water multilamellar systems were performed. The simulated systems only differed in the amount of interbilayer water, ranging from the minimum to the maximum amount of

Overview: Nucleation of clathrate hydrates.

Science.gov (United States)

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

2016-12-07

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

Overview: Nucleation of clathrate hydrates

Science.gov (United States)

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

2016-12-01

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

Optimization of phycocyanin extraction from microalgae Spirulina platensis by sonication as antioxidant

Science.gov (United States)

Dianursanti, Indraputri, Claudia Maya; Taurina, Zarahmaida

2018-02-01

Cardiovascular disease is known as an epidemic disease which has high casualty in the world. One of its trigger factors is the amount of reactive oxygen species (ROS) inside the body. In order to regulate its amount, antioxidant ingestion is compulsory. Microalgae can be adopted as a source of antioxidant. Spirulina platensis is one of the consistently produced microalgae. It contains phycocyanin, a blue pigment, which is known as a nutritious food agent. Phycocyanin could be assumed as an antioxidant and has been clinically validated both in vitro and in vivo. This research is proposed to determine the optimum extraction time. The experiment was conducted by sonication at 37 kHz using phosphate buffer as the solvent. The result exhibited that increasing the sonication time would increase the yield until it achieved the optimum yield. Based on the experiment, the optimum extraction time was 25 minutes with yield of 8.25 mg/g dry biomass and purity of 0.6. It can be summarized that extraction time also affected the extraction efficiency and its antioxidant activity. This paper shows a prospect on future development in cultivating micro flora in Indonesia, particularly in Depok.

Hydration status regulates sodium flux and inflammatory pathways through epithelial sodium channel (ENaC) in the skin.

Science.gov (United States)

Xu, Wei; Hong, Seok Jong; Zeitchek, Michael; Cooper, Garry; Jia, Shengxian; Xie, Ping; Qureshi, Hannan A; Zhong, Aimei; Porterfield, Marshall D; Galiano, Robert D; Surmeier, D James; Mustoe, Thomas A

2015-03-01

Although it is known that the inflammatory response that results from disruption of epithelial barrier function after injury results in excessive scarring, the upstream signals remain unknown. It has also been observed that epithelial disruption results in reduced hydration status and that the use of occlusive dressings that prevent water loss from wounds decreases scar formation. We hypothesized that hydration status changes sodium homeostasis and induces sodium flux in keratinocytes, which result in activation of pathways responsible for keratinocyte-fibroblast signaling and ultimately lead to activation of fibroblasts. Here, we demonstrate that perturbations in epithelial barrier function lead to increased sodium flux in keratinocytes. We identified that sodium flux in keratinocytes is mediated by epithelial sodium channels (ENaCs) and causes increased secretion of proinflammatory cytokines, which activate fibroblast via the cyclooxygenase 2 (COX-2)/prostaglandin E2 (PGE2) pathway. Similar changes in signal transduction and sodium flux occur by increased sodium concentration, which simulates reduced hydration, in the media in epithelial cultures or human ex vivo skin cultures. Blockade of ENaC, prostaglandin synthesis, or PGE2 receptors all reduce markers of fibroblast activation and collagen synthesis. In addition, employing a validated in vivo excessive scar model in the rabbit ear, we demonstrate that utilization of either an ENaC blocker or a COX-2 inhibitor results in a marked reduction in scarring. Other experiments demonstrate that the activation of COX-2 in response to increased sodium flux is mediated through the PIK3/Akt pathway. Our results indicate that ENaC responds to small changes in sodium concentration with inflammatory mediators and suggest that the ENaC pathway is a potential target for a strategy to prevent fibrosis.

Ceramide 1 and ceramide 3 act synergistically on skin hydration and the transepidermal water loss of sodium lauryl sulfate-irritated skin.

Science.gov (United States)

Huang, Huey-Chun; Chang, Tsong-Min

2008-08-01

Stratum corneum intercellular lipids, such as ceramides, play an important role in the regulation of skin water barrier homeostasis and water-holding capacity. Aim To evaluate the potential water retention capacity of control emulsion and three oil-in-water (o/w) emulsions containing ceramide 1, ceramide 3, or both. Fifteen healthy Asian women (age, 20-30 years) with healthy skin, pretreated with sodium lauryl sulfate (SLS), applied the tested emulsions twice daily over a period of 28 days. Skin hydration and transepidermal water loss (TEWL) values were measured on the indicated days with a Corneometer(R)825 and a TEWAMETER TM210, respectively. The maximum increase in skin humidity was reached after 4 weeks, with values of 21.9 +/- 1.8% and 8.9 +/- 0.9% for emulsion C and control emulsion, respectively. The maximum decrease in TEWL was also reached after 4 weeks, with values of 36.7 +/- 4.7% and 5.1 +/- 0.8% for the same emulsions. It can be concluded that all the tested ceramide-containing emulsions improved skin barrier function when compared with untreated skin. There was some indication that ceramides 1 and 3 contained in emulsion C might exert a beneficial synergistic effect on skin biochemical properties, such as skin hydration and TEWL, and play a key role in the protection mechanism against SLS irritation.

Phase equilibrium condition measurements in nitrogen and air clathrate hydrate forming systems at temperatures below freezing point of water

International Nuclear Information System (INIS)

Yasuda, Keita; Oto, Yuya; Shen, Renkai; Uchida, Tsutomu; Ohmura, Ryo

2013-01-01

Highlights: • Phase equilibrium conditions in the nitrogen and modelled air hydrate forming systems are measured. • Measurements are conducted at temperatures below the freezing point of water. • Results have relevance to the air hydrate formation in the ice sheets. • Measured data are quantitatively compared with the previously reported values. • Range of the equilibrium measurements was from (242 to 268) K. -- Abstract: Contained in this paper are the three phase equilibrium conditions of the (ice + clathrate hydrate + guest-rich) vapour in the (nitrogen + water) and the modelled (air + water) systems at temperatures below the freezing point of water. The precise determination of the equilibrium conditions in those systems are of importance for the analysis of the past climate change using the cored samples from the ice sheets at Antarctica and Greenland because the air hydrates keep the ancient climate signals. The mole ratio of the modelled air composed of nitrogen and oxygen is 0.790:0.210. The equilibrium conditions were measured by the batch, isochoric procedure. The temperature range of the measurements in the nitrogen hydrate forming system is (244.05 < T < 266.55) K and the corresponding equilibrium pressure range is (7.151 < p < 12.613) MPa. The temperature range of the measurements in the modelled air hydrate forming system is (242.55 < T < 267.85) K, and the corresponding equilibrium pressure range is (6.294 < p < 12.144) MPa. The data obtained quantitatively compared with the previously reported data

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

Science.gov (United States)

Scholl, Sarah K; Schmidt, Shelly J

2014-11-01

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

An ab initio and AIM investigation into the hydration of 2-thioxanthine

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Fossey John S

2010-03-01

Full Text Available Abstract Background Hydration is a universal phenomenon in nature. The interactions between biomolecules and water of hydration play a pivotal role in molecular biology. 2-Thioxanthine (2TX, a thio-modified nucleic acid base, is of significant interest as a DNA inhibitor yet its interactions with hydration water have not been investigated either computationally or experimentally. Here in, we reported an ab initio study of the hydration of 2TX, revealing water can form seven hydrated complexes. Results Hydrogen-bond (H-bond interactions in 1:1 complexes of 2TX with water are studied at the MP2/6-311G(d, p and B3LYP/6-311G(d, p levels. Seven 2TX...H2O hydrogen bonded complexes have been theoretically identified and reported for the first time. The proton affinities (PAs of the O, S, and N atoms and deprotonantion enthalpies (DPEs of different N-H bonds in 2TX are calculated, factors surrounding why the seven complexes have different hydrogen bond energies are discussed. The theoretical infrared and NMR spectra of hydrated 2TX complexes are reported to probe the characteristics of the proposed H-bonds. An improper blue-shifting H-bond with a shortened C-H bond was found in one case. NBO and AIM analysis were carried out to explain the formation of improper blue-shifting H-bonds, and the H-bonding characteristics are discussed. Conclusion 2TX can interact with water by five different H-bonding regimes, N-H...O, O-H...N, O-H...O, O-H...S and C-H...O, all of which are medium strength hydrogen bonds. The most stable H-bond complex has a closed structure with two hydrogen bonds (N(7-H...O and O-H...O, whereas the least stable one has an open structure with one H-bond. The interaction energies of the studied complexes are correlated to the PA and DPE involved in H-bond formation. After formation of H-bonds, the calculated IR and NMR spectra of the 2TX-water complexes change greatly, which serves to identify the hydration of 2TX.

Some physical properties of anhydrous and hydrated Brownmillerite doped with NaF

International Nuclear Information System (INIS)

Hassaan, M.Y.; El Desoky, M.M.; Salem, S.M.; Yousif, A.A.

2003-01-01

Different samples of Brownmillerite (the ferrite phase of cement clinker) doped with 0, 1 or 3 wt.% NaF were prepared. At first, the oxide mixture of Brownmillerite was prepared according to the following composition: 4 mol CaO, 1 mol Al 2 O 3 and 1 mol Fe 2 O 3 in addition to 1 or 3 wt.% NaF. Each mixture was mixed very well, introduced into an electric furnace at 1300 deg. C for 1 h in a platinum crucible, and then quenched in air. The product was divided into four portions mixed with 40 wt.% distilled water to form Brownmillerite paste, except for one portion which was left dry. Each paste was molded into two molds; after 24 h, they were immersed in a distilled water and withdrawn after 1 or 3 days of hydration, respectively. The pastes were ground again. The anhydrous powders of Brownmillerites and the hydrated samples were prepared for a.c. conduction measurements by pressing it to be in pellets form. The two surfaces of each pellet were coated with silver paste. The a.c. conductivity and dielectric constant for different samples were measured using four-probe method. The data was collected from 320 up to 670 K. Moessbauer spectra and X-ray diffraction patterns were measured for each sample (anhydrous and hydrated) to confirm the formation of Brownmillerite, identify the iron states and the magnetic properties. The results showed that NaF addition to Brownmillerite expedites the hydration reaction rate. The superparamagnetic relaxation, which appeared in the anhydrous Brownmillerite spectra due to the small particle size, decreases with increasing the hydration time. Also, the Fe 3+ (Oh) state increases while Fe 3+ (Td) decreases with the time of hydration. The a.c. conductivity value at fixed frequency for anhydrous and hydrated samples was found to increase with NaF addition. The a.c. conductivity and Moessbauer measurements can be used as good tools to verify the purity of Brownmillerite phase and, accordingly, the purity of cement

Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

Science.gov (United States)

Weber, J. Mathias; Adams, Christopher L.

2010-06-01

We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

Naphthenic acids hydrates of gases: influence of the water/oil interface on the dispersing properties of an acidic crude oil; Acides naphteniques hydrates de gaz de l'interface eau/huile sur les proprietes dispersantes d'un brut acide

Energy Technology Data Exchange (ETDEWEB)

Arla, D.

2006-01-15

Nowadays, the development of offshore oil production under increasing water depths (high pressures and low temperatures) has led oil companies to focus on gas hydrates risks. Hydrates are crystals containing gas and water molecules which can plug offshore pipelines. It has been shown that some asphaltenic crude oils stabilize water-in-oil emulsions (W/O) during several months and exhibit very good anti-agglomerant properties avoiding hydrate plugs formation. In this work, we have studied the 'anti-hydrate' properties of a West African acidic crude oil called crude AH. This oil contains naphthenic acids, RCOOH hydrocarbons which are sensitive to both the pH and the salinity of the water phase.The emulsifying properties of the crude AH have firstly been explored. It has been shown that heavy resins and asphaltenes are the main compounds of the crude AH responsible for the long term stability of the W/O emulsions whereas the napthenates RCOO{sup -} lead to less stable W/O emulsions. Dealing with hydrates, the crude AH exhibits moderate anti-agglomerant properties due to the presence of heavy resins and asphaltenes. However, the naphthenates RCOO{sup -} drastically increase the formation of hydrate plugs. Moreover, it has been pointed out that hydrate particles agglomeration accelerates the kinetics of hydrate formation and enhances the water/oil separation. In order to explain these behaviours, a mechanism of agglomeration by 'sticking' between a hydrate particle and a water droplet has been proposed. Finally, we have developed a model which describes the physico-chemical equilibria of the naphthenic acids in the binary system water/crude AH, in order to transpose the results obtained in the laboratory to the real oil field conditions. (author)

The Biological Effect of Extremely Low Frequency Electromagnetic Fields and Vibrations on Barley Seed Hydration and Germination

Directory of Open Access Journals (Sweden)

Armine Amyan

2004-01-01

Full Text Available The changes of wet and dry weights and germination of barley seed in different periods of its swelling in nontreated (control, extremely low frequency electromagnetic fields (ELF EMF –treated, and extremely low frequency vibrations (ELFV–treated cold (4°C and warm (20°C distilled water (DW were studied. The metabolic-dependent seed hydration, dry weight dissolving, germination, and water binding in seed were modulated by preliminary EMF- and ELFV-treated DW. Frequency “windows” for the effect of EMF and ELFV on seed hydration, solubility, water binding in seed, and germination were discovered. These “windows” were different for EMF and ELFV, as well as in various phases of seed swelling. It is suggested that EMF-induced water structure modification has a different biological effect on the process of seed hydration, solubility, water binding in seed, and germination compared to ELFV.

Temporal behavior of hydrated electron studied up to 400 deg. C by ultrafast pulse radiolysis and Monte Carlo calculation

International Nuclear Information System (INIS)

Katsumura, Yosuke; Muroya, Yusa; Lin, Mingzhang; Yu, Yan; Mehran, Mostafavi; Sanguanmith, Sunuchakan; Meesungnoen, Jintana; Jay-Gerin, Jean-Paul

2012-09-01

Pulse radiolysis is a very powerful and unique method to observe the transient species and to determine their yields and has been widely used up to now. Since the radiation-induced reactions at elevated temperatures are accelerated, precise measurement becomes difficult by the conventional pulse radiolysis systems. Then, a higher time resolved pulse radiolysis system is highly expected. Recently, an ultrafast pulse radiolysis system has been developed in the University of Tokyo and applied to water radiolysis at elevated temperatures [1]. Temporal behavior of the hydrated electron at elevated temperatures up to 400 deg C has been detected. The time dependent behavior of hydrated electron at elevated temperatures were detected and the latest version of the Monte Carlo simulation code developed at University of Sherbrooke was applied to reproduce the experimental results. From the simulation, it was made clear that the thermalization distance becomes smaller with increasing temperature. In addition, in supercritical water, the initial yield is significantly dependent on density (pressure), which is consistent with our previous evaluation. (authors)

Hydration reactions in pastes C3S+C3A+CaSO4.2aq+H20 at 25°C.I

NARCIS (Netherlands)

Corstanje, W.A.; Stein, H.N.; Stevels, J.M.

1973-01-01

A characteristic retardation of the hydration of C3A is found in pastes C3S+C3A+CaSO4.2aq+H2O of weight ratios 1:3:z:4 at certain values of z, when sulphate concentration becomes insufficient for monosulphate formation. This retardation is ascribed to precipitation of amorphous Al(OH)3, when C3A

Effect of the hydration temperature on the microstructure of Class G cement: C-S-H composition and density

International Nuclear Information System (INIS)

Bahafid, Sara; Ghabezloo, Siavash; Duc, Myriam; Faure, Pamela; Sulem, Jean

2017-01-01

Curing temperature has a significant influence on cement paste microstructure and the properties of its principal hydrate C-S-H. In this paper, the effect of the hydration temperature in the range of 7 °C to 90 °C on the microstructure of a class G oil-well cement is studied. This is done by combining various experimental methods, including X-ray diffraction associated with the Rietveld analysis, thermo-gravimetric analysis, mercury intrusion porosimetry and porosity evaluation by drying. The experimental results show an increase of the capillary porosity and a decrease of the gel porosity by increasing the hydration temperature. This is attributed to a decrease of the C-S-H intrinsic porosity and a corresponding increase of the C-S-H density for higher curing temperatures. The experimental results are used in a simple analysis method to evaluate the density of C-S-H, as well as its C/S ratio and H/S ratio in dry and saturated conditions. The evaluated C-S-H density varies from 1.88 g/cm 3 at 7 °C to 2.10 g/cm 3 at 90 °C. The results also show a decrease of molar C/S ratio with increasing hydration temperature from 1.93 at 7 °C to 1.71 at 90 °C and of the H/S ratio from 5.1 at 7 °C to 2.66 at 90 °C.

Effects of water activity and low molecular weight humectants on skin permeability and hydration dynamics - a double-blind, randomized and controlled study.

Science.gov (United States)

Albèr, C; Buraczewska-Norin, I; Kocherbitov, V; Saleem, S; Lodén, M; Engblom, J

2014-10-01

The mammalian skin is a barrier that effectively separates the water-rich interior of the body from the normally dryer exterior. Changes in the external conditions, for example ambient humidity, have been shown to affect the skin barrier properties. The prime objective of this study was to evaluate the effect of water activity of a topical formulation on skin hydration and permeability. A second objective was to gain more understanding on how two commonly used humectants, urea and glycerol, affect skin barrier function in vivo. Simple aqueous formulations were applied under occlusion to the volar forearm of healthy volunteers. Following 4-h exposure, skin water loss (by transepidermal water loss measurements), skin hydration (by Corneometry) and skin permeability (by time to vasodilation due to benzyl nicotinate exposure) were monitored. The results demonstrate that a relatively small change in the water activity of a topical formulation is sufficient to induce considerable effects on stratum corneum hydration and permeability to exogenous substances. Exposing the skin to high water activity leads to increased skin hydration and also increased permeability. Furthermore, urea and glycerol promote skin hydration and permeability even at reduced water activity of the applied formulation. These results highlight the importance of considering the water activity in topically applied formulations and the potential benefit of using humectants. The results may impact formulation optimization in how to facilitate skin hydration and to modify skin permeability by temporarily open and close the skin barrier. © 2014 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Alcohol cosurfactants in hydrate antiagglomeration.

Science.gov (United States)

York, J Dalton; Firoozabadi, Abbas

2008-08-28

Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at

Transparent hydrogel with enhanced water retention capacity by introducing highly hydratable salt

Energy Technology Data Exchange (ETDEWEB)

Bai, Yuanyuan; Xiang, Feng; Wang, Hong, E-mail: hwang@mail.xjtu.edu.cn, E-mail: suo@seas.harvard.edu [Electronic Materials Research Laboratory, School of Electronics and Information Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Chen, Baohong; Zhou, Jinxiong [State Key Laboratory for Strength and Vibration of Mechanical Structures, International Center for Applied Mechanics and School of Aerospace, Xi' an Jiaotong University, Xi' an 710049 (China); Suo, Zhigang, E-mail: hwang@mail.xjtu.edu.cn, E-mail: suo@seas.harvard.edu [School of Engineering and Applied Sciences, Kavli Institute of Bionano Science and Technology, Harvard University, Cambridge, Massachusetts 02138 (United States)

2014-10-13

Polyacrylamide hydrogels containing salt as electrolyte have been used as highly stretchable transparent electrodes in flexible electronics, but those hydrogels are easy to dry out due to water evaporation. Targeted, we try to enhance water retention capacity of polyacrylamide hydrogel by introducing highly hydratable salts into the hydrogel. These hydrogels show enhanced water retention capacity in different level. Specially, polyacrylamide hydrogel containing high content of lithium chloride can retain over 70% of its initial water even in environment with relative humidity of only 10% RH. The excellent water retention capacities of these hydrogels will make more applications of hydrogels become possible.

Transparent hydrogel with enhanced water retention capacity by introducing highly hydratable salt

International Nuclear Information System (INIS)

Bai, Yuanyuan; Xiang, Feng; Wang, Hong; Chen, Baohong; Zhou, Jinxiong; Suo, Zhigang

2014-01-01

Polyacrylamide hydrogels containing salt as electrolyte have been used as highly stretchable transparent electrodes in flexible electronics, but those hydrogels are easy to dry out due to water evaporation. Targeted, we try to enhance water retention capacity of polyacrylamide hydrogel by introducing highly hydratable salts into the hydrogel. These hydrogels show enhanced water retention capacity in different level. Specially, polyacrylamide hydrogel containing high content of lithium chloride can retain over 70% of its initial water even in environment with relative humidity of only 10% RH. The excellent water retention capacities of these hydrogels will make more applications of hydrogels become possible.

Hydration dynamics in water clusters via quantum molecular dynamics simulations

Energy Technology Data Exchange (ETDEWEB)

Turi, László, E-mail: turi@chem.elte.hu [Department of Physical Chemistry, Eötvös Loránd University, Budapest 112, P. O. Box 32, H-1518 (Hungary)

2014-05-28

We have investigated the hydration dynamics in size selected water clusters with n = 66, 104, 200, 500, and 1000 water molecules using molecular dynamics simulations. To study the most fundamental aspects of relaxation phenomena in clusters, we choose one of the simplest, still realistic, quantum mechanically treated test solute, an excess electron. The project focuses on the time evolution of the clusters following two processes, electron attachment to neutral equilibrated water clusters and electron detachment from an equilibrated water cluster anion. The relaxation dynamics is significantly different in the two processes, most notably restoring the equilibrium final state is less effective after electron attachment. Nevertheless, in both scenarios only minor cluster size dependence is observed. Significantly different relaxation patterns characterize electron detachment for interior and surface state clusters, interior state clusters relaxing significantly faster. This observation may indicate a potential way to distinguish surface state and interior state water cluster anion isomers experimentally. A comparison of equilibrium and non-equilibrium trajectories suggests that linear response theory breaks down for electron attachment at 200 K, but the results converge to reasonable agreement at higher temperatures. Relaxation following electron detachment clearly belongs to the linear regime. Cluster relaxation was also investigated using two different computational models, one preferring cavity type interior states for the excess electron in bulk water, while the other simulating non-cavity structure. While the cavity model predicts appearance of several different hydrated electron isomers in agreement with experiment, the non-cavity model locates only cluster anions with interior excess electron distribution. The present simulations show that surface isomers computed with the cavity predicting potential show similar dynamical behavior to the interior clusters of

Methane hydrate stability and anthropogenic climate change

Directory of Open Access Journals (Sweden)

D. Archer

2007-07-01

Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO₂.

Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

Hydration states of clays followed by water and hydroxyls vibrational analyses in the near infrared: application to saponite and bentonite systems

International Nuclear Information System (INIS)

Rinnert, E.

2004-01-01

The study of the feasibility of a deep geological disposal facility conducted by ANDRA - the French national radioactive waste management agency -, requires the knowledge of water status and water content in clays. Thanks to an original lab-built device coupling vibrational spectroscopies and water adsorption isotherms, adsorbed water and clay's structure are described quantitatively and qualitatively. A multidisciplinary approach allows the description of hydration mechanisms and water molecules network in the inter lamellar space of synthetic saponites. The effects of density and nature of inter-foliar cations and the influence of temperature on hydration are presented. Using mechanisms and important parameters established on saponites, hydration of bentonite MX80 is carried out. In order to describe and quantify simultaneously two different water states, a simple but relevant method of spectra analysis was developed. (author)

Prediction of Water Binding to Protein Hydration Sites with a Discrete, Semiexplicit Solvent Model.

Science.gov (United States)

Setny, Piotr

2015-12-08

Buried water molecules are ubiquitous in protein structures and are found at the interface of most protein-ligand complexes. Determining their distribution and thermodynamic effect is a challenging yet important task, of great of practical value for the modeling of biomolecular structures and their interactions. In this study, we present a novel method aimed at the prediction of buried water molecules in protein structures and estimation of their binding free energies. It is based on a semiexplicit, discrete solvation model, which we previously introduced in the context of small molecule hydration. The method is applicable to all macromolecular structures described by a standard all-atom force field, and predicts complete solvent distribution within a single run with modest computational cost. We demonstrate that it indicates positions of buried hydration sites, including those filled by more than one water molecule, and accurately differentiates them from sterically accessible to water but void regions. The obtained estimates of water binding free energies are in fair agreement with reference results determined with the double decoupling method.

Changes in Transepidermal Water Loss and Skin Hydration according to Expression of Aquaporin-3 in Psoriasis

Science.gov (United States)

Lee, Young; Je, Young-Jin; Lee, Sang-Sin; Li, Zheng Jun; Choi, Dae-Kyoung; Kwon, Yoo-Bin; Sohn, Kyung-Cheol; Im, Myung; Seo, Young Joon

2012-01-01

Background Aquaporins (AQPs) are a family of water transporting proteins present in many mammalian epithelial and endothelial cell types. Among the AQPs, AQP3 is known to be a water/glycerol transporter expressed in human skin. Objective The relationship between the expression level of AQP3 and transpidermal water loss (TEWL) in the lesional and peri-lesional skin of psoriasis-affected patients, and skin hydration in the lesional and peri-lesional skin of psoriasis patients, was investigated. Methods The expression of AQP3 in psoriasis-affected and healthy control skin was determined using immunohistochemical and immunofluroscence staining. TEWL and skin hydration were measured using a Tewameter® TM210 (Courage & Khazaka, Cologne, Germany) and a Corneometer® CM 820 (Courage & Khazaka), respectively. Results AQP3 was mainly expressed in the plasma membrane of stratum corneum and the stratum spinosum in normal epidermis. Unlike the normal epidermis, AQP3 showed decreased expression in the lesional and peri-lesional epidermis of psoriasis. TEWL was increased, and skin hydration was decreased, in the lesional and peri-lesional skin of psoriasis patients, compared with the healthy control sample. Conclusion Although various factors contribute to reduced skin hydration in the lesional and peri-lesional skin of psoriasis, AQP3 appears to be a key factor in the skin dehydration of psoriasis-affected skin. PMID:22577267

Reflective terahertz (THz) imaging: system calibration using hydration phantoms

Science.gov (United States)

Bajwa, Neha; Garritano, James; Lee, Yoon Kyung; Tewari, Priyamvada; Sung, Shijun; Maccabi, Ashkan; Nowroozi, Bryan; Babakhanian, Meghedi; Sanghvi, Sajan; Singh, Rahul; Grundfest, Warren; Taylor, Zachary

2013-02-01

Terahertz (THz) hydration sensing continues to gain traction in the medical imaging community due to its unparalleled sensitivity to tissue water content. Rapid and accurate detection of fluid shifts following induction of thermal skin burns as well as remote corneal hydration sensing have been previously demonstrated in vivo using reflective, pulsed THz imaging. The hydration contrast sensing capabilities of this technology were recently confirmed in a parallel 7 Tesla Magnetic Resonance (MR) imaging study, in which burn areas are associated with increases in local mobile water content. Successful clinical translation of THz sensing, however, still requires quantitative assessments of system performance measurements, specifically hydration concentration sensitivity, with tissue substitutes. This research aims to calibrate the sensitivity of a novel, reflective THz system to tissue water content through the use of hydration phantoms for quantitative comparisons of THz hydration imagery.Gelatin phantoms were identified as an appropriate tissue-mimicking model for reflective THz applications, and gel composition, comprising mixtures of water and protein, was varied between 83% to 95% hydration, a physiologically relevant range. A comparison of four series of gelatin phantom studies demonstrated a positive linear relationship between THz reflectivity and water concentration, with statistically significant hydration sensitivities (p hydration). The THz-phantom interaction is simulated with a three-layer model using the Transfer Matrix Method with agreement in hydration trends. Having demonstrated the ability to accurately and noninvasively measure water content in tissue equivalent targets with high sensitivity, reflective THz imaging is explored as a potential tool for early detection and intervention of corneal pathologies.

Unexpected inhibition of CO₂ gas hydrate formation in dilute TBAB solutions and the critical role of interfacial water structure

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Ngoc N.; Nguyen, Anh V.; Nguyen, Khoi T.; Rintoul, Llew; Dang, Liem X.

2016-12-01

Gas hydrates formed under moderated conditions open up novel approaches to tackling issues related to energy supply, gas separation, and CO₂ sequestration. Several additives like tetra-n-butylammonium bromide (TBAB) have been empirically developed and used to promote gas hydrate formation. Here we report unexpected experimental results which show that TBAB inhibits CO₂ gas hydrate formation when used at minuscule concentration. We also used spectroscopic techniques and molecular dynamics simulation to gain further insights and explain the experimental results. They have revealed the critical role of water alignment at the gas-water interface induced by surface adsorption of tetra-n-butylammonium cation (TBA⁺) which gives rise to the unexpected inhibition of dilute TBAB solution. The water perturbation by TBA⁺ in the bulk is attributed to the promotion effect of high TBAB concentration on gas hydrate formation. We explain our finding using the concept of activation energy of gas hydrate formation. Our results provide a step toward to mastering the control of gas hydrate formation.

Thermoanalytical studies of carbamazepine: hydration/dehydration, thermal decomposition, and solid phase transitions

Directory of Open Access Journals (Sweden)

Mônia Aparecida Lemos Pinto

2014-12-01

Full Text Available Carbamazepine (CBZ, a widely used anticonvulsant drug, can crystallize and exhibits four polymorphic forms and one dihydrate. Anhydrous CBZ can spontaneously absorb water and convert to the hydrate form whose different crystallinity leads to lower biological activity. The present study was concerned to the possibility of recovering the hydrated form by heating. The thermal behavior of spontaneously hydrated carbamazepine was investigated by TG/DTG-DTA and DSC in dynamic atmospheres of air and nitrogen, which revealed that the spontaneous hydration of this pharmaceutical resulted in a Form III hydrate with 1.5 water molecules. After dehydration, this anhydrous Form III converted to Form I, which melted and decomposed in a single event, releasing isocyanic acid, as shown by evolved gas analysis using TG-FTIR. Differential scanning calorimetry analyses revealed that Form III melted and crystallized as Form I, and that subsequent cooling cycles only generated Form I by crystallization. Solid state decomposition kinetic studies showed that there was no change in the substance after the elimination of water by heating to 120 °C. Activation energies of 98 ± 2 and 93 ± 2 kJ mol-1 were found for the hydrated and dried samples, respectively, and similar profiles of activation energy as a function of conversion factor were observed for these samples.

Atomic and nano-scale characterization of a 50-year-old hydrated C3S paste

KAUST Repository

Geng, Guoqing; Taylor, Rae; Bae, Sungchul; Herná ndez-Cruz, Daniel; Kilcoyne, David A.; Emwas, Abdul-Hamid M.; Monteiro, Paulo J M

2015-01-01

This paper investigates the atomic and nano-scale structures of a 50-year-old hydrated alite paste. Imaged by TEM, the outer product C-S-H fibers are composed of particles that are 1.5-2 nm thick and several tens of nanometers long. 29Si NMR shows 47.9% Q1 and 52.1% Q2, with a mean SiO4 tetrahedron chain length (MCL) of 4.18, indicating a limited degree of polymerization after 50 years' hydration. A Scanning Transmission X-ray Microscopy (STXM) study was conducted on this late-age paste and a 1.5 year old hydrated C3S solution. Near Edge X-ray Absorption Fine Structure (NEXAFS) at Ca L3,2-edge indicates that Ca2 + in C-S-H is in an irregular symmetric coordination, which agrees more with the atomic structure of tobermorite than that of jennite. At Si K-edge, multi-scattering phenomenon is sensitive to the degree of polymerization, which has the potential to unveil the structure of the SiO44 - tetrahedron chain. © 2015 Elsevier Ltd. All rights reserved.

Atomic and nano-scale characterization of a 50-year-old hydrated C3S paste

KAUST Repository

Geng, Guoqing

2015-07-15

This paper investigates the atomic and nano-scale structures of a 50-year-old hydrated alite paste. Imaged by TEM, the outer product C-S-H fibers are composed of particles that are 1.5-2 nm thick and several tens of nanometers long. 29Si NMR shows 47.9% Q1 and 52.1% Q2, with a mean SiO4 tetrahedron chain length (MCL) of 4.18, indicating a limited degree of polymerization after 50 years\\' hydration. A Scanning Transmission X-ray Microscopy (STXM) study was conducted on this late-age paste and a 1.5 year old hydrated C3S solution. Near Edge X-ray Absorption Fine Structure (NEXAFS) at Ca L3,2-edge indicates that Ca2 + in C-S-H is in an irregular symmetric coordination, which agrees more with the atomic structure of tobermorite than that of jennite. At Si K-edge, multi-scattering phenomenon is sensitive to the degree of polymerization, which has the potential to unveil the structure of the SiO44 - tetrahedron chain. © 2015 Elsevier Ltd. All rights reserved.

Purification of arsenic contaminated ground water using hydrated manganese dioxide

International Nuclear Information System (INIS)

Raje, N.; Swain, K.K.

2002-01-01

An analytical methodology has been developed for the separation of arsenic from ground water using inorganic material in neutral medium. The separation procedure involves the quantitative retention of arsenic on hydrated manganese dioxide, in neutral medium. The validity of the separation procedure has been checked by a standard addition method and radiotracer studies. Neutron activation analysis (NAA), a powerful measurement technique, has been used for the quantitative determination of arsenic. (author)

Modelling a deep water oil/gas spill under conditions of gas hydrate formation and decomposition

International Nuclear Information System (INIS)

Zheng, L.; Yapa, P.D.

2000-01-01

A model for the behavior of oil and gas spills at deepwater locations was presented. Such spills are subjected to pressures and temperatures that can convert gases to gas hydrates which are lighter than water. Knowing the state of gases as they rise with the plume is important in predicting the fate of an oil or gas plume released in deepwater. The objective of this paper was to develop a comprehensive jet/plume model which includes computational modules that simulate the gas hydrate formation/decomposition of gas bubbles. This newly developed model is based on the kinetics of hydrate formation and decomposition coupled with mass and heat transfer phenomena. The numerical model was successfully tested using results of experimental data from the Gulf of Mexico. Hydrate formation and decomposition are integrated with an earlier model by Yapa and Zheng for underwater oil or gas jets and plumes. The effects of hydrate on the behavior of an oil or gas plume was simulated to demonstrate the models capabilities. The model results indicate that in addition to thermodynamics, the kinetics of hydrate formation/decomposition should be considered when studying the behavior of oil and gas spills. It was shown that plume behavior changes significantly depending on whether or not the local conditions force the gases to form hydrates. 25 refs., 4 tabs., 12 figs

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

Science.gov (United States)

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

Effect of hydration on the amide I band in the binary solvents dioxane-D2O and dioxane-H2O

International Nuclear Information System (INIS)

Kobayashi, M.; Kobayashi, M.

1980-01-01

Hydration of amides in aqueous solutions has been studied by measuring the infrared spectra of amides (benzamide, p-methoxybenzamide, and ropionamide) in dioxane-D 2 O and dioxane-H 2 O mixtures. The absorption due to the C=O stretching (or amide I band) exhibited a very remarkable red shift accompanied by a characteristic change of the band shape as the water content in the medium increased. The spectral change is attributed to the change of the hydration state at the carbonyl oxygen. In the aqueous mixtures, amide molecules participate in an equilibrium among various states of hydration. The weighted mean frequency of the ν/sub C = O/ absorption, anti ν/sub C = O/, varied in proportion to the water contained in the medium. The difference between the anti ν/sub C = O/ value in pure water and that in pure dioxane,Δ anti ν, was used as a measure of the maximum degree of hydration. It was larger for propionamide than for the aromatic amides, suggesting that the steric effect of the substituents is of major importance in hydration. The isotope effect, Δ anti ν/sub D 2 O//Δ anti ν/sub H 2 O/, in the range from 1.4 to 1.6 for all cases examined, indicated that stronger hydration of amides occurred with D 2 O than with H 2 O

Gas hydrates forming and decomposition conditions analysis

Directory of Open Access Journals (Sweden)

А. М. Павленко

2017-07-01

Full Text Available The concept of gas hydrates has been defined; their brief description has been given; factors that affect the formation and decomposition of the hydrates have been reported; their distribution, structure and thermodynamic conditions determining the gas hydrates formation disposition in gas pipelines have been considered. Advantages and disadvantages of the known methods for removing gas hydrate plugs in the pipeline have been analyzed, the necessity of their further studies has been proved. In addition to the negative impact on the process of gas extraction, the hydrates properties make it possible to outline the following possible fields of their industrial use: obtaining ultrahigh pressures in confined spaces at the hydrate decomposition; separating hydrocarbon mixtures by successive transfer of individual components through the hydrate given the mode; obtaining cold due to heat absorption at the hydrate decomposition; elimination of the open gas fountain by means of hydrate plugs in the bore hole of the gushing gasser; seawater desalination, based on the hydrate ability to only bind water molecules into the solid state; wastewater purification; gas storage in the hydrate state; dispersion of high temperature fog and clouds by means of hydrates; water-hydrates emulsion injection into the productive strata to raise the oil recovery factor; obtaining cold in the gas processing to cool the gas, etc.

Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

KAUST Repository

Kirchheim, A. P.; Fernà ndez-Altable, V.; Monteiro, P. J. M.; Dal Molin, D. C. C.; Casanova, I.

2009-01-01

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

KAUST Repository

Kirchheim, A. P.

2009-02-26

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

Experimental flowloop study on methane hydrate formation and agglomeration in high water cut emulsion systems

OpenAIRE

Pham , Trung-Kien; Cameirao , Ana ,; Herri , Jean-Michel

2016-01-01

Thème de cette communication: International Conference on Integrated Petroleum Engineering (IPE); International audience; hydrate risk also increases. Especially in the offshore systems, operating at low temperature and high pressure, conditions are favourable to the formation of gas hydrate, from the combination of liquid water and gas molecules, under the form of a solid phase. It is a serious issue in the flow assurance; it may cause many troubles, up to plugging.This work brings new under...

Phase equilibrium condition of marine carbon dioxide hydrate

International Nuclear Information System (INIS)

Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

2013-01-01

Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

Science.gov (United States)

Burchwell, A.; Cook, A.

2015-12-01

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

Hydrates on tap: scientists say natural gas hydrates may be tough nut to crack

Energy Technology Data Exchange (ETDEWEB)

Mahoney, J.

2001-12-01

Gas hydrates are methane molecules trapped in cages of water molecules, yielding a substance with a slushy, sherbet-like consistency. Drilling for hydrates is similar to conventional oil and gas drilling, however, the secret to economic production still remains hidden. Hydrates exist in abundance in such places as deep ocean floor and below ground in some polar regions. The real challenge lies in producing gas from this resource, inasmuch as there is no existing technology for production of gas specifically from methane hydrates. This paper describes an international research program, involving a five-country partnership to spud the first of three wells into the permafrost of the Mackenzie River Delta in the Northwest Territories. The project, worth about $15 million, has brought together public funding and expertise from Japan, Germany, India as well as the Canadian and US Geological Surveys and the US Dept. of Energy in an effort to gain information on the production response of gas hydrates. The operator of the project is Japan Petroleum Exploration Company of Canada, a subsidiary of Japan National Oil Corporation. Since Japan is poor in domestic hydrocarbon resources, but is surrounded by deep water that contains potential for gas hydrates, Japan has a great deal riding on the success of this project. Germany and the United States are also very much interested. Current thinking is that gas is in contact with the hydrates and that it should be possible to develop a free gas reservoir as if it were a conventional deposit. As the free gas is drawn off, the pressure is reduced on the hydrates in contact with it , the hydrates dissociate from the gas and replenish the conventional reservoir. So far this is still only a theory, but it appears to be a sensible approach to hydrate production. 1 photo.

Hysteresis of methane hydrate formation/decomposition at subsea geological conditions

International Nuclear Information System (INIS)

Klapproth, Alice; Piltz, Ross; Peterson, Vanessa K.; Kennedy, Shane J.; Kozielski, Karen A.; Hartley, Patrick G.

2009-01-01

Full text: Gas hydrates are a major risk when transporting oil and gas in offshore subsea pipelines. Under typical conditions in these pipelines (at high pressure and low temperature) the formation of gas hydrates is favourable. The hydrates form large solid plugs that can block pipelines and can even cause them to burst. This represents a major problem for the gas mining industry, which currently goes to extreme measures to reduce the risk of hydrate formation because there is no reliable experimental data on hydrate processes. The mechanisms of gas hydrate formation, growth and inhibition are poorly understood. A clear understanding of the fundamental processes will allow development of cost effective technologies to avoid production losses in gas pipelines. We are studying the nucleation of the methane hydrates by measuring the hysteresis of hydrate formation/decomposition by neutron diffraction. When a gas hydrate is decomposed (melted) the resulting water has a 'supposed memory effect' raising the probability of rapid hydrate reformation. This rapid reformation does not occur for pure water where nucleation can be delayed by several hours (induction time) due to metastability [1]. The memory effect can only be destroyed by extreme heating of the effected area. Possible causes of this effect include residual water structure, persistent hydrate crystal lites remaining in solution and remaining dissolved gas. We will compare the kinetics of formation and the stability region of hydrate formation of 'memory' water for comparison with pure water. This information has important implications for the oil and gas industry because it should provide a better understanding of the role of multiple dissociation and reformation of gas hydrates in plug formation.

A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy

International Nuclear Information System (INIS)

Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Jorgen

2006-01-01

Recent 27 Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ iso = 5.0 ppm and the quadrupole product parameter P Q = 1.2 MHz, has been characterized in detail by 27 Al MAS and 27 Al{ 1 H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH) 6 3- or O x Al(OH) 6-x (3+x)- units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 o C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al 3+ for Ca 2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed

Thermal conductivity measurements in unsaturated hydrate-bearing sediments

Science.gov (United States)

Dai, Sheng; Cha, Jong-Ho; Rosenbaum, Eilis J.; Zhang, Wu; Seol, Yongkoo

2015-08-01

Current database on the thermal properties of hydrate-bearing sediments remains limited and has not been able to capture their consequential changes during gas production where vigorous phase changes occur in this unsaturated system. This study uses the transient plane source (TPS) technique to measure the thermal conductivity of methane hydrate-bearing sediments with various hydrate/water/gas saturations. We propose a simplified method to obtain thermal properties from single-sided TPS signatures. Results reveal that both volume fraction and distribution of the pore constituents govern the thermal conductivity of unsaturated specimens. Thermal conductivity hysteresis is observed due to water redistribution and fabric change caused by hydrate formation and dissociation. Measured thermal conductivity increases evidently when hydrate saturation Sh > 30-40%, shifting upward from the geometric mean model prediction to a Pythagorean mixing model. These observations envisage a significant drop in sediment thermal conductivity when residual hydrate/water saturation falls below ~40%, hindering further gas production.

Investigation of C3 S hydration mechanism by transmission electron microscope (TEM) with integrated Super-XTM EDS system.

Science.gov (United States)

Sakalli, Y; Trettin, R

2017-07-01

Tricalciumsilicate (C 3 S, Alite) is the major component of the Portland cement clinker. Hydration of Alite is decisive in influencing the properties of the resulting material. This is due to its high content in cement. The mechanism of the hydration of C 3 S is very complicated and not yet fully understood. There are different models describing the hydration of C 3 S in various ways. In this work for a better understanding of hydration mechanism, the hydrated C 3 S was investigated by using the transmission electron microscope (TEM) and for the first time, the samples for the investigations were prepared by using of focused ion beam from sintered pellets of C 3 S. Also, an FEI Talos F200x with an integrated Super-X EDS system was used for the investigations. FEI Talos F200X combines outstanding high-resolution S/TEM and TEM imaging with energy dispersive X-ray spectroscopy signal detection, and 3D chemical characterization with compositional mapping. TEM is a very powerful tool for material science. A high energy beam of electrons passes through a very thin sample, and the interactions between the electrons and the atoms can be used to observe the structure of the material and other features in the structure. TEM can be used to study the growth of layers and their composition. TEM produces high-resolution, two-dimensional images and will be used for a wide range of educational, science and industry applications. Chemical analysis can also be performed. The purpose of these investigations was to get the information about the composition of the C-S-H phases and some details of the nanostructure of the C-S-H phases. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Structures and energetics of hydrated deprotonated cis-pinonic acid anion clusters and their atmospheric relevance

Energy Technology Data Exchange (ETDEWEB)

Hou, Gao-Lei; Zhang, Jun; Valiev, Marat; Wang, Xue-Bin

2017-01-01

Pinonic acid, a C10-monocarboxylic acid with a hydrophilic –CO₂H group and a hydrophobic hydrocarbon backbone, is a key intermediate oxidation product of α-pinene – an important monoterpene compound in biogenic emission processes that influences the atmosphere. Molecular interaction between cis-pinonic acid and water is essential for understanding its role in the formation and growth of pinene-derived secondary organic aerosols. In this work, we studied the structures, energetics, and optical properties of hydrated clusters of cis-pinonate anion (cPA–), the deprotonated form of cis-pinonic acid, by negative ion photoelectron spectroscopy and ab initio theoretical calculations. Our results show that cPA– can adopt two different structural configurations – open and folded. In the absence of waters, the open configuration has the lowest energy and provides the best agreement with the experiment. The addition waters, which mainly interact with the negatively charged -CO₂– group, gradually stabilize the folded configuration and lower its energy difference relative to the most stable open-configured structure. Thermochemical and equilibrium hydrate distribution analysis suggests that the mono- and di- hydrates are likely to exist in humid atmospheric environment with high populations. The detailed molecular description of cPA– hydrated clusters unraveled in this study provides a valuable reference for understanding the initial nucleation process and aerosol formation involving organics containing both hydrophilic and hydrophobic groups, as well as for analyzing the optical properties of those organic aerosols.

Influence of hydration water on CH3NH3PbI3 perovskite films prepared through one-step procedure.

Science.gov (United States)

Wang, Ziyi; Yuan, Sijian; Li, Dahai; Jin, Feng; Zhang, Rongjun; Zhan, Yiqiang; Lu, Ming; Wang, Songyou; Zheng, Yuxiang; Guo, Junpeng; Fan, Zhiyong; Chen, Liangyao

2016-10-31

Organic-inorganic perovskites were fabricated through a one-step procedure with different levels of hydration water in precursor solutions. The optical properties of CH3NH3PbI3 films were investigated through spectroscopic ellipsometry and photoluminescence measurements. With the measured optical constants, the efficiency limit of perovskite solar cells is predicted with a detailed balance model. By comparing the optical measurement to that of planar heterojunction solar cells, we conclude that the radiative efficiency and porosity of the perovskite film significantly influence the performance of perovskite solar cells. An optimized hydration-water concentration is obtained for the 3CH3NH3I:1PbAc2•xH2O precursor solution. The results can provide guidance for further optimization of the device performance of perovskite solar cells by utilizing hydration water.

Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C{sub 3}S, {beta}-C{sub 2}S and their blends; Caracterizacion textural y mecanica de geles C-S-H formados en la hidratacion de muestras sinteticas T1-C{sub 3}S, {beta}-C{sub 2}S y sus mezclas

Energy Technology Data Exchange (ETDEWEB)

Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

2011-07-01

The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C{sub 3}S, {beta}-C{sub 2}S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of {beta}-C{sub 2}S and the 30-70 (T1-C{sub 3}S and {beta}-C{sub 2}S mixture) are higher than those from hydration of T1-C{sub 3}S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the {beta}-C{sub 2}S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from {sup 2}9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

The effect of mineral-based alkaline water on hydration status and the metabolic response to short-term anaerobic exercise

Directory of Open Access Journals (Sweden)

Jakub Chycki

2017-04-01

Full Text Available Previously it was demonstrated that mineralization and alkalization properties of mineral water are important factors influencing acid-base balance and hydration in athletes. The purpose of this study was to investigate the effects of drinking different types of water on urine pH, specific urine gravity, and post-exercise lactate utilization in response to strenuous exercise. Thirty-six male soccer players were divided into three intervention groups, consuming around 4.0 l/day of different types of water for 7 days: HM (n=12; highly mineralized water, LM (n=12; low mineralized water, and CON (n=12; table water. The athletes performed an exercise protocol on two occasions (before and after intervention. The exercise protocol consisted of 5 bouts of intensive 60-s (120% VO2max cycling separated by 60 s of passive rest. Body composition, urinalysis and lactate concentration were evaluated – before (t0, immediately after (t1, 5’ (t2, and 30’ (t3 after exercise. Total body water and its active transport (TBW – total body water / ICW – intracellular water / ECW – extracellular water showed no significant differences in all groups, at both occasions. In the post-hydration state we found a significant decrease of specific urine gravity in HM (1021±4.2 vs 1015±3.8 g/L and LM (1022±3.1 vs 1008±4.2 g/L. We also found a significant increase of pH and lactate utilization rate in LM. In conclusion, the athletes hydrated with alkaline, low mineralized water demonstrated favourable changes in hydration status in response to high-intensity interval exercise with a significant decrease of specific urine gravity, increased urine pH and more efficient utilization of lactate after supramaximal exercise.

Ductile flow of methane hydrate

Science.gov (United States)

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

2003-01-01

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

Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

Directory of Open Access Journals (Sweden)

Shuhua LIU

2017-02-01

Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

Hydration of urea and alkylated urea derivatives

Science.gov (United States)

Kaatze, Udo

2018-01-01

Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

2014-01-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.

2014-07-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

Hydration states of AFm cement phases

Energy Technology Data Exchange (ETDEWEB)

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

2015-07-15

The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

Water distribution and related morphology in human stratum corneum at different hydration levels

NARCIS (Netherlands)

Bouwstra, J.A.; Graaff, de A.; Gooris, G.S.; Nijsse, J.; Wiechers, J.W.; Aelst, van A.C.

2003-01-01

This study focused on the water distribution in human stratum corneum and on the swelling of the corneocytes. For this purpose stratum corneum was hydrated to various levels and used either for Fourier transform infrared spectroscopy or for cryo-scanning electron microscopy. The images were analyzed

Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

Science.gov (United States)

Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

2016-09-14

Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined.

Hydration dynamics of hyaluronan and dextran.

Science.gov (United States)

Hunger, Johannes; Bernecker, Anja; Bakker, Huib J; Bonn, Mischa; Richter, Ralf P

2012-07-03

Hyaluronan is a polysaccharide, which is ubiquitous in vertebrates and has been reported to be strongly hydrated in a biological environment. We study the hydration of hyaluronan in solution using the rotational dynamics of water as a probe. We measure these dynamics with polarization-resolved femtosecond-infrared and terahertz time-domain spectroscopies. Both experiments reveal that a subensemble of water molecules is slowed down in aqueous solutions of hyaluronan amounting to ∼15 water molecules per disaccharide unit. This quantity is consistent with what would be expected for the first hydration shell. Comparison of these results to the water dynamics in aqueous dextran solution, a structurally similar polysaccharide, yields remarkably similar results. This suggests that the observed interaction with water is a common feature for hydrophilic polysaccharides and is not specific to hyaluronan. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

In-situ membrane hydration measurement of proton exchange membrane fuel cells

Science.gov (United States)

Lai, Yeh-Hung; Fly, Gerald W.; Clapham, Shawn

2015-01-01

Achieving proper membrane hydration control is one of the most critical aspects of PEM fuel cell development. This article describes the development and application of a novel 50 cm2 fuel cell device to study the in-situ membrane hydration by measuring the through-thickness membrane swelling via an array of linear variable differential transducers. Using this setup either as an air/air (dummy) cell or as a hydrogen/air (operating) cell, we performed a series of hydration and dehydration experiments by cycling the RH of the inlet gas streams at 80 °C. From the linear relationship between the under-the-land swelling and the over-the-channel water content, the mechanical constraint within the fuel cell assembly can suppress the membrane water uptake by 11%-18%. The results from the air/air humidity cycling test show that the membrane can equilibrate within 120 s for all RH conditions and that membrane can reach full hydration at a RH higher than 140% in spite of the use of a liquid water impermeable Carbel MP30Z microporous layer. This result confirms that the U.S. DOE's humidity cycling mechanical durability protocol induces sufficient humidity swings to maximize hygrothermal mechanical stresses. This study shows that the novel experimental technique can provide a robust and accurate means to study the in-situ hydration of thin membranes subject to a wide range of fuel cell conditions.

Evidencing of collagen polypeptide sequences responsible of hydration by means of 13 C NMR spectra

International Nuclear Information System (INIS)

Trandafir, Viorica; Georgescu, Mariana; Albu, Bujor; Popescu, G.; Akutsu, Hiroshi; Nechifor, Gheorghe

2000-01-01

The aim of these studies is to prepare biomaterials of high biocompatibility to the human body, provided for a long lifetime. Among these important biomaterials also accounts the collagen, with a large application area in medicine, pharmaceutics, cosmetics, etc. Collagen biomaterials of various hydration levels (between 23 - 83%) were prepared by a particular technique, using a matrix of 23% initial humidity. In order to investigate the structural and conformational changes from the collagen macromolecules by denaturation - renaturation, hydration - dehydration, the high-resolution 13 C - NMR solid state and also pore size distribution analysis were carried out. The collagen biomaterials can be made in a large range of shapes and can have structures of mimesis, close to those of the live tissues, when hydrated. (authors)

Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

KAUST Repository

Kirchheim, A. P.

2011-02-21

This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C3A or 3CaO·Al2O 3) and Na-doped tricalcium aluminate (orthorhombic C3A or Na2Ca8Al6O18), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the early phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by 27Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C3A hydration during the early stages. There are differences in the hydration mechanism between the two types of C3A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C3A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C3A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping. © 2011 American Chemical Society.

Barley seed radiosensitivity following post-hydration in oxygen-, nitrogen- and nitrous oxide-saturated water, 1; Influence of caffeine and t-butyl alcohol

Energy Technology Data Exchange (ETDEWEB)

Singh, S.P.; Kesavan, P.C. (Jawaharlal Nehru Univ., New Delhi (India). School of Life Sciences)

1990-06-01

Dry ({approx}3.5 and 4.0 per cent moisture content) barley seeds were exposed to 350 Gy of {sup 60}Co-{gamma}-rays in vacuo and post-hydrated at 4degC for 8 h in O{sub 2}-, N{sub 2}-, or N{sub 2}O-saturated water. The effect of caffeine and t-butyl alcohol (t-BuOH) dissolved in the post-hydration medium on the magnitude of damage developing under these three different gaseous circumstances was studied. The post-irradiation damage and its modification by caffeine and t-BuOH was assessed in terms of 8-day-old seedling injury, peroxidase activity and total peroxides in the 8-day-old seedlings. Post-irradiation O{sub 2}-saturated hydration caused maximal 8-day-old seedling injury, and increased peroxidase activity with concomitant reduction in total peroxides. Both caffeine and t-BuOH afforded significant radioprotection against post-irradiation O{sub 2}-dependent damage. Post-irradiation N{sub 2}O-saturated hydration was even more significantly radioprotective than the N{sub 2}-saturated post-hydration. Under these circumstances, t-BuOH exerted no effect whatsoever on the N{sub 2}- and N{sub 2}O-mediated post-irradiation damage. Caffeine, on the other hand, significantly potentiated these two components of damage. A brief consideration of the physicochemical events which possibly account for the observed effects is presented. (author).

Application of various water soluble polymers in gas hydrate inhibition

DEFF Research Database (Denmark)

Kamal, Muhammad Shahzad; Hussein, Ibnelwaleed A.; Sultan, Abdullah S.

2016-01-01

. This review presents the various types of water soluble polymers used for hydrate inhibition, including conventional and novel polymeric inhibitors along with their limitations. The review covers the relevant properties of vinyl lactam, amide, dendrimeric, fluorinated, and natural biodegradable polymers....... The factors affecting the performance of these polymers and the structure-property relationships are reviewed. A comprehensive review of the techniques used to evaluate the performance of the polymeric inhibitors is given. This review also addresses recent developments, current and future challenges...

Characteristics of Methane Hydrate Formation in Artificial and Natural Media

Directory of Open Access Journals (Sweden)

Qingbai Wu

2013-03-01

Full Text Available The formation of methane hydrate in two significantly different media was investigated, using silica gel as an artificial medium and loess as a natural medium. The methane hydrate formation was observed through the depletion of water in the matrix, measured via the matrix potential and the relationship between the matrix potential and the water content was determined using established equations. The velocity of methane hydrate nucleation slowed over the course of the reaction, as it relied on water transfer to the hydrate surfaces with lower Gibbs free energy after nucleation. Significant differences in the reactions in the two types of media arose from differences in the water retention capacity and lithology of media due to the internal surface area and pore size distributions. Compared with methane hydrate formation in silica gel, the reaction in loess was much slower and formed far less methane hydrate. The results of this study will advance the understanding of how the properties of the environment affect the formation of gas hydrates in nature.

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.; Santamarina, Carlos

2018-01-01

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.

2018-04-02

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

Acid-base balance and hydration status following consumption of mineral-based alkaline bottled water

Directory of Open Access Journals (Sweden)

Heil Daniel P

2010-09-01

Full Text Available Abstract Background The present study sought to determine whether the consumption of a mineral-rich alkalizing (AK bottled water could improve both acid-base balance and hydration status in young healthy adults under free-living conditions. The AK water contains a naturally high mineral content along with Alka-PlexLiquid™, a dissolved supplement that increases the mineral content and gives the water an alkalizing pH of 10.0. Methods Thirty-eight subjects were matched by gender and self-reported physical activity (SRPA, hrs/week and then split into Control (12 women, 7 men; Mean +/- SD: 23 +/- 2 yrs; 7.2 +/- 3.6 hrs/week SRPA and Experimental (13 women, 6 men; 22 +/- 2 yrs; 6.4 +/- 4.0 hrs/week SRPA groups. The Control group consumed non-mineralized placebo bottled water over a 4-week period while the Experimental group consumed the placebo water during the 1st and 4th weeks and the AK water during the middle 2-week treatment period. Fingertip blood and 24-hour urine samples were collected three times each week for subsequent measures of blood and urine osmolality and pH, as well as total urine volume. Dependent variables were analyzed using multivariate repeated measures ANOVA with post-hoc focused on evaluating changes over time within Control and Experimental groups (alpha = 0.05. Results There were no significant changes in any of the dependent variables for the Control group. The Experimental group, however, showed significant increases in both the blood and urine pH (6.23 to 7.07 and 7.52 to 7.69, respectively, a decreased blood and increased urine osmolality, and a decreased urine output (2.51 to 2.05 L/day, all during the second week of the treatment period (P Conclusions Consumption of AK water was associated with improved acid-base balance (i.e., an alkalization of the blood and urine and hydration status when consumed under free-living conditions. In contrast, subjects who consumed the placebo bottled water showed no changes over the

Phase behavior of methane hydrate in silica sand

International Nuclear Information System (INIS)

Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang; Liu, Yu-Feng

2014-01-01

Highlights: • Hydrate p-T trace in coarse-grained sediment is consistent with that in bulk water. • Fine-grained sediment affects hydrate equilibrium for the depressed water activity. • Hydrate equilibrium in sediment is related to the pore size distribution. • The application of hydrate equilibrium in sediment depends on the actual condition. -- Abstract: Two kinds of silica sand powder with different particle size were used to investigate the phase behavior of methane hydrate bearing sediment. In coarse-grained silica sand, the measured temperature and pressure range was (281.1 to 284.2) K and (5.9 to 7.8) MPa, respectively. In fine-grained silica sand, the measured temperature and pressure range was (281.5 to 289.5) K and (7.3 to 16.0) MPa, respectively. The results show that the effect of coarse-grained silica sand on methane hydrate phase equilibrium can be ignored; however, the effect of fine-grained silica sand on methane hydrate phase equilibrium is significant, which is attributed to the depression of water activity caused by the hydrophilicity and negatively charged characteristic of silica particle as well as the pore capillary pressure. Besides, the analysis of experimental results using the Gibbs–Thomson equation shows that methane hydrate phase equilibrium is related to the pore size distribution of silica sand. Consequently, for the correct application of phase equilibrium data of hydrate bearing sediment, the geological condition and engineering requirement should be taken into consideration in gas production, resource evaluation, etc

Gas hydrate cool storage system

Science.gov (United States)

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

1984-09-12

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

Time-series measurements of bubble plume variability and water column methane distribution above Southern Hydrate Ridge, Oregon

Science.gov (United States)

Philip, Brendan T.; Denny, Alden R.; Solomon, Evan A.; Kelley, Deborah S.

2016-03-01

An estimated 500-2500 gigatons of methane carbon is sequestered in gas hydrate at continental margins and some of these deposits are associated with overlying methane seeps. To constrain the impact that seeps have on methane concentrations in overlying ocean waters and to characterize the bubble plumes that transport methane vertically into the ocean, water samples and time-series acoustic images were collected above Southern Hydrate Ridge (SHR), a well-studied hydrate-bearing seep site ˜90 km west of Newport, Oregon. These data were coregistered with robotic vehicle observations to determine the origin of the seeps, the plume rise heights above the seafloor, and the temporal variability in bubble emissions. Results show that the locations of seep activity and bubble release remained unchanged over the 3 year time-series investigation, however, the magnitude of gas release was highly variable on hourly time scales. Bubble plumes were detected to depths of 320-620 m below sea level (mbsl), in several cases exceeding the upper limit of hydrate stability by ˜190 m. For the first time, sustained gas release was imaged at the Pinnacle site and in-between the Pinnacle and the Summit area of venting, indicating that the subseafloor transport of fluid and gas is not restricted to the Summit at SHR, requiring a revision of fluid-flow models. Dissolved methane concentrations above background levels from 100 to 300 mbsl are consistent with long-term seep gas transport into the upper water column, which may lead to the build-up of seep-derived carbon in regional subsurface waters and to increases in associated biological activity.

Examination of Hydrate Formation Methods: Trying to Create Representative Samples

Energy Technology Data Exchange (ETDEWEB)

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

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 controlled 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

Skin hydration and cooling effect produced by the Voltaren® vehicle gel.

Science.gov (United States)

Hug, Agnes M; Schmidts, Thomas; Kuhlmann, Jens; Segger, Dörte; Fotopoulos, Grigorios; Heinzerling, Johanna

2012-05-01

Voltaren vehicle gel is the carrier substance of the topical Voltaren products. This vehicle gel is especially formulated to be easily applied on the skin, while providing some sensory benefits. The present study aims to substantiate the widely perceived hydrating and cooling effect of Voltaren vehicle gel. Volar forearm skin hydration and transepidermal water loss (TEWL) were measured and user satisfaction was evaluated by questionnaires, after application in 31 healthy, female volunteers. The cooling effect was investigated for 40 min with thermal imaging on 12 forearm sites of six healthy subjects. Voltaren vehicle gel application increased skin hydration by 13.1% (P = 0.0002) when compared with the untreated site, 8 h after the final treatment after 2 weeks. TEWL decreased on both treated (0.37 g/m(2) /h) and untreated (0.74 g/m(2) /h) forearm sites after 2 weeks (8 h after last treatment), demonstrating a relative increase of 6.5% in water loss. Voltaren vehicle gel application resulted in a rapid reduction of skin surface temperature by 5.1°C after only 3 min with an average maximum reduction of 5.8°C after 10 min. The cooling effect was experienced by 94% subjects, while 74% felt that their skin became softer. No adverse events, including skin irritation, were reported during the study and by the 37 participants. This study showed a statistically significant increase in skin hydration as well as a rapid cooling effect lasting approximately 30 min, after application of Voltaren vehicle gel. The small relative increase in water loss may be attributed to an additional skin surface water loss secondary to the increased water content brought into the skin by the Voltaren vehicle gel. The use did not induce any skin irritation and was found acceptable to use by the majority of participants. © 2011 John Wiley & Sons A/S.

Influence of aggregate and supplementary cementitious materials on the properties of hydrated lime (CL90s mortars

Directory of Open Access Journals (Sweden)

S. Pavía

2016-11-01

Full Text Available Hydrated lime is a historic material currently used in conservation. It hardens slowly by carbonation slowing construction however, supplementary cementitious materials accelerate hardening enhancing strength. Hydrated-lime mortars with rice husk ash–RHA-; ground granulated blastfurnace slag–GGBS- and increasing amounts of two aggregates were studied. Increasing aggregate lowered strength as interfacial zones proliferate; it lowered hygric properties and raised water demand. Aggregate content/composition didn’t affect the high water retention. For the higher aggregate contents (90 days, limestone mortars are c.20% stronger than silica mortars while the (1:1 silica sand mortars are 56% stronger in flexion. Additions increased strength with little impact on hygric properties. GGBS increased strength c.six times. RHA increased strength with little impact on hygric properties due to its great specific surface and high water-demand increasing porosity. GGBS and RHA properties ruling hydrate production and the kinetics of the pozzolanic reaction are considered partially responsible for the mortar property variation.

Is Br2 hydration hydrophobic?

Science.gov (United States)

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

2017-02-28

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

Study on molecular controlled mining system of methane hydrate; Methane hydrate no bunshi seigyo mining ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

Kuriyagawa, M; Saito, T; Kobayashi, H; Karasawa, H; Kiyono, F; Nagaoki, R; Yamamoto, Y; Komai, T; Haneda, H; Takahashi, Y [National Institute for Resources and Environment, Tsukuba (Japan); Nada, H [Science and Technology Agency, Tokyo (Japan)

1997-02-01

Basic studies are conducted for the collection of methane from the methane hydrate that exists at levels deeper than 500m in the sea. The relationship between the hydrate generation mechanism and water cluster structure is examined by use of mass spectronomy. It is found that, among the stable liquid phase clusters, the (H2O)21H{sup +} cluster is the most stable. Stable hydrate clusters are in presence in quantities, and participate in the formation of hydrate crystal nuclei. For the elucidation of the nucleus formation mechanism, a kinetic simulation is conducted of molecules in the cohesion system consisting of water and methane molecules. Water molecules that array near methane molecules at the normal pressure is disarrayed under a higher pressure for rearray into a hydrate structure. Hydrate formation and breakdown in the three-phase equilibrium state of H2O, CH4, and CO2 at a low temperature and high pressure are tested, which discloses that supercooling is required for formation, that it is possible to extract CH4 first for replacement by guest molecule CO2 since CO2 is stabler than CH4 at a lower pressure or higher temperature, and that formation is easier to take place when the grain diameter is larger at the formation point since larger grain diameters result in a higher formation temperature. 3 figs.

Prediction of hydroxyl concentrations in cement pore water using a numerical cement hydration model

NARCIS (Netherlands)

Eijk, van R.J.; Brouwers, H.J.H.

2000-01-01

In this paper, a 3D numerical cement hydration model is used for predicting alkali and hydroxyl concentrations in cement pore water. First, this numerical model is calibrated for Dutch cement employing both chemical shrinkage and calorimetric experiments. Secondly, the strength development of some

Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties; Hydratation des argiles gonflantes: sequence d'hydratation multi-echelle determination des energies macroscopiques a partir des proprietes microscopiques

Energy Technology Data Exchange (ETDEWEB)

Salles, F

2006-10-15

Smectites have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon; Santamarina, Carlos

2016-01-01

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon

2016-06-20

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

Historical methane hydrate project review

Science.gov (United States)

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

2013-01-01

In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

The Structure and Transport of Water and Hydrated Ions Within Hydrophobic, Nanoscale Channels

International Nuclear Information System (INIS)

Holt, J.K.; Herberg, J.L.; Wu, Y.; Schwegler, E.; Mehta, A.

2009-01-01

The purpose of this project includes an experimental and modeling investigation into water and hydrated ion structure and transport at nanomaterials interfaces. This is a topic relevant to understanding the function of many biological systems such as aquaporins that efficiently shuttle water and ion channels that permit selective transport of specific ions across cell membranes. Carbon nanotubes (CNT) are model nanoscale, hydrophobic channels that can be functionalized, making them artificial analogs for these biological channels. This project investigates the microscopic properties of water such as water density distributions and dynamics within CNTs using Nuclear Magnetic Resonance (NMR) and the structure of hydrated ions at CNT interfaces via X-ray Absorption Spectroscopy (XAS). Another component of this work is molecular simulation, which can predict experimental measurables such as the proton relaxation times, chemical shifts, and can compute the electronic structure of CNTs. Some of the fundamental questions this work is addressing are: (1) what is the length scale below which nanoscale effects such as molecular ordering become important, (2) is there a relationship between molecular ordering and transport?, and (3) how do ions interact with CNT interfaces? These are questions of interest to the scientific community, but they also impact the future generation of sensors, filters, and other devices that operate on the nanometer length scale. To enable some of the proposed applications of CNTs as ion filtration media and electrolytic supercapacitors, a detailed knowledge of water and ion structure at CNT interfaces is critical.

Development of hydrate risk quantification in oil and gas production

Science.gov (United States)

Chaudhari, Piyush N.

Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

CH4 fluxes across the seafloor at three district gas hydrate fields: Impacts on ocean and atmosphere chemistry

Energy Technology Data Exchange (ETDEWEB)

Kastner, M.; Bartlett, D.; MacDonald, I.; Solomon, E.

2005-07-01

The role of methane hydrate in the global methane budget is poorly documented because relatively little is known about the transport of methane through the seafloor into the ocean and atmosphere, and the extent of en route water-column methanotrophy. Pore fluids and water column samples within and adjacent to methane plumes were analyzed for methane, dissolved inorganic C (DIC), sulfide/sulfate, alkalinity, and major element concentrations, and for delta{sup 13}C-CH4 and DIC, at three distinct gas hydrate environments. The three environments are: Bush Hill (BH) in the northern Gulf of Mexico (GOM), Eel River (ER) offshore Northern California, and North and South Hydrate Ridges (HR), Cascadia, Oregon margin. The methane source at these sites ranges from mostly thermogenic at GOM to primarily biogenic at HR. At these three distinct gas hydrate environments, at all the sites a significant enrichment in {sup 13}C-CH4 along isopycnals away from the methane plumes is observed, indicating extensive aerobic bacterial methane oxidation in the water column, and correspondingly of oxygen consumption. This is principally pronounced in the mostly biogenic methane setting. The delta{sup 13}C-CH4 values range from approx. 12 to -67 , PDB, at the Hydrate Ridges, from approx. 34 to -52 at Eel River, and from approx. 41 to -67 at Bush Hill. The large variation in methane C isotope ranges between the sites suggests that major differences exist in both the rates of aerobic methane oxidation and system openness at the studied locations. Methane fluxes across the sediment/seawater interface were measured, with a flux meter, MOSQUITO (Multiple Orifice Sampler and Quantitative Injection Tracer Observers) only at BH (Solomon et al., 2005). Water column methane concentrations are on average lower at HR than at ER and GOM. Preliminary estimates suggests that aerobic oxidation is nearly complete, consumes most to all of the water column methane at HR, but at the GOM only approx. 80% to a

Acoustical method of whole-body hydration status monitoring

Science.gov (United States)

Sarvazyan, A. P.; Tsyuryupa, S. N.; Calhoun, M.; Utter, A.

2016-07-01

An acoustical handheld hydration monitor (HM) for assessing the water balance of the human body was developed. Dehydration is a critical public health problem. Many elderly over age of 65 are particularly vulnerable as are infants and young children. Given that dehydration is both preventable and reversible, the need for an easy-to-perform method for the detection of water imbalance is of the utmost clinical importance. The HM is based on an experimental fact that ultrasound velocity in muscle is a linear function of water content and can be referenced to the hydration status of the body. Studies on the validity of HM for the assessment of whole-body hydration status were conducted in the Appalachian State University, USA, on healthy young adults and on elderly subjects residing at an assisted living facility. The HM was able to track changes in total body water during periods of acute dehydration and rehydration in athletes and day-to-day and diurnal variability of hydration in elderly. Results of human studies indicate that HM has a potential to become an efficient tool for detecting abnormal changes in the body hydration status.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

2018-05-01

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

Well log characterization of natural gas-hydrates

Science.gov (United States)

Collett, Timothy S.; Lee, Myung W.

2012-01-01

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

Ab initio modelling of methane hydrate thermophysical properties.

Science.gov (United States)

Jendi, Z M; Servio, P; Rey, A D

2016-04-21

The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

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

Science.gov (United States)

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.

Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

Science.gov (United States)

Avdellidou, C.; Delbo', M.; Fienga, A.

2018-04-01

Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

X-ray spectra and theoretical elastic properties of crystalline calcium silicate hydrates: comparison with cement hydrated gels

Directory of Open Access Journals (Sweden)

Ayuela, A.

2010-09-01

Full Text Available For 22 crystalline Calcium Silicates Hydrates, we have calculated their structure and their elastic properties by atomistic force field methods as well as simulate their Xray diffraction patterns. From the computed Young moduli, it can be suggested that the key parameters to determine the elastic properties of crystalline Calcium Silicate Hydrates are densities and water content. We have compared these trends with those of cementitious C-S-H gel and synthetic C-S-H type I as a function of their C/S ratios and nominal water content. Our comparison show that the experimentally suggested values of density and Young moduli for C-S-H gel lie in the range of the calculated CSH crystals. However, we conclude that a detailed correspondence might require investigating structurally within CSH gels the role of water and especially of Ca and Si sites through their C/S ratio.

En este trabajo se han calculado para 22 Silicatos Cálcicos Hidratados cristalinos, su estructura y sus propiedades elásticas mediante métodos atomísticos “force field”, así como simulado sus espectros de difracción de rayos X. De los módulos de Young calculados se puede deducir, que los parámetros clave que determinan las propiedades elásticas de los Silicatos Cálcicos Hidratados cristalinos son la densidad y el contenido en agua. Nuestros resultados muestran que los valores experimentales de la densidad y de los módulos de Young para el gel C-S-H están dentro del rango de los cristales de CSH calculados. Sin embargo, podemos concluir que para establecer una correlación más directa sería necesario investigar el papel que juegan el agua y sobre todo el Ca y Si, mediante la relación C/S, en la estructura del gel CSH.

Residue specific hydration of primary cell wall potato pectin identified by solid-state 13C single-pulse MAS and CP/MAS NMR spectroscopy

DEFF Research Database (Denmark)

Larsen, Flemming Hofmann; Chrestensen, Inge Byg; Damager, Iben

2011-01-01

Hydration of rhamnogalacturonan-I (RG-I) derived from potato cell wall was analyzed by 13C single-pulse (SP) magic-angle-spinning (MAS) and 13C cross-polarization (CP) MAS nuclear magnetic resonance (NMR) and supported by 2H SP/MAS NMR experiments. The study shows that the arabinan side chains...... hydrate more readily than the galactan side chains and suggests that the overall hydration properties can be controlled by modifying the ratio of these side chains. Enzymatic modification of native (NA) RG-I provided samples with reduced content of arabinan (sample DA), galactan (sample DG), or both side...... chains (sample DB). Results of these samples suggested that hydration properties were determined by the length and character of the side chains. NA and DA exhibited similar hydration characteristics, whereas DG and DB were difficult to hydrate because of the less hydrophilic properties of the rhamnose...

Methane Production from Gas Hydrate Deposits through Injection of Supercritical CO₂

Directory of Open Access Journals (Sweden)

Matthias Haeckel

2012-06-01

Full Text Available The recovery of natural gas from CH₄-hydrate deposits in sub-marine and sub-permafrost environments through injection of CO₂ is considered a suitable strategy towards emission-neutral energy production. This study shows that the injection of hot, supercritical CO₂ is particularly promising. The addition of heat triggers the dissociation of CH₄-hydrate while the CO₂, once thermally equilibrated, reacts with the pore water and is retained in the reservoir as immobile CO₂-hydrate. Furthermore, optimal reservoir conditions of pressure and temperature are constrained. Experiments were conducted in a high-pressure flow-through reactor at different sediment temperatures (2 °C, 8 °C, 10 °C and hydrostatic pressures (8 MPa, 13 MPa. The efficiency of both, CH₄ production and CO₂ retention is best at 8 °C, 13 MPa. Here, both CO₂- and CH₄-hydrate as well as mixed hydrates can form. At 2 °C, the production process was less effective due to congestion of transport pathways through the sediment by rapidly forming CO₂-hydrate. In contrast, at 10 °C CH₄ production suffered from local increases in permeability and fast breakthrough of the injection fluid, thereby confining the accessibility to the CH₄ pool to only the most prominent fluid channels. Mass and volume balancing of the collected gas and fluid stream identified gas mobilization as equally important process parameter in addition to the rates of methane hydrate dissociation and hydrate conversion. Thus, the combination of heat supply and CO₂ injection in one supercritical phase helps to overcome the mass transfer limitations usually observed in experiments with cold liquid or gaseous CO₂.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

Science.gov (United States)

Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2012-12-01

The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by

Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

Science.gov (United States)

Hofer, Thomas S.; Hünenberger, Philippe H.

2018-06-01

The absolute intrinsic hydration free energy GH+,w a t ◦ of the proton, the surface electric potential jump χwa t ◦ upon entering bulk water, and the absolute redox potential VH+,w a t ◦ of the reference hydrogen electrode are cornerstone quantities for formulating single-ion thermodynamics on absolute scales. They can be easily calculated from each other but remain fundamentally elusive, i.e., they cannot be determined experimentally without invoking some extra-thermodynamic assumption (ETA). The Born model provides a natural framework to formulate such an assumption (Born ETA), as it automatically factors out the contribution of crossing the water surface from the hydration free energy. However, this model describes the short-range solvation inaccurately and relies on the choice of arbitrary ion-size parameters. In the present study, both shortcomings are alleviated by performing first-principle calculations of the hydration free energies of the sodium (Na+) and potassium (K+) ions. The calculations rely on thermodynamic integration based on quantum-mechanical molecular-mechanical (QM/MM) molecular dynamics (MD) simulations involving the ion and 2000 water molecules. The ion and its first hydration shell are described using a correlated ab initio method, namely resolution-of-identity second-order Møller-Plesset perturbation (RIMP2). The next hydration shells are described using the extended simple point charge water model (SPC/E). The hydration free energy is first calculated at the MM level and subsequently increased by a quantization term accounting for the transformation to a QM/MM description. It is also corrected for finite-size, approximate-electrostatics, and potential-summation errors, as well as standard-state definition. These computationally intensive simulations provide accurate first-principle estimates for GH+,w a t ◦, χwa t ◦, and VH+,w a t ◦, reported with statistical errors based on a confidence interval of 99%. The values obtained

A new combined nanoSIMS and continuous-flow IRMS approach to measure hydrogen isotopes from water in hydrated rhyolitic glass

Science.gov (United States)

Gatti, E.; Kitchen, N.; Newman, S.; Guan, Y.; Westgate, J.; Pearce, N. J. G.; Nikolic, D.; Eiler, J. M.

2016-12-01

The hydrogen-isotope value of water of hydration (or secondary water) preserved in rhyolitic glasses may provide significant insights regarding the climate at the time of their deposition and the impact of super-eruptions upon the environment. However, the ability of the glass to retain the environmental D/H isotopic signal after hydration needs to be tested, since modifications to the D/H systematics may result from the continuous exchange of D/H with the atmosphere or condensed water after initial glass hydration. Ideal geological archives to test whether the glass retains its original hydrogen signal are sediments in natural waters and ice cores, which preserve tephra in constrained horizons that can be independently isotopically characterised. However, tephra in marine and fresh water sediments and ice cores are often present in concentrations of the order of 1000 grains/cm3 (IRMS methods require much more material ( 100-500 mg) and therefore cannot be applied. We present here a new integrated nanoSIMS and continuous flow IRMS approach to understand how water is distributed within single glass grains (diffusion profiles), quantify the time of hydration of young (Holocene) and old (Miocene) already well-characterised rhyolitic glasses, and measure the D/H ratio of the hydration water on single grains and bulk material consisting of only approximately 0.1-1 mg. The IRMS method measures the absolute abundance of hydrogen released from the sample by continuous-flow mass spectrometry. Current data indicates that the method can accurately measure a hydrogen signal from a rock sample containing at least 400 nanomoles of H2, corresponding to 70 µg of water, which translates to 1 mg of hydrous glass (>3 wt%) or 15 mg of dry ( 0.5 wt%) obsidian chips. The method can be improved by reducing the blank to IRMS method will be compared to sub-micron mapping of single-grains using a high-resolution ion microprobe, the CAMECA NanoSIMS 50L, in the Microanalysis Center for

Nuclear magnetic resonance study of diffusion and relaxation in hydrating white cement pastes of different water content

International Nuclear Information System (INIS)

Nestle, Nikolaus; Galvosas, Petrik; Geier, Oliver; Zimmermann, Christian; Dakkouri, Marwan; Karger, Jorg

2001-01-01

While the nuclear spin relaxation time changes in hydrating cement materials have been widely studied by various groups during the last 20 years, data on the self-diffusion behavior of the pore water during hydration of a cement paste are much scarcer. Taking advantage of improved spectrometer hardware for pulsed field gradient diffusometry and a specialized pulse sequence which is designed to compensate the detrimental effects of inner magnetic field gradients in the sample we have studied the water self-diffusion behavior in pastes prepared from white cement at various water/cement ratios. For the same mixtures, studies of the transverse spin relaxation behavior were also conducted. A comparison of the results from both techniques shows that the diffusion coefficient starts to decrease only much later than the relaxation times for all pastes studied. [copyright] 2001 American Institute of Physics

Towards CO2 sequestration and applications of CO2 hydrates: the effects of tetrahydrofuran on the phase equilibria of CO2 hydrates

International Nuclear Information System (INIS)

Khalik, M.S.; Peters, C.J.

2006-01-01

The increasing quantity of carbon dioxide (CO 2 ) in the atmosphere has caused widespread global concerns. Capturing CO 2 from its sources and stored it in the form of gas hydrates and application of CO 2 hydrates are among the proposed methods to overcome this problem. In order to make hydrate-based process more attractive, the use of cyclic ethers as promoters is suggested to reduce the required hydrate formation pressure and enhancing the corresponding kinetic rate. In the present work, tetrahydrofuran (THF) is chosen as a hydrate promoter, participating in forming hydrates and produces mixed hydrate together with CO 2 . The pressure and temperature ranges of hydrate stability region are carefully determined through phase equilibrium measurement of the ternary CO 2 , tetrahydrofuran (THF) and water systems. From the experimental results, it is confirmed that the presence of THF in CO 2 + water systems will extend the hydrate formation region to higher temperature at a constant pressure. The extension of the hydrate stability region is depended on the overall concentration of the ternary system. Moreover, four-phase equilibrium of H-Lw-Lv-V is observed in the system, which may be due to a liquid phase split. In the region where the four-phase equilibrium exists, the ternary system loses its concentration dependency of the hydrate equilibrium conditions. (Author)

A thermodynamic approach to the hydration of sulphate-resisting Portland cement

International Nuclear Information System (INIS)

Lothenbach, Barbara; Wieland, Erich

2006-01-01

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials

Failure of cement hydrates: freeze-thaw and fracture

Science.gov (United States)

Ioannidou, Katerina; Del Gado, Emanuela; Ulm, Franz-Josef; Pellenq, Roland

Mechanical and viscoelastic behavior of concrete crucially depends on cement hydrates, the ``glue'' of cement. Even more than the atomistic structure, the mesoscale amorphous texture of cement hydrates over hundreds of nanometers plays a crucial role for material properties. We use simulations that combine information of the nano-scale building units of cement hydrates and on their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles.Our mesoscale model was able to reconcile different experimental results ranging from small-angle neutron scattering, SEM, adsorption/desorption of N2, and water to nanoindentation and gain the new fundamental insights into the microscopic origin of the properties measured. Our results suggest that heterogeneities developed during the early stages of hydration persist in the structure of C-S-H, impacting the rheological and mechanical performance of the hardened cement paste. In this talk I discuss recent investigation on failure mechanism at the mesoscale of hardened cement paste such as freeze-thaw and fracture. Using correlations between local volume fractions and local stress we provide a link between structural and mechanical heterogeneities during the failure mechanisms.

Authigenic rhodochrosite from a gas hydrate-bearing structure in Lake Baikal

Science.gov (United States)

Krylov, Alexey A.; Hachikubo, Akihiro; Minami, Hirotsugu; Pogodaeva, Tatyana V.; Zemskaya, Tamara I.; Krzhizhanovskaya, Mariya G.; Poort, Jeffrey; Khlystov, Oleg M.

2018-02-01

Early diagenetic carbonates are rare in Lake Baikal. Siderite (Fe carbonate) concretions in the sediments were discovered only recently. Here, we discuss the first finding of rhodochrosite concretions (Mn carbonate) discovered in the near-bottom sediments of the gas hydrate-bearing seepage structure St. Petersburg-2 in the deep water environment of the Central Baikal Basin. The crystal lattice of rhodochrosite contains iron and calcium substituting to manganese. Based on pore water geochemistry and of δ 13C values of rhodochrosite (- 23.3 and - 29.4‰), carbon dioxide (+ 3.8 to - 16.1‰) and methane (- 63.2 to - 67.8‰), we show that carbonate crystallization most likely occurred during microbial anaerobic oxidation of organic matter, and that part of the oxygen making up the rhodochrosite seems to be derived from the 18O-rich water released from dissociating gas hydrates.

Effect of compositions in nanostructured lipid carriers (NLC) on skin hydration and occlusion.

Science.gov (United States)

Loo, Ch; Basri, M; Ismail, R; Lau, Hln; Tejo, Ba; Kanthimathi, Ms; Hassan, Ha; Choo, Ym

2013-01-01

To study the effects of varying lipid concentrations, lipid and oil ratio, and the addition of propylene glycol and lecithin on the long-term physical stability of nanostructured lipid nanocarriers (NLC), skin hydration, and transepidermal water loss. The various NLC formulations (A1-A5) were prepared and their particle size, zeta potential, viscosity, and stability were analyzed. The formulations were applied on the forearms of the 20 female volunteers (one forearm of each volunteer was left untreated as a control). The subjects stayed for 30 minutes in a conditioned room with their forearms uncovered to let the skin adapt to the temperature (22°C ± 2°C) and humidity (50% ± 2%) of the room. Skin hydration and skin occlusion were recorded at day one (before treatment) and day seven (after treatment). Three measurements for skin hydration and skin occlusion were performed in each testing area. NLC formulations with the highest lipid concentration, highest solid lipid concentration, and additional propylene glycol (formulations A1, A2, and A5) showed higher physical stability than other formulations. The addition of propylene glycol into an NLC system helped to reduce the particle size of the NLC and enhanced its long-term physical stability. All the NLC formulations were found to significantly increase skin hydration compared to the untreated controls within 7 days. All NLC formulations exhibited occlusive properties as they reduced the transepidermal water loss within 7 days. This effect was more pronounced with the addition of propylene glycol or lecithin into an NLC formulation, whereby at least 60% reduction in transepidermal water loss was observed. NLCs with high lipid content, solid lipid content, phospholipid, and lecithin are a highly effective cosmetic delivery system for cosmetic topical applications that are designed to boost skin hydration.

The potential for methane hydrate formation in deep repositories of spent nuclear fuel in granitic rocks

International Nuclear Information System (INIS)

Tohidi, Bahman; Chapoy, Antonin; Smellie, John; Puigdomenech, Ignasi

2010-12-01

The main aim of this work was to establish whether the pertaining pressure and temperature conditions and dissolved gas concentration in groundwater is conducive to gas hydrate formation using a modelling approach. The hydrate stability pressure-temperature zone of dissolved methane in the presence of salt has been obtained through calculations which show that a decrease in the system pressure and/or an increase in salt concentration favours hydrate formation, as both factors reduce equilibrium gas solubility in the aqueous phase. This behaviour is unlike that of the system including a gas phase, where the water phase is always saturated with methane, and hence the methane solubility in water is not a limiting factor. The main conclusion is that hydrate formation is not possible at the reported methane concentrations and water salinities for the Forsmark and Laxemar sites in Sweden and Olkiluoto in Finland. At the highest salinities and methane concentrations encountered, namely ∼0.00073 mole fraction methane and ∼10 mass % NaCl at a depth of 1,000 m in Olkiluoto, Finland, hydrates could form if the system temperatures and pressures are below 2.5 deg C and 60 bar, respectively, i.e. values that are much lower than those prevailing at that depth (∼20 deg C and ∼100 bar, respectively). Furthermore, the calculated results provide the necessary data to estimate the effect of increase in dissolved methane concentration on potential hydrate formation, as well as two phase flow. The available depth dependency of methane concentration at the sites studied in Sweden and Finland was used in another study to estimate the diffusive flow of methane in the rock volumes. These diffusion rates, which are highest at Olkiluoto, indicate that even if the conditions were to become favourable to methane hydrate formation, then it would take several millions of years before a thin layer of hydrates could be formed, a condition which is outside the required period of satisfactory

The potential for methane hydrate formation in deep repositories of spent nuclear fuel in granitic rocks

Energy Technology Data Exchange (ETDEWEB)

Tohidi, Bahman; Chapoy, Antonin (Hydrafact Ltd, Inst. of Petroleum Engineering, Heriot-Watt Univ., Edinburgh (United Kingdom)); Smellie, John (Conterra AB, Uppsala (Sweden)); Puigdomenech, Ignasi (Swedish Nuclear Fuel and Waste Management Co., Stockholm (Sweden))

2010-12-15

The main aim of this work was to establish whether the pertaining pressure and temperature conditions and dissolved gas concentration in groundwater is conducive to gas hydrate formation using a modelling approach. The hydrate stability pressure-temperature zone of dissolved methane in the presence of salt has been obtained through calculations which show that a decrease in the system pressure and/or an increase in salt concentration favours hydrate formation, as both factors reduce equilibrium gas solubility in the aqueous phase. This behaviour is unlike that of the system including a gas phase, where the water phase is always saturated with methane, and hence the methane solubility in water is not a limiting factor. The main conclusion is that hydrate formation is not possible at the reported methane concentrations and water salinities for the Forsmark and Laxemar sites in Sweden and Olkiluoto in Finland. At the highest salinities and methane concentrations encountered, namely approx0.00073 mole fraction methane and approx10 mass % NaCl at a depth of 1,000 m in Olkiluoto, Finland, hydrates could form if the system temperatures and pressures are below 2.5 deg C and 60 bar, respectively, i.e. values that are much lower than those prevailing at that depth (approx20 deg C and approx100 bar, respectively). Furthermore, the calculated results provide the necessary data to estimate the effect of increase in dissolved methane concentration on potential hydrate formation, as well as two phase flow. The available depth dependency of methane concentration at the sites studied in Sweden and Finland was used in another study to estimate the diffusive flow of methane in the rock volumes. These diffusion rates, which are highest at Olkiluoto, indicate that even if the conditions were to become favourable to methane hydrate formation, then it would take several millions of years before a thin layer of hydrates could be formed, a condition which is outside the required period of

Experimental Determination of Refractive Index of Gas Hydrates

DEFF Research Database (Denmark)

Bylov, Martin; Rasmussen, Peter

1997-01-01

. For methane hydrate (structure I) the refractive index was found to be 1.346 and for natural gas hydrate (structure II) it was found to be 1.350. The measurements further suggest that the gas hydrate growth rate increases if the water has formed hydrates before. The induction time, on the other hand, seems......The refractive indexes of methane hydrate and natural gas hydrate have been experimentally determined. The refractive indexes were determined in an indirect manner making use of the fact that two non-absorbing materials will have the same refractive index if they cannot be distinguished visually...

Hydrate phase equilibria of furan, acetone, 1,4-dioxane, TBAC and TBAF

International Nuclear Information System (INIS)

Kamran-Pirzaman, Arash; Pahlavanzadeh, Hassan; Mohammadi, Amir H.

2013-01-01

Highlights: • Experimental hydrate dissociation conditions are reported for CO 2 /methane + some water soluble/insoluble hydrate formers. • An isochoric pressure-search method was used to generate the experimental data. • The data are compared with the corresponding literature data in the presence of pure water. • The hydrate promotion effects of acetone, 1,4-dioxane, furan, TBAC and TBAF are discussed. -- Abstract: In this communication, we first report experimental hydrate dissociation pressures for the methane/carbon dioxide + furan/acetone/1,4-dioxane + water and the methane + tetra n-butyl ammonium chloride (TBAC) + water as well as the carbon dioxide + tetra n-butyl ammonium floride (TBAF) + water systems in the temperature ranges of (269.9 to 303.3) K. An isochoric pressure-search method was used to generate the experimental data. The hydrate dissociation data are compared with the corresponding literature data, if exists, and the literature data in the presence of pure water and acceptable agreement is observed. A discussion is made on hydrate promotion effects of acetone, 1,4-dioxane, furan, TBAC and TBAF

Effect of compositions in nanostructured lipid carriers (NLC on skin hydration and occlusion

Directory of Open Access Journals (Sweden)

Loo CH

2012-12-01

Full Text Available CH Loo,1,2 M Basri,2 R Ismail,1 HLN Lau,1 BA Tejo,2 MS Kanthimathi,3 HA Hassan,1 YM Choo11Malaysian Palm Oil Board, Bandar Baru Bangi, 2Department of Chemistry, Universiti Putra Malaysia, Serdang, 3Department of Molecular Medicine, University of Malaya, Kuala Lumpur, MalaysiaPurpose: To study the effects of varying lipid concentrations, lipid and oil ratio, and the addition of propylene glycol and lecithin on the long-term physical stability of nanostructured lipid nanocarriers (NLC, skin hydration, and transepidermal water loss.Methods: The various NLC formulations (A1–A5 were prepared and their particle size, zeta potential, viscosity, and stability were analyzed. The formulations were applied on the forearms of the 20 female volunteers (one forearm of each volunteer was left untreated as a control. The subjects stayed for 30 minutes in a conditioned room with their forearms uncovered to let the skin adapt to the temperature (22°C ± 2°C and humidity (50% ± 2% of the room. Skin hydration and skin occlusion were recorded at day one (before treatment and day seven (after treatment. Three measurements for skin hydration and skin occlusion were performed in each testing area.Results: NLC formulations with the highest lipid concentration, highest solid lipid concentration, and additional propylene glycol (formulations A1, A2, and A5 showed higher physical stability than other formulations. The addition of propylene glycol into an NLC system helped to reduce the particle size of the NLC and enhanced its long-term physical stability. All the NLC formulations were found to significantly increase skin hydration compared to the untreated controls within 7 days. All NLC formulations exhibited occlusive properties as they reduced the transepidermal water loss within 7 days. This effect was more pronounced with the addition of propylene glycol or lecithin into an NLC formulation, whereby at least 60% reduction in transepidermal water loss was observed

Experimental determination of methane hydrate formation in the presence of ammonia

Energy Technology Data Exchange (ETDEWEB)

Dong, T.B.; Wang, L.Y.; Liu, A.X.; Guo, X.Q.; Chen, G.J.; Ma, Q.L.; Li, G.W. [China Univ. of Petroleum, Beijng (China). State Key Laboratory of Heavy Oil Processing

2008-07-01

Gas hydrates are non-stoichiometric inclusion compounds that are created by a lattice of water molecules. The host molecule has a strong hydrogen bond and encages low molecular weight gases or volatile liquids. The guest molecules favor hydrate formation. Historically, gas hydrates have been thought to be problematic during natural gas transportation because the formed solid hydrate can block pipelines and cause tubing and casing collapse. However, the discovery of huge deposits of gas hydrates in deep-sea sediments and in permafrost has renewed interest in gas hydrates as a new energy resource. This paper discussed a study that is a part of an ongoing experimental and computational program dealing with the thermodynamics of gas hydrate formation in ammonia-water systems. The purpose of the study was to develop a new method to separate and recycle the vent gas of ammonia synthesis by forming or dissociating hydrate. The hydrate-forming conditions of methane in ammonia and water system were studied and reported in this paper with reference to the experimental apparatus and procedure. The materials and preparation of samples were also explained. The experimental results showed that the ammonia had an inhibitive effect on the hydrate formation. 26 refs., 2 tabs., 3 figs.

Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties

International Nuclear Information System (INIS)

Salles, F.

2006-10-01

Smectites have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism

Science.gov (United States)

Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

2015-01-01

Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in-situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h~0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding. PMID:25856773

Formation of submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Soloviev, V.; Ginsburg, G.D. (Reserch Institute of Geology and Mineral Resources of the Ocean ' ' VNII Okeangeologia' ' , St. Petersburg (Russian Federation))

1994-03-01

Submarine gas hydrates have been discoverd in the course of deep-sea drilling (DSDP and ODP) and bottom sampling in many offshore regions. This paper reports on expeditions carried out in the Black, Caspian and Okhotsk Seas. Gas hydrate accumulations were discovered and investigated in all these areas. The data and an analysis of the results of the deep-sea drilling programme suggest that the infiltration of gas-bearing fluids is a necessary condition for gas hydrate accumulation. This is confirmed by geological observations at three scale levels. Firstly, hydrates in cores are usually associated with comparatively coarse-grained, permeable sediments as well as voids and fractures. Secondly, hydrate accumulations are controlled by permeable geological structures, i.e. faults, diapirs, mud volcanos as well as layered sequences. Thirdly, in the worldwide scale, hydrate accumulations are characteristic of continental slopes and rises and intra-continental seas where submarine seepages also are widespread. Both biogenic and catagenic gas may occur, and the gas sources may be located at various distances from the accumulation. Gas hydrates presumably originate from water-dissolved gas. The possibility of a transition from dissolved gas into hydrate is confirmed by experimental data. Shallow gas hydrate accumulations associated with gas-bearing fluid plumes are the most convenient features for the study of submarine hydrate formation in general. These accumulations are known from the Black, Caspian and Okhotsk Seas, the Gulf of Mexico and off northern California. (au) (24 refs.)