Drosophila divalent metal ion transporter Malvolio is required in dopaminergic neurons for feeding decisions.

Science.gov (United States)

Søvik, E; LaMora, A; Seehra, G; Barron, A B; Duncan, J G; Ben-Shahar, Y

2017-06-01

Members of the natural resistance-associated macrophage protein (NRAMP) family are evolutionarily conserved metal ion transporters that play an essential role in regulating intracellular divalent cation homeostasis in both prokaryotes and eukaryotes. Malvolio (Mvl), the sole NRAMP family member in insects, plays a role in food choice behaviors in Drosophila and other species. However, the specific physiological and cellular processes that require the action of Mvl for appropriate feeding decisions remain elusive. Here, we show that normal food choice requires Mvl function specifically in the dopaminergic system, and can be rescued by supplementing food with manganese. Collectively, our data indicate that the action of the Mvl transporter affects food choice behavior via the regulation of dopaminergic innervation of the mushroom bodies, a principle brain region associated with decision-making in insects. Our studies suggest that the homeostatic regulation of the intraneuronal levels of divalent cations plays an important role in the development and function of the dopaminergic system and associated behaviors. © 2017 John Wiley & Sons Ltd and International Behavioural and Neural Genetics Society.

Dispersion relations of the acoustic modes in divalent liquid metals

Directory of Open Access Journals (Sweden)

Inui Masanori

2017-01-01

Full Text Available Collective dynamics in liquid Ca and liquid Cd was studied by inelastic x-ray scattering (IXS. Using our experimental technique to prepare proper sample cells and high performance of an IXS beamline (BL35XU at SPring-8 in Japan, the dynamic structure factor with reasonable statistics was obtained for these divalent liquid metals. For both liquids, the dynamic structure factor at low Q exhibits a central peak with a shoulder or small hump clearly visible on each side, and the inelastic excitation energy determined using the model function composed of Lorentzian and the damped harmonic oscillator function disperses with increasing Q. The dispersion curves of these liquids were compared with that of the longitudinal acoustic phonon in each crystalline phase. From these results, clear difference in the interatomic interaction be- tween liquid Ca and liquid Cd was inferred.

Divalent Metal Ions Induced Osteogenic Differentiation of MC3T3E1

Science.gov (United States)

Wang, Guoshou; Su, Wenta; Chen, Pohung; Huang, Teyang

2017-12-01

Biomaterial scaffolds blended with biochemical signal molecules with adequate osteoinductive and osteoconductive properties have attracted significant interest in bone tissue engineering regeneration. The divalent metal ions can gradually release from the scaffold into the culture medium and then induced osteoblastic differentiation of MC3T3E1. These MC3T3E1 cells expressed high activity of alkaline phosphatase, bone-related gene expression of collagen type I, Runx2, osteopontin, osteocalcin, and significantly enhanced deposited minerals on scaffold after 21 days of culture. This experiment provided a useful inducer for osteogenic differentiation in bone repair.

Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from sulfolobus solfataricus

DEFF Research Database (Denmark)

Hansen, Dennis K.; Webb, Helen; Nielsen, Jonas Willum

2015-01-01

Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the-1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous e......, although less dramatically with some activating metal ions. No major differences in the pH dependence between wild-type and mutant enzymes were found in the presence of different metal ions. The pH optimum was 5, but enzyme instability was observed at pH...

Interaction of divalent metal ions with Zn(2+)-glycerophosphocholine cholinephosphodiesterase from ox brain.

Science.gov (United States)

Lee, K J; Kim, M R; Kim, Y B; Myung, P K; Sok, D E

1997-12-01

The effect of divalent metal ions on the activity of glycerophosphocholine cholinephosphodiesterse from ox brain was examined. Zn(2+)- and Co(2+)-glycerophosphocholine cholinephosphodiesterases were prepared from the exposure of apoenzyme to Zn2+ and Co2+, respectively, and the properties of two metallo-phosphodiesterases were compared to those of native phosphodiesterase. Although two metallo-enzymes were similar in expressing Km value, optimum pH or sensitivity to Cu2+, they differed in the susceptibility to the inhibition by thiocholine or tellurite; while Co(2+)-phosphodiesterase was more sensitive to tellurites, Zn(2+)-phosphodiesterase was more susceptible to inhibition by thiocholine. In addition, Zn(2+)-phosphodiesterase was more thermo-stable than Co2+ enzyme. Separately, when properties of native phosphodiesterase were compared to those of each metallo-phosphodiesterase, native phosphodiesterase was found to be quite similar to Zn(2+)-phosphodiesterase in many respects. Even in thermo-stability, native enzyme resembled Zn(2+)-phosphodiesterase rather than Co(2+)-enzyme. Consistent with this, the stability of native phosphodiesterase was maintained in the presence of Zn2+, but not Co2+, Mn2+ was also as effective as Zn2+ in the stabilization of the enzyme. Noteworthy, the native enzyme was found to be inhibited competitively by Cu2+ with a Ki value of 20 microM, and its inhibitory action was antagonized effectively by Zn2+ or Co2+. Also, choline, another competitive inhibitor of the enzyme, appeared to antagonize the inhibitory action of Cu2+. Taken together, it is suggested that there may be multiple binding sites for divalent metal ions in the molecule of glycerophosphocholine cholinephosphodiesterase.

Toxic and biochemical effects of divalent metal ions in Drosophila: correlation to effects in mice and to chemical softness parameters

Energy Technology Data Exchange (ETDEWEB)

Jacobson, K B; Turner, J E; Christie, N T; Owenby, R K

1983-01-01

The mechanism of toxicity of 11 divalent cations was evaluated by determining the effects of dietary administration to Drosophila melanogaster and measurement of the frequency of lethality at 4 days, alterations in the developmental patterns of proteins, and changes in specific transfer RNAs. The relative effectiveness of divalent cations to kill Drosophila is significantly correlated to the relative values of the coordinate bond energy of the metal ions. The resistance of Drosophila to cadmium toxicity appears to be genetically determined since different inbred strains vary markedly. Also, the resistance is maximal in the young adult. Two different genetic strains seem to respond to different cations (Cd/sup 2 +/, Hg/sup 2 +/, Cu/sup 2 +/, Co/sup 2 +/, Ba/sup 2 +/, and Sr/sup 2 +/) in a similar manner. Basic mechanisms of toxicity may be studied in Drosophila as well as mice since the chemical properties of the metals reflect their toxic effects on the former as closely as the latter. 25 references, 5 figures, 1 table.

Binding of Divalent Cations to Polygalacturonate: A Mechanism Driven by the Hydration Water.

Science.gov (United States)

Huynh, Uyen T D; Lerbret, Adrien; Neiers, Fabrice; Chambin, Odile; Assifaoui, Ali

2016-02-11

We have investigated the interactions between polygalacturonate (polyGal) and four divalent cations (M(2+) = Ba(2+), Ca(2+), Mg(2+), Zn(2+)) that differ in size and affinity for water. Our results evidence that M(2+)-polyGal interactions are intimately linked to the affinity of M(2+) for water. Mg(2+) interacts so strongly with water that it remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. In contrast, the other cations form transient ionic pairs with polyGal by releasing preferentially one water molecule (for Zn(2+)) or two (for Ca(2+) and Ba(2+)), which corresponds to monodentate and bidentate binding modes with carboxylates, respectively. The mechanism for the binding of these three divalent cations to polyGal can be described by two steps: (i) monocomplexation and formation of point-like cross-links between polyGal chains (at low M(2+)/Gal molar ratios, R) and (ii) dimerization (at higher R). The threshold molar ratio, R*, between these two steps depends on the nature of divalent cations and is lower for calcium ions (R* 0.3). This difference may be explained by the intermediate affinity of Ca(2+) for water with respect to those of Zn(2+) and Ba(2+), which may induce the formation of cross-links of intermediate flexibility. By comparison, the lower and higher flexibilities of the cross-links formed by Zn(2+) and Ba(2+), respectively, may shift the formation of dimers to higher molar ratios (R*).

Influence of divalent metal ions on degradation of dimethylsulphide ...

African Journals Online (AJOL)

SERVER

2007-06-04

Jun 4, 2007 ... Dimethylsulphide degradation by intact cells of Thiobacillus thioparus TK-m was stimulated by the addition of divalent .... plastic vials in ice-cooled water. .... tization of authotrophic sulphur bacteria oxidizing dimethyldisulphide.

Identification of a divalent metal cation binding site in herpes simplex virus 1 (HSV-1) ICP8 required for HSV replication.

Science.gov (United States)

Bryant, Kevin F; Yan, Zhipeng; Dreyfus, David H; Knipe, David M

2012-06-01

Herpes simplex virus 1 (HSV-1) ICP8 is a single-stranded DNA-binding protein that is necessary for viral DNA replication and exhibits recombinase activity in vitro. Alignment of the HSV-1 ICP8 amino acid sequence with ICP8 homologs from other herpesviruses revealed conserved aspartic acid (D) and glutamic acid (E) residues. Amino acid residue D1087 was conserved in every ICP8 homolog analyzed, indicating that it is likely critical for ICP8 function. We took a genetic approach to investigate the functions of the conserved ICP8 D and E residues in HSV-1 replication. The E1086A D1087A mutant form of ICP8 failed to support the replication of an ICP8 mutant virus in a complementation assay. E1086A D1087A mutant ICP8 bound DNA, albeit with reduced affinity, demonstrating that the protein is not globally misfolded. This mutant form of ICP8 was also recognized by a conformation-specific antibody, further indicating that its overall structure was intact. A recombinant virus expressing E1086A D1087A mutant ICP8 was defective in viral replication, viral DNA synthesis, and late gene expression in Vero cells. A class of enzymes called DDE recombinases utilize conserved D and E residues to coordinate divalent metal cations in their active sites. We investigated whether the conserved D and E residues in ICP8 were also required for binding metal cations and found that the E1086A D1087A mutant form of ICP8 exhibited altered divalent metal binding in an in vitro iron-induced cleavage assay. These results identify a novel divalent metal cation-binding site in ICP8 that is required for ICP8 functions during viral replication.

Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

Energy Technology Data Exchange (ETDEWEB)

Kayaaltı, Zeliha, E-mail: kayaalti@ankara.edu.tr; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

2015-02-15

Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metal trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels. �

Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

International Nuclear Information System (INIS)

Kayaaltı, Zeliha; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

2015-01-01

Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metal trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels. �

Characterisation of products of tricalcium silicate hydration in the presence of heavy metals

International Nuclear Information System (INIS)

Chen, Q.Y.; Hills, C.D.; Tyrer, M.; Slipper, I.; Shen, H.G.; Brough, A.

2007-01-01

The hydration of tricalcium silicate (C 3 S) in the presence of heavy metal is very important to cement-based solidification/stabilisation (s/s) of waste. In this work, tricalcium silicate pastes and aqueous suspensions doped with nitrate salts of Zn 2+ , Pb 2+ , Cu 2+ and Cr 3+ were examined at different ages by X-ray powder diffraction (XRD), thermal analysis (DTA/TG) and 29 Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). It was found that heavy metal doping accelerated C 3 S hydration, even though Zn 2+ doping exhibited a severe retardation effect at an early period of time of C 3 S hydration. Heavy metals retarded the precipitation of portlandite due to the reduction of pH resulted from the hydrolysis of heavy metal ions during C 3 S hydration. The contents of portlandite in the control, Cr 3+ -doped, Cu 2+ -doped, Pb 2+ -doped and Zn 2+ -doped C 3 S pastes aged 28 days were 16.7, 5.5, 5.5, 5.5, and 2 Cr(OH) 7 .3H 2 O, Ca 2 (OH) 4 4Cu(OH) 2 .2H 2 O and CaZn 2 (OH) 6 .2H 2 O). These compounds were identified as crystalline phases in heavy metal doping C 3 S suspensions and amorphous phases in heavy metal doping C 3 S pastes. 29 Si NMR data confirmed that heavy metals promoted the polymerisation of C-S-H gel in 1-year-old of C 3 S pastes. The average numbers of Si in C-S-H gel for the Zn 2+ -doped, Cu 2+ -doped, Cr 3+ -doped, control, and Pb 2+ -doped C 3 S pastes were 5.86, 5.11, 3.66, 3.62, and 3.52. And the corresponding Ca/Si ratios were 1.36, 1.41, 1.56, 1.57 and 1.56, respectively. This study also revealed that the presence of heavy metal facilitated the formation of calcium carbonate during C 3 S hydration process in the presence of carbon dioxide

Hydration number of alkali metal ions determined by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen

2008-01-01

of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

Halides of BET-TTF: novel hydrated molecular metals

Energy Technology Data Exchange (ETDEWEB)

Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

2000-01-07

A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

Influence of commercial (Fluka) naphthenic acids on acid volatile sulfide (AVS) production and divalent metal precipitation.

Science.gov (United States)

McQueen, Andrew D; Kinley, Ciera M; Rodgers, John H; Friesen, Vanessa; Bergsveinson, Jordyn; Haakensen, Monique C

2016-12-01

Energy-derived waters containing naphthenic acids (NAs) are complex mixtures often comprising a suite of potentially problematic constituents (e.g. organics, metals, and metalloids) that need treatment prior to beneficial use, including release to receiving aquatic systems. It has previously been suggested that NAs can have biostatic or biocidal properties that could inhibit microbially driven processes (e.g. dissimilatory sulfate reduction) used to transfer or transform metals in passive treatment systems (i.e. constructed wetlands). The overall objective of this study was to measure the effects of a commercially available (Fluka) NA on sulfate-reducing bacteria (SRB), production of sulfides (as acid-volatile sulfides [AVS]), and precipitation of divalent metals (i.e. Cu, Ni, Zn). These endpoints were assessed following 21-d aqueous exposures of NAs using bench-scale reactors. After 21-days, AVS molar concentrations were not statistically different (pAVS production was sufficient in all NA treatments to achieve ∑SEM:AVS AVS) could be used to treat metals occurring in NAs affected waters. Copyright © 2016 Elsevier Inc. All rights reserved.

Determination of membrane hydration numbers of alkali metal ions by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen; Junaid Mohamed Jafeen, Mohamed; Careem, M.A.

2010-01-01

, and a secondary (or outer) solvation shell, consisting of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior...... may depend on the details of ion hydration. Although the solvation of alkali metal ions in aqueous solution has been discussed for many years, there is still no clear consensus. Part of the discrepancy is simply that different methods measure over different time scales, and therefore do...... not necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique...

Determining the selectivity of divalent metal cations for the carboxyl group of alginate hydrogel beads during competitive sorption.

Science.gov (United States)

An, Byungryul; Lee, Healim; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

2015-11-15

To investigate the competitive sorption of divalent metal ions such as Ca(2+), Cu(2+), Ni(2+), and Pb(2+) on alginate hydrogel beads, batch and column tests were conducted. The concentration of carboxyl group was found to be limited in the preparation of spherical hydrogel beads. From kinetic test results, 80% of sorption was observed within 4h, and equilibrium was attained in 48 h. According to the comparison of the total uptake and release, divalent metal ions were found to stoichiometrically interact with the carboxyl group in the alginate polymer chain. From the Langmuir equation, the maximum capacities of Pb(2+), Cu(2+), and Ni(2+) were calculated to be 1.1, 0.48, and 0.13 mmol/g, respectively. The separation factor (α) values for αPb/Cu, αPb/Ni, and αCu/Ni were 14.0, 98.9, and 7.1, respectively. The sorption capacity of Pb(2+) was not affected by the solution pH; however, the sorption capacities of Cu(2+) and Ni(2+) decreased with increasing solution pH, caused by competition with hydrogen. According to the result from the fixed column test, Pb(2+) exhibited the highest affinity, followed by Cu(2+) and Ni(2+), which is in exact agreement with those of kinetic and isotherm tests. The sorbent could be regenerated using 4% HCl, and the regenerated sorbent exhibited 90% capacity upto 9 cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

OpenAIRE

Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

1993-01-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

Optical study of gamma irradiated sodium metaphosphate glasses containing divalent metal oxide MO (ZnO or CdO

Directory of Open Access Journals (Sweden)

E. Nabhan

Full Text Available Sodium metaphosphate glasses containing divalent metal oxide, ZnO or CdO with composition 50 P2O5 – (50 − x Na2O – x MO (ZnO, or CdO where x = 0, 10, 20 (mol% were prepared by conventional melt method. UV/visible spectroscopy and FTIR spectroscopy are measured before and after exposing to successive gamma irradiation doses (5–80 kGy. The optical absorption spectra results of the samples before irradiation reveal a strong UV absorption band at (∼230 nm which is related to unavoided iron impurities. The effects of gamma irradiation on the optical spectral properties of the various glasses have been compared. From the optical absorption spectral data, the optical band gap is evaluated. The main structural groups and the influence of both divalent metal oxide and gamma irradiation effect on the structural vibrational groups are realized through IR spectroscopy. The FTIR spectra of γ-irradiated samples are characterized by the stability of the number and position for the main characteristic band of phosphate groups. To better understood the structural changes during γ-irradiation, a deconvolution of FTIR spectra in the range 650–1450 cm−1 is made. The FTIR deconvolution results found evidence that, the changes occurring after gamma irradiation have been related to irradiation induced structural defects and compositional changes. Keywords: Sodium metaphosphate glass, UV–visible spectra, IR spectra, Deconvolution, Optical band gap, Gamma ray

Production of Hydrated Metal Ions by Fast Ion or Atom Beam Sputtering. Collision-Induced Dissociation and Successive Hydration Energies of Gaseous Cu+ with 1-4 Water Molecules

NARCIS (Netherlands)

Magnera, Thomas F.; David, Donald E.; Stulik, Dusan; Orth, Robert G.; Jonkman, Harry T.; Michl, Josef

1989-01-01

Low-temperature sputtering of frozen aqueous solutions of metal salts, of hydrated crystalline transition-metal salts, of frosted metal surfaces, and of frosted metal salts with kiloelectronvolt energy rare gas atoms or ions produces copious amounts of cluster ions, among which M+(H2O)n and/or

Hydration forces and liquid-like layer on the ice/metal interface

International Nuclear Information System (INIS)

Daikhin, Leonid; Tsionsky, Vladimir

2007-01-01

A model to describe the phenomenon of the liquid-like layer is proposed. It is based on the theory of the hydration forces proposed by Gruen and Marcelja (1983 J. Chem. Soc. Faraday Trans. II 79 225), taking into account the influence of ions on the free energy of water. The model was applied to experimental data obtained with the quartz-crystal microbalance, in a study of the liquid-like layer between metal and frozen aqueous electrolytes and between metal and ice

Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

KAUST Repository

Ye, Min

2016-10-01

A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

KAUST Repository

Ye, Min; Wen, Yuelu; Li, Huifang; Fu, Yejuan; Wang, Qinghao

2016-01-01

A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

Divalent cations in tears, and their influence on tear film stability in humans and rabbits.

Science.gov (United States)

Wei, Xiaojia Eric; Markoulli, Maria; Millar, Thomas J; Willcox, Mark D P; Zhao, Zhenjun

2012-06-05

Reduced tear film stability is reported to contribute to dry eye. Rabbits are known to have a more stable tear film than humans. Thus, we sought to examine the tears of rabbits and humans for metal cations, and to test how they influence tear film stability. Tears were collected from 10 healthy humans and 6 rabbits. Tear osmolality was measured by vapor pressure osmometer, and metals analyzed using inductively coupled plasma (ICP) mass spectrometry or ICP atomic emission spectroscopy. The influence of divalent cations on tears was analyzed by measuring surface tension using the Langmuir trough in vitro, using different concentrations of cations in the subphase, and grading the tear break-up in rabbits in vivo after instillation of chelating agents. Rabbit tears had a higher osmolality compared to humans. Major metals did not differ between species; however, rabbits had higher levels of Mg(2+) (1.13 vs. 0.39 mM) and Ca(2+) (0.75 vs. 0.36 mM). In rabbit tears in vitro, diminishing divalent cations resulted in a decrease in the maximum surface pressure from 37 to 30 mN/m. In vivo, an increase in the amount of tear film that was broken-up was found. In contrast, when changing divalent cation concentrations in human tears, the maximum surface pressure remained at 26 mN/m. The normal osmolality of rabbit tears is significantly higher than that in humans. While divalent cations had little influence on human tears, they appear to have an important role in maintaining tear film stability in rabbits.

New 14-membered octaazamacrocyclic complexes of divalent transition metal ions with their antimicrobial and spectral studies

Science.gov (United States)

Singh, D. P.; Kumar, Krishan; Sharma, Chetan

2010-01-01

A novel series of macrocyclic complexes of the type [M(C 18H 14N 10S 2)X 2]; where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); X = Cl -, NO 3-, CH 3COO - has been synthesized by [2+2] condensation of thiocarbohydrazide and isatin in the presence of divalent metal salts in methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic measurements, electronic, NMR and infrared spectral studies. The low value of molar conductance indicates them to be non-electrolytes. On the basis of various studies a distorted octahedral geometry may be proposed for all of these complexes. These metal complexes were also tested for their in vitro antimicrobial activities against some Gram-positive bacteria viz. Staphylococcus aureus, Bacillus subtilis, and some Gram-negative bacteria Escherichia coli, Pseudomonas aeruginosa and some fungal strains Aspergillus niger, Aspergillus flavus (molds), Candida albicans, Saccharomyces cerevisiae (yeasts). The results obtained were compared with standard antibiotic: Ciprofloxacin and the standard antifungal drug: Amphotericin-B.

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

Science.gov (United States)

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Studies on the effect of divalent metal ions on exfoliative toxins from Staphylococcus hyicus: indications of ExhA and ExhB being metalloproteins.

Science.gov (United States)

Andresen, L O

1999-04-01

The exfoliative toxins ExhA and ExhB produced by Staphylococcus hyicus strains NCTC10350 and 1289D-88, respectively, were investigated with regard to the effect of divalent metal ions on toxin production as measured in indirect enzyme-linked immunosorbent assay (ELISA) using monoclonal antibodies. Data were obtained as endpoint titer values and used as semiquantitative measures for the amount of exfoliative toxin detected in culture supernatants. It was shown that the endpoint titers of ExhA in supernatants from cultures of strain NCTC10350 grown in the presence of 0.5 mM CaCl2, Cu(NO3)2 or ZnSO4 were higher compared to titers obtained by growth in medium supplemented with a number of other divalent metal salts. The titer of ExhB as determined in the indirect ELISA was increased by addition of 0.5 mM CoCl2, Cu(NO3)2 or CuSO4 to the growth medium. When ExhA or ExhB, prepared without addition of metal salt to the liquid growth medium, was subsequently incubated with 25 mM of Co2+, Cu2+ or Zn2+, the endpoint titers of the toxins were increased. Dialysis of ExhA and ExhB prepared with Zn2+ and Co2+, respectively, against certain metal chelators, resulted in a reduction of the titer determined in ELISA. Other metal chelators had varied effect in the detection of the toxins in ELISA. It was, however, not possible to restore the recognition of toxins by the monoclonal antibodies by incubation of EDDHA-dialyzed toxin preparations with Co2+, Cu2+ or Zn2+. The results of this study suggest that ExhA and ExhB are metalloproteins.

Kinetics of the reactions of hydrated electrons with metal complexes

International Nuclear Information System (INIS)

Korsse, J.

1983-01-01

The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

Science.gov (United States)

Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

1993-11-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between

Divalent Metal Ion Transport across Large Biological Ion Channels and Their Effect on Conductance and Selectivity

Directory of Open Access Journals (Sweden)

Elena García-Giménez

2012-01-01

Full Text Available Electrophysiological characterization of large protein channels, usually displaying multi-ionic transport and weak ion selectivity, is commonly performed at physiological conditions (moderate gradients of KCl solutions at decimolar concentrations buffered at neutral pH. We extend here the characterization of the OmpF porin, a wide channel of the outer membrane of E. coli, by studying the effect of salts of divalent cations on the transport properties of the channel. The regulation of divalent cations concentration is essential in cell metabolism and understanding their effects is of key importance, not only in the channels specifically designed to control their passage but also in other multiionic channels. In particular, in porin channels like OmpF, divalent cations modulate the efficiency of molecules having antimicrobial activity. Taking advantage of the fact that the OmpF channel atomic structure has been resolved both in water and in MgCl2 aqueous solutions, we analyze the single channel conductance and the channel selectivity inversion aiming to separate the role of the electrolyte itself, and the counterion accumulation induced by the protein channel charges and other factors (binding, steric effects, etc. that being of minor importance in salts of monovalent cations become crucial in the case of divalent cations.

Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

International Nuclear Information System (INIS)

Sabil, Khalik M.; Roman, Vicente R.; Witkamp, Geert-Jan; Peters, Cor J.

2010-01-01

In the present work, experimental data on the equilibrium conditions of mixed CO 2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO 2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L W ), liquid organic (L V ), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO 2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF 2 2 . Among the cations studied, the strength of hydrate inhibition increases in the following order: K + + 2+ 2+ . Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br - > Cl - > F - . Based on the results, it is suggested that the probability of formation and the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water

Polymerization of a divalent/tetravalent metal-storing atom-mimicking dendrimer

OpenAIRE

Albrecht, Ken; Hirabayashi, Yuki; Otake, Masaya; Mendori, Shin; Tobari, Yuta; Azuma, Yasuo; Majima, Yutaka; Yamamoto, Kimihisa

2016-01-01

The phenylazomethine dendrimer (DPA) has a layer-by-layer electron density gradient that is an analog of the Bohr atom (atom mimicry). In combination with electron pair mimicry, the polymerization of this atom-mimicking dendrimer was achieved. The valency of the mimicked atom was controlled by changing the chemical structure of the dendrimer. By mimicking a divalent atom, a one-dimensional (1D) polymer was obtained, and by using a planar tetravalent atom mimic, a 2D polymer was obtained. Thes...

Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

Science.gov (United States)

Craciun, Smaranda; Donald, Kelling J

2009-07-06

We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

International Nuclear Information System (INIS)

Bilewicz, A.; Narbutt, J.; Dybczynski, R.

1992-01-01

The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(II), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10 -3 *mol*dm -3 . Cations of zinc, manganese and mercury which form much weaker ammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions. (author) 10 refs.; 4 figs.; 1 tab

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.

Interactions of chlorphenesin and divalent metal ions with phosphodiesterase.

Science.gov (United States)

Edelson, J; McMullen, J P

1976-09-01

Chlorphenesin inhibition of the hydrolysis of cyclic AMP by guinea-pig lung phosphodiesterase was reversed by the addition of exogenous magnesium ions. Chlorphenesin and theophylline inhibition of this enzyme was shown to be noncompetitive when the substrate concentration was low. Kinetic studies of the inhibition of beef heart phosphodiesterase by chlorphenesin and theophylline indicated that the substrate concentration was a factor in determining whether inhibition was competitive or noncompetitive. Calcium, cobalt and copper ions were inhibitory to guinea-pig lung phosphodiesterase. The inhibition due to chlorphenesin was partially reversed by low (40 mM or less) concentrations of barium ions; high concentrations of barium ions, or manganese ions, were inhibitory. The concentration of the divalent cation did not affect the type of inhibition that was observed.

Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO{sub 2} hydrate equilibria

Energy Technology Data Exchange (ETDEWEB)

Sabil, Khalik M., E-mail: khalik_msabil@petronas.com.m [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Universiti Teknologi PETRONAS, Chemical Engineering Programme, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Roman, Vicente R.; Witkamp, Geert-Jan [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Peters, Cor J., E-mail: C.J.Peters@tudelft.n [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Petroleum Institute, Chemical Engineering Program, Bu Hasa Building, Room 2207A, P.O. Box 2533, Abu Dhabi (United Arab Emirates)

2010-03-15

In the present work, experimental data on the equilibrium conditions of mixed CO{sub 2} and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), magnesium chloride (MgCl{sub 2}), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO{sub 2} and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L{sub W}), liquid organic (L{sub V}), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO{sub 2} and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl{sub 2} < MgCl{sub 2}. Among the cations studied, the strength of hydrate inhibition increases in the following order: K{sup +} < Na{sup +} < Ca{sup 2+} < Mg{sup 2+}. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br{sup -} > Cl{sup -} > F{sup -}. Based on the results, it is suggested that the probability of formation and

Studies on the competitive sorption of divalent metal ions to natural soil samples using a multitracer technique

International Nuclear Information System (INIS)

Fujiyoshi, R.; Hirashima, H.; Sawamura, S.

1997-01-01

Speciation of minor or trace amount of pollutants, such as heavy metals and radionuclides released from atmospheric precipitation and water streams have been studied in order to elucidate their fates in the environment through 'in situ' observations or laboratory experiments. The authors have investigated sorption of heavy metals on various natural samples radiometrically ( 65 Zn as a tracer). A sequential extraction technique was found to be very effective to elucidate possible scavengers (minerals) of heavy metals in some cases. A sediment with low CEC does not sorb Zn (ii) ions to a great extent. It is thus considered that the zinc sorption occurs competitively with protons present in the aqueous media. Divalent copper and cadmium ions also behaved similarly to Zn(II), which was obtained electrochemically with the ion selective electrodes of Cu(II) and Cd(II). This time the authors investigated the competitive sorption of Mn(ii) and Zn(II) to natural soils using a radiotracer technique, which was considered to be useful to evaluate relative importance of the sorption of each metal ion without serious matrix effects. Quite different properties appeared among those metal ions used independently or simultaneously as a tracer. Proton exchange process may be important for the Zn(II) sorption, whereas a solid-solution partition is supposed to control the Mn(ii) uptake, when each of them was examined independently as a sorbate. In contrast, simultaneous use of those tracers to a soil suspension had great effects on the result; the maximum sorption (A m ) of Zn(II) increased, and Mn(II) behaved like a sorbate which tends to occupy specific sites of the soil surfaces. Those results indicate that the sorption of minor and/or trace elements to natural soils would not be evaluated through a series of experiments with a single sorbate

Reversible CO binding enables tunable CO/H₂ and CO/N₂ separations in metal-organic frameworks with exposed divalent metal cations.

Science.gov (United States)

Bloch, Eric D; Hudson, Matthew R; Mason, Jarad A; Chavan, Sachin; Crocellà, Valentina; Howe, Joshua D; Lee, Kyuho; Dzubak, Allison L; Queen, Wendy L; Zadrozny, Joseph M; Geier, Stephen J; Lin, Li-Chiang; Gagliardi, Laura; Smit, Berend; Neaton, Jeffrey B; Bordiga, Silvia; Brown, Craig M; Long, Jeffrey R

2014-07-30

Six metal-organic frameworks of the M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) structure type are demonstrated to bind carbon monoxide reversibly and at high capacity. Infrared spectra indicate that, upon coordination of CO to the divalent metal cations lining the pores within these frameworks, the C-O stretching frequency is blue-shifted, consistent with nonclassical metal-CO interactions. Structure determinations reveal M-CO distances ranging from 2.09(2) Å for M = Ni to 2.49(1) Å for M = Zn and M-C-O angles ranging from 161.2(7)° for M = Mg to 176.9(6)° for M = Fe. Electronic structure calculations employing density functional theory (DFT) resulted in good agreement with the trends apparent in the infrared spectra and crystal structures. These results represent the first crystallographically characterized magnesium and zinc carbonyl compounds and the first high-spin manganese(II), iron(II), cobalt(II), and nickel(II) carbonyl species. Adsorption isotherms indicate reversible adsorption, with capacities for the Fe, Co, and Ni frameworks approaching one CO per metal cation site at 1 bar, corresponding to loadings as high as 6.0 mmol/g and 157 cm(3)/cm(3). The six frameworks display (negative) isosteric heats of CO adsorption ranging from 52.7 to 27.2 kJ/mol along the series Ni > Co > Fe > Mg > Mn > Zn, following the Irving-Williams stability order. The reversible CO binding suggests that these frameworks may be of utility for the separation of CO from various industrial gas mixtures, including CO/H2 and CO/N2. Selectivities determined from gas adsorption isotherm data using ideal adsorbed solution theory (IAST) over a range of gas compositions at 1 bar and 298 K indicate that all six M2(dobdc) frameworks could potentially be used as solid adsorbents to replace current cryogenic distillation technologies, with the choice of M dictating adsorbent regeneration energy and the level of purity of the resulting gases.

Metal resistance sequences and transgenic plants

Science.gov (United States)

Meagher, Richard Brian; Summers, Anne O.; Rugh, Clayton L.

1999-10-12

The present invention provides nucleic acid sequences encoding a metal ion resistance protein, which are expressible in plant cells. The metal resistance protein provides for the enzymatic reduction of metal ions including but not limited to divalent Cu, divalent mercury, trivalent gold, divalent cadmium, lead ions and monovalent silver ions. Transgenic plants which express these coding sequences exhibit increased resistance to metal ions in the environment as compared with plants which have not been so genetically modified. Transgenic plants with improved resistance to organometals including alkylmercury compounds, among others, are provided by the further inclusion of plant-expressible organometal lyase coding sequences, as specifically exemplified by the plant-expressible merB coding sequence. Furthermore, these transgenic plants which have been genetically modified to express the metal resistance coding sequences of the present invention can participate in the bioremediation of metal contamination via the enzymatic reduction of metal ions. Transgenic plants resistant to organometals can further mediate remediation of organic metal compounds, for example, alkylmetal compounds including but not limited to methyl mercury, methyl lead compounds, methyl cadmium and methyl arsenic compounds, in the environment by causing the freeing of mercuric or other metal ions and the reduction of the ionic mercury or other metal ions to the less toxic elemental mercury or other metals.

Synthesis and Characterization of Divalent Manganese, Iron, and Cobalt Complexes in Tripodal Phenolate/N-Heterocyclic Carbene Ligand Environments

DEFF Research Database (Denmark)

Käß, Martina; Hohenberger, Johannes; Adelhardt, Mario

2014-01-01

. The complete ligand series offers a convenient way of tuning the electronic and steric environment around the metal center, thus, allowing for control of the complex’s reactivity. This series of divalent complexes of Mn, Fe, and Co was synthesized and characterized by 1H NMR, IR, and UV/vis spectroscopy...... as well as by single-crystal X-ray diffraction studies. Variable-temperature SQUID magnetization measurements in the range from 2 to 300 K confirmed high-spin ground states for all divalent complexes and revealed a trend of increasing zero-field splitting |D| from Mn(II), to Fe(II), to Co(II) complexes...

Highly reversible open framework nanoscale electrodes for divalent ion batteries.

Science.gov (United States)

Wang, Richard Y; Wessells, Colin D; Huggins, Robert A; Cui, Yi

2013-01-01

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg(2+), Ca(2+), Sr(2+), and Ba(2+). We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

Method of microbially producing metal gallate spinel nano-objects, and compositions produced thereby

Science.gov (United States)

Duty, Chad E.; Jellison, Jr., Gerald E.; Love, Lonnie J.; Moon, Ji Won; Phelps, Tommy J.; Ivanov, Ilia N.; Kim, Jongsu; Park, Jehong; Lauf, Robert

2018-01-16

A method of forming a metal gallate spinel structure that includes mixing a divalent metal-containing salt and a gallium-containing salt in solution with fermentative or thermophilic bacteria. In the process, the bacteria nucleate metal gallate spinel nano-objects from the divalent metal-containing salt and the gallium-containing salt without requiring reduction of a metal in the solution. The metal gallate spinel structures, as well as light-emitting structures in which they are incorporated, are also described.

Divalent metal (Ca, Cd, Mn, Zn) uptake and interactions in the aquatic insect Hydropsyche sparna.

Science.gov (United States)

Poteat, Monica D; Díaz-Jaramillo, Mauricio; Buchwalter, David B

2012-05-01

Despite their ecological importance and prevalent use as ecological indicators, the trace element physiology of aquatic insects remains poorly studied. Understanding divalent metal transport processes at the water-insect interface is important because these metals may be essential (e.g. Ca), essential and potentially toxic (e.g. Zn) or non-essential and toxic (e.g. Cd). We measured accumulation kinetics of Zn and Cd across dissolved concentrations ranging 4 orders of magnitude and examined interactions with Ca and Mn in the caddisfly Hydropsyche sparna. Here, we provide evidence for at least two transport systems for both Zn and Cd, the first of which operates at concentrations below 0.8 μmol l(-1) (and is fully saturable for Zn). We observed no signs of saturation of a second lower affinity transport system at concentrations up to 8.9 μmol l(-1) Cd and 15.3 μmol l(-1) Zn. In competition studies at 0.6 μmol l(-1) Zn and Cd, the presence of Cd slowed Zn accumulation by 35% while Cd was unaffected by Zn. At extreme concentrations (listed above), Cd accumulation was unaffected by the presence of Zn whereas Zn accumulation rates were reduced by 58%. Increasing Ca from 31.1 μmol l(-1) to 1.35 mmol l(-1) resulted in only modest decreases in Cd and Zn uptake. Mn decreased adsorption of Cd and Zn to the integument but not internalization. The L-type Ca(2+) channel blockers verapamil and nifedipine and the plasma membrane Ca(2+)-ATPase inhibitor carboxyeosin had no influence on Ca, Cd or Zn accumulation rates, while Ruthenium Red, a Ca(2+)-ATPase inhibitor, significantly decreased the accumulation of all three in a concentration-dependent manner.

The role of electrolyte anions (ClO4-, NO3-, and Cl-) in divalent metal (M2+) adsorption on oxide and hydroxide surfaces in salt solutions

International Nuclear Information System (INIS)

Criscenti, L.J.; Sverjensky, D.A.

1999-01-01

Adsorption of divalent metal ions (M 2+ ) onto oxide and hydroxide surfaces from solutions of strong electrolytes has typically been inferred to take place without the involvement of the electrolyte anion. Only in situations where M 2+ forms a strong enough aqueous complex with the electrolyte anion (for example, CdCl + or PbCl + ) has it been frequently suggested that the metal and the electrolyte anion adsorb simultaneously. A review of experimental data for the adsorption of Cd 2+ , Pb 2+ , Co 2+ , UO 2 2+ , Zn 2+ , Cu 2+ , Ba 2+ , Sr 2+ , and Ca 2+ onto quartz, silica, goethite, hydrous ferric oxide, corundum, γ-alumina, anatase, birnessite, and magnetite, from NaNO 3 , KNO 3 , NaCl, and NaClO 4 solutions over a wide range of ionic strengths (0.0001 M-1.0 M), reveals that transition and heavy metal adsorption behavior with ionic strength is a function of the type of electrolyte. In NaNO 3 solutions, metal adsorption exhibits little or no dependence on the ionic strength of the solution. However, in NaCl solutions, transition and heavy metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption exhibits little dependence on ionic strength but is often suggestive of an increase in metal adsorption with increasing ionic strength. Analysis of selected adsorption edges was carried out using the extended triple-layer model and aqueous speciation models that included metal-nitrate, metal-chloride, and metal-hydroxide complexes

Mechanistic studies on E. coli DNA topoisomerase I: Divalent ion effects

International Nuclear Information System (INIS)

Domanico, P.L.; Tse-Dinh, Y.C.

1991-01-01

E. coli DNA topoisomerase I catalyzes the hydrolysis of short, single stranded oligodeoxynucleotides. It also forms a covalent protein-DNA complex with negatively supercoiled DNA in the absence of Mg2+ but requires Mg2+ for the relaxation of negatively supercoiled DNA. In this paper we investigate the effects of various divalent metals on catalysis. For the relaxation reaction, maximum enzyme activity plateaus after 2.5 mM Mg2+. However, the rate of cleavage of short oligodeoxynucleotide increased linearly between 0 and 15 mM Mg2+. In the oligodeoxynucleotide cleavage reaction, Ca2+, Mn2+, Co2+, and Zn2+ inhibit enzymatic activity. When these metals are coincubated with Mg2+ at equimolar concentrations, the normal effect of Mg2+ is not detectable. Of these metals, only Ca2+ can be substituted for Mg2+ as a metal cofactor in the relaxation reaction. And when Mg2+ is coincubated with Mn2+, Co2+, or Zn2+ at equimolar concentrations, the normal effect of Mg2+ on relaxation is not detectable. The authors propose that Mg2+ allows the protein-DNA complex to assume a conformation necessary for strand passage and enhance the rate of enzyme turnover

Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

Science.gov (United States)

Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

2017-05-01

Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand

Science.gov (United States)

Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

2018-01-01

A series of novel coordination polyurethanes [HTPU-M, where M = Mn(II) 'd5', Ni(II) 'd8', and Zn(II) 'd10'] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, sbnd OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II) > HTPU-Mn(II) > HTPU-Zn(II) > HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants.

Comparative sensitivity of rat cerebellar neurons to dysregulation of divalent cation homeostasis and cytotoxicity caused by methylmercury

International Nuclear Information System (INIS)

Edwards, Joshua R.; Marty, M. Sue; Atchison, William D.

2005-01-01

The objective of the present study was to determine the relative effectiveness of methylmercury (MeHg) to alter divalent cation homeostasis and cause cell death in MeHg-resistant cerebellar Purkinje and MeHg-sensitive granule neurons. Application of 0.5-5 μM MeHg to Purkinje and granule cells grown in culture caused a concentration- and time-dependent biphasic increase in fura-2 fluorescence. At 0.5 and 1 μM MeHg, the elevations of fura-2 fluorescence induced by MeHg were biphasic in both cell types, but significantly delayed in Purkinje as compared to granule cells. Application of the heavy-metal chelator, TPEN, to Purkinje cells caused a precipitous decline in a proportion of the fura-2 fluorescence signal, indicating that MeHg causes release of Ca 2+ and non-Ca 2+ divalent cations. Purkinje cells were also more resistant than granule cells to the neurotoxic effects of MeHg. At 24.5 h after-application of 5 μM MeHg, 97.7% of Purkinje cells were viable. At 3 μM MeHg there was no detectable loss of Purkinje cell viability. In contrast, only 40.6% of cerebellar granule cells were alive 24.5 h after application of 3 μM MeHg. In conclusion, Purkinje neurons in primary cultures appear to be more resistant to MeHg-induced dysregulation of divalent cation homeostasis and subsequent cell death when compared to cerebellar granule cells. There is a significant component of non-Ca 2+ divalent cation released by MeHg in Purkinje neurons

Effect of hydrated salts on the microstructure and phase transformation of poly(vinylidenefluoride-hexafluoropropylene) composites

Science.gov (United States)

Yuennan, Jureeporn; Sukwisute, Pisan; Muensit, Nantakan

2018-05-01

The present work has investigated a means of fabricating porous, β phase P(VDF-HFP) film by adding two kinds of hydrated metal salts. Without the use of mechanical stretching or electrical poling treatments, MgCl2 · 6H2O and AlCl3 · 6H2O are found to induce the formation of β phase crystals in porous film derived from the solution casting method. Trivalent Al ions have been found to effectively promote the self-oriented β phase of the P(VDF-HFP) film greater than divalent Mg ions. The overall β content is achieved about 38% and 42% for adding 0.25 wt% Mg- and Al-salts, respectively. The average pore sizes and surface roughness of porous P(VDF-HFP) films are increased with increasing salt concentration. The dielectric constant of about 5 for pure P(VDF-HFP) film (at 100 Hz) has been boosted up to 13–19 when adding the salts. In addition, the P(VDF-HFP) films filled with Al-salt exhibit the largest piezoelectric coefficient of 20 pC/N. Thus, the modified polymers are one of candidate materials for using in dielectric and piezoelectric applications.

Fast x-ray fluorescence microtomography of hydrated biological samples.

Directory of Open Access Journals (Sweden)

Enzo Lombi

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

Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

International Nuclear Information System (INIS)

Yang Bingping; Prosvirin, Andrey V.; Zhao, Han-Hua; Mao, Jiang-Gao

2006-01-01

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH 2 PO 3 H 2 ) 2 (H 4 L) afforded three new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2 and Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3. When HO 2 C(CH 2 ) 3 N(CH 2 PO 3 H 2 ) 2 was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 with a pillared layered architecture was obtained. The NH(CH 2 PO 3 ) 2 anion resulted from the cleavage of the HO 2 C(CH 2 ) 3 -group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu 2 O 2 dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO 6 octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2, Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3 and {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is

ADR salt pill design and crystal growth process for hydrated magnetic salts

Science.gov (United States)

Shirron, Peter J. (Inventor); DiPirro, Michael J. (Inventor); Canavan, Edgar R. (Inventor)

2013-01-01

A process is provided for producing a salt pill for use in very low temperature adiabatic demagnetization refrigerators (ADRs). The method can include providing a thermal bus in a housing. The thermal bus can include an array of thermally conductive metal conductors. A hydrated salt can be grown on the array of thermally conductive metal conductors. Thermal conductance can be provided to the hydrated salt.

Stability constants for some divalent metal ion/crown ether complexes in methanol determined by polarography and conductometry

NARCIS (Netherlands)

Chen, L.; Bos, M.; Grootenhuis, P.D.J.; Christenhusz, A.; Hoogendam, E.; Reinhoudt, David; van der Linden, W.E.

1987-01-01

Stability constants in methanol at 25.0°C were evaluated for the complexes of the divalent cations Ca2+, Ni2+, Zn2+, Pb2+, Mg2+, Co2+ and Cu2+ with the macrocyclic polyethers 15-crown-5 (15C5), 18-crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6) and dibenzo-24-crown-8 (DB24C8). The log K values of

Adsorptive behaviour of mercury on algal biomass: Competition with divalent cations and organic compounds

International Nuclear Information System (INIS)

Carro, Leticia; Barriada, Jose L.; Herrero, Roberto; Sastre de Vicente, Manuel E.

2011-01-01

Highlights: → Native and protonated macroalga S. muticum are good materials for mercury removal. → Fast kinetic process and high mercury uptakes have been found for those materials. → Diffusion control is the rate limiting step of the process. → Competition effects by organic compounds, inorganic salts and divalent cations were analyzed. → Continuous flow experiments allowed identification of mercury reduction during metal removal. - Abstract: Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed.

Reaction of N,N'-dimethylformamide and divalent viologen molecule to generate an organic dopant for molybdenum disulfide

Science.gov (United States)

Fukui, A.; Miura, K.; Ichimiya, H.; Tsurusaki, A.; Kariya, K.; Yoshimura, T.; Ashida, A.; Fujimura, N.; Kiriya, D.

2018-05-01

Tuning the carrier concentration is essential for semiconducting materials to apply optoelectronic devices. Molybdenum disulfide (MoS2) is a semiconducting material composed of atomically thin (˜0.7 nm thickness) layers. To dope thin MoS2, instead of using conventional atom/ion injection processes, a surface charge transfer method was successfully applied. In this study, we report a simple preparation method of a molecular dopant applicable to the doping process. The method follows a previous report for producing a molecular dopant, benzyl viologen (BV) which shows electron doping to MoS2. To prepare dopant BV molecules, a reduction process with a commercially available divalent BV by sodium borohydride (NaBH4) is required; however, the reaction requires a large consumption of NaBH4. NaBH4 drastically reacts with the solvent water itself. We found a reaction process of BV in an organic solvent, N,N'-dimethylformamide (DMF), by adding a small amount of water dissolving the divalent BV. The reaction is mild (at room temperature) and is autonomous once DMF comes into contact with the divalent BV aqueous solution. The reaction can be monitored with a UV-Vis spectrometer, and kinetic analysis indicates two reaction steps between divalent/monovalent/neutral viologen isomers. The product was soluble in toluene and did not dissolve in water, indicating it is similar to the reported dopant BV. The synthesized molecule was found to act as a dopant for MoS2 by applying a metal-oxide-semiconductor field-effect-transistor (MOSFET) structure. The process is a general method and applicable to other viologen-related dopants to tune the electronic structure of 2D materials to facilitate generating atomically thin devices.

Reaction of N,N’-dimethylformamide and divalent viologen molecule to generate an organic dopant for molybdenum disulfide

Directory of Open Access Journals (Sweden)

A. Fukui

2018-05-01

Full Text Available Tuning the carrier concentration is essential for semiconducting materials to apply optoelectronic devices. Molybdenum disulfide (MoS2 is a semiconducting material composed of atomically thin (∼0.7 nm thickness layers. To dope thin MoS2, instead of using conventional atom/ion injection processes, a surface charge transfer method was successfully applied. In this study, we report a simple preparation method of a molecular dopant applicable to the doping process. The method follows a previous report for producing a molecular dopant, benzyl viologen (BV which shows electron doping to MoS2. To prepare dopant BV molecules, a reduction process with a commercially available divalent BV by sodium borohydride (NaBH4 is required; however, the reaction requires a large consumption of NaBH4. NaBH4 drastically reacts with the solvent water itself. We found a reaction process of BV in an organic solvent, N,N’-dimethylformamide (DMF, by adding a small amount of water dissolving the divalent BV. The reaction is mild (at room temperature and is autonomous once DMF comes into contact with the divalent BV aqueous solution. The reaction can be monitored with a UV-Vis spectrometer, and kinetic analysis indicates two reaction steps between divalent/monovalent/neutral viologen isomers. The product was soluble in toluene and did not dissolve in water, indicating it is similar to the reported dopant BV. The synthesized molecule was found to act as a dopant for MoS2 by applying a metal-oxide-semiconductor field-effect-transistor (MOSFET structure. The process is a general method and applicable to other viologen-related dopants to tune the electronic structure of 2D materials to facilitate generating atomically thin devices.

Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

Science.gov (United States)

Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

2017-11-07

Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

Influence of Divalent Counterions on the Dynamics in DNA as Probed by Using a Minor-Groove Binder.

Science.gov (United States)

Paul, Sneha; Ahmed, Tasnim; Samanta, Anunay

2017-08-05

DNA dynamics, to which water, counterions, and DNA motions contribute, is a topic of considerable interest because it is closely related to the efficiency of biological functions performed by it. Simulation studies and experiments suggest that the counterion dynamics in DNA probed by a minor-groove binder are similar for various monovalent counterions. To date, the influence on DNA dynamics of higher-valence counterions, which are also present around DNA and are known to bind more strongly to it than monovalent ions, has not been studied. Herein we investigated DNA dynamics in the presence of Mg 2+ and Ca 2+ , chosen for their relative abundance in cells, by using minor-groove binder 4',6-diamidino-2-phenylindole (DAPI) as a fluorescence probe. The dynamics, as measured from the time-resolved fluorescence Stokes shifts of DAPI bound to calf thymus DNA on a subpicosecond-to-nanosecond timescale, were found to be very similar in the presence of both the divalent ions and Na + ions. The observation is explained by considering the screening of the electric field of the divalent ion by its hydration shell, preferential binding of the ions to the phosphate groups, and displacement of ions from the minor groove by DAPI due to the stronger binding interaction of the latter. Furthermore, the similarity of our results in the presence of Na + to those reported for smaller oligonucleotides suggests that the chain length of DNA does not influence the DNA dynamics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of radiation-chemical behaviour of divalent palladium in perchloric acid solutions

International Nuclear Information System (INIS)

Vladimirova, M.V.; Kalinina, S.V.

1988-01-01

Gamma-radiolysis of divalent palladium in perchloric acid solutions is studied. Absorption spectra of intermediate palladium compounds formed in the irradiated solution are taken. The analysis of literature data as well as comparative analysis of the absorption spectra obtained under irradiation of palladium (2) perchloric acid solutions with absorption spectra of palladium chlorocomplexes allows to suppose that the mentioned compounds are chlorocomplexes of palladium (2) of different composition depending on HClO 4 concentration in the initial solution and absorbed radiation dose. Radiation-chemical reduction of palladium (2) up to metal is stated to take place in the whole studied range of initial concentrations of components of the system and dose rates. Kinetic dependences of metallic palladium formation are obtained. Values of radiation-chemical yields of metallic palladium formation depending on the initial concentrations of palladium (2) and perchloric acid are given. A mechanism of radiolytic reduction of palladium (2) in the investigated system is suggested based on the experimental data, and a theoretical value of the radiation-chemical yield of palladium (2) reduction being in a good agreement with experimentally found values is calculated

On the valence state of Yb and Ce in transition metal intermetallic compounds

International Nuclear Information System (INIS)

Boer, F.R. de; Dijkman, W.H.; Mattens, W.C.M.

1979-01-01

In the pure state Yb is a divalent metal, similar to Ca; in alloys it can become trivalent like the majority of the rare earth metals. Using a value of 38 kJ (mol Yb) -1 for the energy difference between divalent and trivalent Yb metal and using model calculations for the heat of formation of intermetallic compounds, the authors are able to account for the existing information on the valence state of Yb in transition metal compounds. A similar analysis of compounds of Ce with transition metals shows that a model in which the 4f electron is treated as a core electron, i.e. being absent in the tetravalent modification of Ce and present as a fully localized electron in trivalent Ce, does not apply. (Auth.)

Divalent cations as modulators of neuronal excitability: Emphasis on copper and zinc

Directory of Open Access Journals (Sweden)

RICARDO DELGADO

2006-01-01

Full Text Available Based on indirect evidence, a role for synaptically released copper and zinc as modulators of neuronal activity has been proposed. To test this proposal directly, we studied the effect of copper, zinc, and other divalent cations on voltage-dependent currents in dissociated toad olfactory neurons and on their firing rate induced by small depolarizing currents. Divalent cations in the nanomolar range sped up the activation kinetics and increased the amplitude of the inward sodium current. In the micromolar range, they caused a dose dependent inhibition of the inward Na+ and Ca2+ currents (I Na and I Ca and reduced de amplitude of the Ca2+-dependent K+ outward current (I Ca-K. On the other hand, the firing rate of olfactory neurons increased when exposed to nanomolar concentration of divalent cations and decreased when exposed to micromolar concentrations. This biphasic effect of divalent cations on neuronal excitability may be explained by the interaction of these ions with high and low affinity sites in voltage-gated channels. Our results support the idea that these ions are normal modulators of neuronal excitability

Biosynthesis of (+)-cis- and (+)-trans-sabinene hydrate from geranyl pyrophosphate by a soluble enzyme system from sweet marjoram (Majorana hortensis)

International Nuclear Information System (INIS)

Hallahan, T.W.

1988-01-01

A soluble enzyme preparation from the leaves of sweet marjoram (Majorana hortensis Moench) catalyzes the divalent cation-dependent cyclization of [1- 3 H]geranyl pyrophosphate to the bicyclic monoterpene alcohols (+)-cis- and (+)-trans-[6 3 H]sabinene hydrate, providing labeling patterns consistent with current mechanistic considerations. The two enzymatic activities were inseparable by several chromatographic procedures, and differential inactivation studies suggesting that the two activities reside with the same enzyme. The enzymatic cyclization is considered to proceed by the initial ionization and isomerization of geranyl pyrophosphate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this enzyme bound tertiary allylic intermediate to the monocyclic (+)-(4R)-α-terpinyl cation. A 1,2-hydride shift and a second cyclization with water capture of the resulting cation completes the reaction sequence. No free intermediates were detectable in the conversion of geranyl pyrophosphate to the sabinene hydrates as determined by isotopic dilution experiments

Cryo magnetic separation adaptation to environment technologies: application to industrial effluents; Adaptation de la separation cryomagnetique aux technologies de l`environnement: application a l`epuration d`effluents liquides industriels

Energy Technology Data Exchange (ETDEWEB)

Bureau, V

1993-12-20

Cryomagnetic separation adaptation to environment technologies application to industrial liquid effluents. The performance, obtained by superconducting high filed - high gradient magnetic separation, permitted to foresee the magnetic treatment of heavy metals in rinse waters, derived from the surface finishing industry. The paramagnetic ions, precipitated in basic media as hydroxides, present a very hydrated amorphous structure, which masks their subjacent magnetic properties. Coprecipitation of a `magnetic carrier`, jointly with the heavy metals, has been studied: ferric chloride forms in basic media, an hydrated iron oxide. Its structure is of the goethite type, and it stabilizes as hematite. The magnetic susceptibility of the obtained product is still weak and its crystalline structure is not enough affirmative to utilize magnetic filtration with efficiency. Mixture of ferrous sulphate and ferric chloride forms, in a basic media, an hydrated magnetite. Initial ideal ratio between divalent iron and trivalent iron, varies between 0,5 and 1,2. This mixture, coprecipitated with the heavy metals, permits to optimize the magnetic cleaning of the fluids in a high field - high gradient filter. (author)

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

Science.gov (United States)

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

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...

Ultra-thin, conformal, and hydratable color-absorbers using silk protein hydrogel

Science.gov (United States)

Umar, Muhammad; Min, Kyungtaek; Jo, Minsik; Kim, Sunghwan

2018-06-01

Planar and multilayered photonic devices offer unprecedented opportunities in biological and chemical sensing due to strong light-matter interactions. However, uses of rigid substances such as semiconductors and dielectrics confront photonic devices with issues of biocompatibility and a mechanical mismatch for their application on humid, uneven, and soft biological surfaces. Here, we report that favorable material traits of natural silk protein led to the fabrication of an ultra-thin, conformal, and water-permeable (hydratable) metal-insulator-metal (MIM) color absorber that was mapped on soft, curved, and hydrated biological interfaces. Strong absorption was induced in the MIM structure and could be tuned by hydration and tilting of the sample. The transferred MIM color absorbers reached the exhibition of a very strong resonant absorption in the visible and near infra-red ranges. In addition, we demonstrated that the conformal resonator could function as a refractometric glucose sensor applied on a contact lens.

Hydration and leaching characteristics of cement pastes made from electroplating sludge.

Science.gov (United States)

Chen, Ying-Liang; Ko, Ming-Sheng; Lai, Yi-Chieh; Chang, Juu-En

2011-06-01

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the (29)Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

Zirconium molybdate hydrate precipitates in spent nuclear fuel reprocessing

International Nuclear Information System (INIS)

Magnaldo, A.; Noire, M.H.; Esbelin, E.; Dancausse, J.P.; Picart, S.

2004-01-01

This paper presents through 2 posters a general overview studies realised by CEA teams on deposits observed in the La Hague plant dissolution facilities. Their main constituents are metallic debris bound together with zirconium molybdate hydrate. A comprehensive study of zirconium molybdate hydrate formation included nucleation and growth kinetics was developed. Fouling mechanisms were consequently explained as influenced by the operation conditions. Pu insertion was also overviewed. Its behaviour is important when curative and preventive chemical treatments are considered. (authors)

Adsorption performances and mechanisms of the newly synthesized N,N'-di (carboxymethyl) dithiocarbamate chelating resin toward divalent heavy metal ions from aqueous media

International Nuclear Information System (INIS)

Jing Xiaosheng; Liu Fuqiang; Yang Xin; Ling Panpan; Li Lanjuan; Long Chao; Li Aimin

2009-01-01

N,N'-di (carboxymethyl) dithiocarbamate chelating resin (PSDC) was synthesized by anchoring the chelating agent of N,N'-di (carboxymethyl) dithiocarbamate to the chloromethylated PS-DVB (Cl-PS-DVB) matrix, as a new adsorbent for removing divalent heavy metal ions from waste-stream. The physicochemical structures of Cl-PS-DVB and PSDC were elaborately characterized using Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and were further morphologically characterized using BET and BJH methods. The adsorption performances of PSDC towards heavy metals such as Cu(II), Pb(II) and Ni(II) were systematically investigated, based upon which the adsorption mechanisms were deeply exploited. For the above target, the classic batch adsorption experiments were conducted to explore the kinetics and isotherms of the removal processes with pH-value, initial concentration, temperature, and contact time as the controlling parameters. The kinetic and isotherm data could be well elucidated with Lagergren-second-order equation and Langmuir model respectively. The strong affinity of PSDC toward these target soft acids could be well demonstrated with the electrostatic attraction and chelating interaction caused by IDA moiety and sulphur which were namely soft bases on the concept of hard and soft acids and bases (HASB). Thermodynamic parameters, involving ΔH o , ΔS o and ΔG o were also calculated from graphical interpretation of the experimental data. The standard heats of adsorption (ΔH o ) were found to be endothermic and the entropy change values (ΔS o ) were calculated to be positive for the adsorption of Cu(II), Pb(II) and Ni(II) ions onto the tested adsorbents. Negative values of ΔG o indicated that adsorption processes for all tested metal ions onto PSDC were spontaneous.

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

Science.gov (United States)

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

2011-10-01

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

Divalent thulium triflate. A structural and spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Xemard, Mathieu; Jaoul, Arnaud; Cordier, Marie; Nocton, Gregory [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Molton, Florian; Duboc, Carole [Grenoble Univ., Saint Martin d' Heres (France). Dept. de Chimie Moleculaire; Cador, Olivier; Le Guennic, Boris [Univ. de Rennes 1 (France). Inst. des Sciences Chimique de Rennes, UMR 6226 CNRS; Maury, Olivier [Univ. Claude Bernard Lyon 1 (France). Lab. de Chimie; Clavaguera, Carine [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Univ. Paris Sud, Univ. Paris-Saclay, Orsay (France). Lab. de Chimie Physique, CNRS

2017-04-03

The first molecular Tm{sup II} luminescence measurements are reported along with rare magnetic, X and Q bands EPR studies. Access to simple and soluble molecular divalent lanthanide complexes is highly sought for small-molecule activation studies and organic transformations using single-electron transfer processes. However, owing to their low stability and propensity to disproportionate, these complexes are hard to synthetize and their electronic properties are therefore almost unexplored. Herein we present the synthesis of [Tm(μ-OTf){sub 2}(dme){sub 2}]{sub n}, a rare and simple coordination compound of divalent thulium that can be seen as a promising starting material for the synthesis of more elaborated complexes. This reactive complex was structurally characterized by X-ray diffraction analysis and its electronic structure has been compared with that of its halide cousin TmI{sub 2}(dme){sub 3}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

Science.gov (United States)

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

2017-12-01

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

Immobilisation of heavy metal in cement-based solidification/stabilisation: A review

International Nuclear Information System (INIS)

Chen, Q.Y.; Tyrer, M.; Hills, C.D.; Yang, X.M.; Carey, P.

2009-01-01

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C 3 S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H + attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C 3 S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29 Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique

Dehydration and hydration behavior of metal-salt-modified materials for chemical heat pumps

International Nuclear Information System (INIS)

Ishitobi, Hirokazu; Uruma, Keirei; Takeuchi, Masato; Ryu, Junichi; Kato, Yukitaka

2013-01-01

Lithium chloride (LiCl) modified magnesium hydroxide (Mg(OH) 2 ) is a potential new material for chemical heat pumps. However, there is insufficient information concerning its dehydration and hydration behavior. In this study, the dehydration and hydration reactions, corresponding to the heat storage and the heat output operations, respectively, of authentic Mg(OH) 2 and LiCl-modified Mg(OH) 2 were investigated by thermogravimetric methods and near infrared spectroscopy. The dehydration of authentic Mg(OH) 2 proceeded as a one-step reaction. In contrast, the dehydration of LiCl-modified Mg(OH) 2 occurred in two steps. The dehydration reaction rates were increased by LiCl modification of the Mg(OH) 2 surface, while the activation energy for the first-order dehydration reaction was lowered. The mechanism for the hydration reaction of magnesium oxide (MgO) was different to that for the hydration of LiCl-modified MgO. This difference was explained by the effect of the LiCl on the MgO particle surface. - Highlights: ► LiCl-modified Mg(OH) 2 is a candidate material for chemical heat pumps. ► The dehydration reaction of LiCl-modified Mg(OH) 2 is a two-step reaction. ► The dehydration reaction of Mg(OH) 2 was enhanced by LiCl modification. ► The hydration mechanisms of authentic MgO and LiCl-modified MgO were different.

Development of Magnesium Silicate Hydrate cement system for nuclear waste encapsulation

International Nuclear Information System (INIS)

Zhang, T.; Vandeperre, L.J.; Cheeseman, C.R.

2012-01-01

A novel low pH cement system for encapsulating nuclear industry wastes containing aluminium has been developed using blends of MgO and silica fume (SF). Identification of the hydrated phases in MgO/silica fume samples showed that brucite formed in early stages of hydration and then reacted with the silica fume to produce a magnesium silicate hydrate (M-S-H) gel phase. When all brucite reacts with silica fume a cement system with an equilibrium pH just below 10 was achieved. Selected mixes have been characterized for hydration reactions, setting time and strength development. Mortar samples with w/s ratios of 0.5 and 50% by weight of sand added achieved compressive strengths in excess of 95 MPa after 28 days. The addition of MgCO 3 buffered the early pH and the addition of fine sand particles eliminated shrinkage cracking. The interaction of the optimised mortar with Al metal has been investigated. Al metal strips were firmly bound into the MgO:SF:sand samples and no H 2 gas detected, and this indicates that the novel systems developed in this work have potential for encapsulating certain types of problematic legacy wastes from the nuclear industry. (authors)

Trace Metal Requirements and Interactions in Symbiodinium kawagutii

Directory of Open Access Journals (Sweden)

Irene B. Rodriguez

2018-02-01

Full Text Available Photosynthetic organisms need trace metals for various biological processes and different groups of microalgae have distinctive obligate necessities due to their respective biochemical requirements and ecological niches. We have previously shown that the dinoflagellate Symbiodinium kawagutii requires high concentrations of bioavailable Fe to achieve optimum growth. Here, we further explored the trace metal requirements of S. kawagutii with intensive focus on the effect of individual metal and its interaction with other divalent metals. We found that low Zn availability significantly decreases growth rates and results in elevated intracellular Mn, Co, Ni, and Fe quotas in the dinoflagellate. The results highlight the complex interaction among trace metals in S. kawagutii and suggest either metal replacement strategy to counter low Zn availability or enhanced uptake of other metals by non-specific divalent metal transporters. In this work, we also examined the Fe requirement of S. kawagutii using continuous cultures. We validated that 500 pM of Fe′ was sufficient to support maximum cell density during steady state growth period either at 26 or 28°C. This study shows that growth of S. kawagutii was limited by metal availability in the following order, Fe > Zn > Mn > Cu > Ni > Co. The fundamental information obtained for the free-living Symbiodinium shall provide insights into how trace metal availability, either from ambient seawater or hosts, affects growth and proliferation of symbiotic dinoflagellates and the interaction between symbiont and their hosts.

Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

Directory of Open Access Journals (Sweden)

Abdelatty Mohamed Radalla

2015-06-01

Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

CE of phytosiderophores and related metal species in plants.

Science.gov (United States)

Xuan, Yue; Scheuermann, Enrico B; Meda, Anderson R; Jacob, Peter; von Wirén, Nicolaus; Weber, Günther

2007-10-01

Phytosiderophores (PS) and the closely related substance nicotianamine (NA) are key substances in metal uptake into graminaceous plants. Here, the CE separation of these substances and related metal species is demonstrated. In particular, the three PS 2'-deoxymugineic acid (DMA), mugineic acid (MA), and 3-epi-hydroxymugineic acid (epi-HMA), and NA, are separated using MES/Tris buffer at pH 7.3. Moreover, three Fe(III) species of the different PS are separated without any stability problems, which are often present in chromatographic analyses. Also divalent metal species of Cu, Ni, and Zn with the ligands DMA and NA are separated with the same method. By using a special, zwitterionic CE capillary, even the separation of two isomeric Fe(III) chelates with the ligand ethylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid (EDDHA) is possible (i.e., meso-Fe(III)-EDDHA and rac-Fe(III)-EDDHA), and for fast separations of NA and respective divalent and trivalent metal species, a polymer CE microchip with suppressed EOF is described. The proposed CE method is applicable to real plant samples, and enables to detect changes of metal species (Cu-DMA, Ni-NA), which are directly correlated to biological processes.

Assessment of metal sorption mechanisms by aquatic macrophytes using PIXE analysis

Energy Technology Data Exchange (ETDEWEB)

Módenes, A.N., E-mail: anmodenes@yahoo.com.br [Department of Chemical Engineering-Postgraduate Program, West Parana State University, Campus of Toledo, rua da Faculdade 645, Jd. La Salle, 85903-000 Toledo, PR (Brazil); Espinoza-Quiñones, F.R.; Santos, G.H.F.; Borba, C.E. [Department of Chemical Engineering-Postgraduate Program, West Parana State University, Campus of Toledo, rua da Faculdade 645, Jd. La Salle, 85903-000 Toledo, PR (Brazil); Rizzutto, M.A. [Physics Institute, University of São Paulo, Rua do Matão s/n, Travessa R 187, 05508-900 São Paulo, SP (Brazil)

2013-10-15

Highlights: • Divalent metal ion removals by Egeria densa biosorbent. • Multielements concentrations in biosorbent samples by PIXE analysis. • Elements mass balance in liquid and solid phase before and after metal removals. • Assessment of the mechanisms involved in Cd{sup 2+} and Zn{sup 2+} removal by biosorbent. • Confirmation of the signature of ion exchange process in metal removal. -- Abstract: In this work, a study of the metal sorption mechanism by dead biomass has been performed. All batch metal biosorption experiments were performed using the aquatic macrophyte Egeria densa as biosorbent. Divalent cadmium and zinc solutions were used to assess the sorption mechanisms involved. Using a suitable equilibrium time of 2 h and a mixture of 300 mg biosorbent and 50 mL metal solution at pH 5, monocomponent sorption experiments were performed. In order to determine the residual amounts of metals in the aqueous solutions and the concentrations of removed metals in the dry biomass, Particle Induced X-ray Emission (PIXE) measurements in thin and thick target samples were carried out. Based on the strong experimental evidence from the mass balance among the major elements participating in the sorption processes, an ion exchange process was identified as the mechanism responsible for metal removal by the dry biomass.

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

High pressure metallization of Mott Insulators: Magnetic, structural and electronic properties

International Nuclear Information System (INIS)

Pasternak, M.P.; Hearne, G.; Sterer, E.; Taylor, R.D.; Jeanloz, R.

1993-01-01

High pressure studies of the insulator-metal transition in the (TM)I 2 (TM = V, Fe, Co and Ni) compounds are described. Those divalent transition-metal iodides are structurally isomorphous and classified as Mott Insulators. Resistivity, X-ray diffraction and Moessbauer Spectroscopy were employed to investigate the electronic, structural, and magnetic properties as a function of pressure both on the highly correlated and on the metallic regimes

Raman and infrared spectroscopic studies of the structure of water (H2O, HOD, D2O) in stoichiometric crystalline hydrates and in electrolyte solutions

International Nuclear Information System (INIS)

Buanam-Om, C.

1981-01-01

The chapter of reviews presents in particular the Badger-Bauer-rule, distance and angle dependence of O-H...Y hydrogen bond and the structure of aqueous electrolyte solutions. A chapter of vibrational spectroscopic investigations of crystalline hydrates - metal perchlorate hydrates follows. Two further chapters just so investigate metal halide hydrates and some sulfate hydrates and related systems. The following chapter describes near infrared spectroscopic investigations of HOD(D 2 O) and its electrolyte solutions. The concluding chapter contains thermodynamic consequences and some properties of electrolyte solutions from vibrational spectroscopic investigations. (SPI) [de

Modelling the effects of waste components on cement hydration

NARCIS (Netherlands)

van Eijk, R.J.; Brouwers, Jos

2000-01-01

Ordinary Portland Cement (OPC) is often used for the Solidification/Stabilization (S/S) of waste containing heavy metals and salts. These waste componenents will precipitate in the form of insoluble compounds onto unreacted cement clinker grains preventing further hydration. In this study the long

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

Acidic pH and divalent cation sensing by PhoQ are dispensable for systemic salmonellae virulence.

Science.gov (United States)

Hicks, Kevin G; Delbecq, Scott P; Sancho-Vaello, Enea; Blanc, Marie-Pierre; Dove, Katja K; Prost, Lynne R; Daley, Margaret E; Zeth, Kornelius; Klevit, Rachel E; Miller, Samuel I

2015-05-23

Salmonella PhoQ is a histidine kinase with a periplasmic sensor domain (PD) that promotes virulence by detecting the macrophage phagosome. PhoQ activity is repressed by divalent cations and induced in environments of acidic pH, limited divalent cations, and cationic antimicrobial peptides (CAMP). Previously, it was unclear which signals are sensed by salmonellae to promote PhoQ-mediated virulence. We defined conformational changes produced in the PhoQ PD on exposure to acidic pH that indicate structural flexibility is induced in α-helices 4 and 5, suggesting this region contributes to pH sensing. Therefore, we engineered a disulfide bond between W104C and A128C in the PhoQ PD that restrains conformational flexibility in α-helices 4 and 5. PhoQ(W104C-A128C) is responsive to CAMP, but is inhibited for activation by acidic pH and divalent cation limitation. phoQ(W104C-A128C) Salmonella enterica Typhimurium is virulent in mice, indicating that acidic pH and divalent cation sensing by PhoQ are dispensable for virulence.

Adiabatic differential scanning calorimetric study of divalent cation induced DNA - DPPC liposome formulation compacted for gene delivery

Directory of Open Access Journals (Sweden)

Erhan Süleymanoglu

2004-11-01

Full Text Available Complexes between nucleic acids and phospholipid vesicles have been developed as stable non-viral gene delivery vehicles. Currently employed approach uses positively charged lipid species and a helper zwitterionic lipid, the latter being applied for the stabilization of the whole complex. However, besides problematic steps during their preparation, cationic lipids are toxic for cells. The present work describes some energetic issues pertinent to preparation and use of neutral lipid-DNA self-assemblies, thus avoiding toxicity of lipoplexes. Differential scanning calorimetry data showed stabilization of polynucleotide helix upon its interaction with liposomes in the presence of divalent metal cations. It is thus possible to suggest this self-assembly as an improved formulation for use in gene delivery.

Gas hydrate nucleation

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-12-31

The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

Gas hydrate nucleation

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-12-31

The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

Rust in the Apollo 16 rocks. [hydration and oxidation processes in lunar environment

Science.gov (United States)

Taylor, L. A.; Mao, H. K.; Bell, P. M.

1973-01-01

Apollo 16 samples of all four rock types and from all stations contain evidence for hydration and oxidation - i.e., the presence of hydrated iron oxide, probably goethite. Rock 66095 contains native FeNi grains with a characteristic intergrowth of schreibersite and, to lesser extents, of cohenite. Troilite also contains sphalerite. The goethite contains 1.5-4.6 wt.% chlorine and occurs mainly on the edges of FeNi metal, causing a rust color in the cracks and space around the native metal grains, which also contain abundant chlorine. This observation suggests the presence of lawrencite (FeCl2), a phase that deliquesces and oxidizes very rapidly upon exposure to water or to a moist atmosphere.

Gas hydrates

Digital Repository Service at National Institute of Oceanography (India)

Ramprasad, T.

, not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

One-step synthesis of gold bimetallic nanoparticles with various metal-compositions

International Nuclear Information System (INIS)

Bratescu, Maria Antoaneta; Takai, Osamu; Saito, Nagahiro

2013-01-01

Highlights: ► Synthesis of bimetallic nanoparticles in an aqueous solution discharge. ► Alloying gold with divalent sp metals, trivalent sp metals, 3d or 4d metals. ► Formation mechanism of bimetallic nanoparticles by metal reduction and gold erosion. ► Blue and red shift of surface plasmon resonance. -- Abstract: A rapid, one-step process for the synthesis of bimetallic nanoparticles by simultaneous metal reduction and gold erosion in an aqueous solution discharge was investigated. Gold bimetallic nanoparticles were obtained by alloying gold with various types of metals belonging to one of the following categories: divalent sp metals, trivalent sp metals, 3d or 4d metals. The composition of the various gold bimetallic nanoparticles obtained depends on electrochemical factors, charge transfer between gold and other metal, and initial concentration of metal in solution. Transmission electron microscopy and energy dispersive spectroscopy show that the gold bimetallic nanoparticles were of mixed pattern, with sizes of between 5 and 20 nm. A red-shift of the surface plasmon resonance band in the case of the bimetallic nanoparticles Au–Fe, Au–Ga, and Au–In, and a blue-shift of the plasmon band of the Au–Ag nanoparticles was observed. In addition, the interaction of gold bimetallic nanoparticles with unpaired electrons, provided by a stable free radical molecule, was highest for those NPs obtained by alloying gold with a 3d metal

Solubility of hydrogen in transition metals

International Nuclear Information System (INIS)

Lee, H.M.

1976-01-01

Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

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

Effect of divalent ions on the optical emission behavior of protein thin films

Energy Technology Data Exchange (ETDEWEB)

Bhowal, Ashim Chandra, E-mail: ashimbhowal111@gmail.com; Kundu, Sarathi [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam 781035 (India)

2016-05-06

Photoluminescence behaviors of proteinthin film, bovine serum albumin (BSA) have been studied in the presence of three divalent ions (Mg{sup 2+}, Ca{sup 2+} and Ba{sup 2+}) at different temperatures using fluorescence spectroscopy. Film thickness and morphology have been studied using atomic force microscopy. Variation of different physicochemical parameters like temperature, solvent polarity, pH, ionic strength, substrate binding etc. can make conformational changes in the protein structure and hence influences the emission behavior.In thin film conformation of BSA, dynamic quenching behavior has beenidentified in the presence of all the three divalent ions at pH≈ 5.5. Depending upon the charge density of the divalent ions interaction with protein molecules modifies and as a result quenching efficiency varies. Also after heat treatment, conformation of the protein molecules changes and as a result the quenching efficiency enhances than that of the unheated films. Studies on such protein-ion interactions and conformational variation may explore various functions of protein when it will adsorb on soft surfaces like membranes, vesicles, etc.

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.

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.

Cross-sectional study of expression of divalent metal transporter-1, transferrin, and hepcidin in blood of smelters who are occupationally exposed to manganese

Directory of Open Access Journals (Sweden)

Qiyuan Fan

2016-09-01

Full Text Available Background Manganese (Mn is widely used in industries including the manufacture of Mn-iron (Fe alloy. Occupational Mn overexposure causes manganism. Mn is known to affect Fe metabolism; this study was designed to test the hypothesis that workers exposed to Mn may have an altered expression of mRNAs encoding proteins in Fe metabolism. Methods Workers occupationally exposed to Mn (n = 71 from a Mn–Fe alloy factory and control workers without Mn-exposure (n = 48 from a pig-iron plant from Zunyi, China, were recruited for this study. Blood samples were collected into Trizol-containing tubes. Total RNA was isolated, purified, and subjected to real-time RT-PCR analysis. Metal concentrations were quantified by atomic absorption spectrophotometry. Results Working environment and genetic background of both groups were similar except for marked differences in airborne Mn concentrations (0.18 mg/m3 in Mn–Fe alloy factory vs. 0.0022 mg/m3 in pig-Fe plant, and in blood Mn levels (34.3 µg/L vs. 10.4 µg/L. Mn exposure caused a significant decrease in the expression of divalent metal transporter-1 (DMT1, transferrin (Tf and hepcidin by 58.2%, 68.5% and 61.5%, respectively, as compared to controls, while the expression of transferrin receptor (TfR was unaltered. Linear regression analysis revealed that expressions of DMT1, Tf and hepcidin were inversely correlated with the accumulative Mn exposure; the correlation coefficients (r are −0.47, −0.54, and −0.49, respectively (p < 0.01. Conclusion The data suggest that occupational Mn exposure causes decreased expressions of DMT1, Tf and hepcidin in blood cells; the finding will help understand the mechanism underlying Mn exposure-associated alteration in Fe homeostasis among workers.

Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

Science.gov (United States)

Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

2018-04-01

Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

Energy Technology Data Exchange (ETDEWEB)

Smith, Robert W.; Fujita, Yoshiko

2007-11-07

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Strontium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

International Nuclear Information System (INIS)

Smith, Robert W.; Fujita, Yoshiko

2007-01-01

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

Catalytic properties of lanthanide amide, imide and nitride formed by thermal degradation of liquid ammonia solutions of Eu and Yb metal

International Nuclear Information System (INIS)

Imamura, H.; Mizuno, K.; Ohishi, K.; Suda, E.; Kanda, K.; Sakata, Y.; Tsuchiya, S.

1998-01-01

The catalytic properties of lanthanide amide, imide and nitride prepared by the use of liquid ammonia solutions of lanthanide metals (Ln=Eu and Yb) were studied for catalytic hydrogenation. The reaction of Eu or Yb metal solutions in liquid ammonia with silica yielded SiO 2 -grafted lanthanide amide in the divalent state. The divalent amide showed catalytic activity for the selective hydrogenation of dienes and benzene. It was found that partial hydrogenation of benzene occurred with a very high selectivity for cyclohexene. Amides of calcium, strontium and barium were examined similarly in connection with catalytic studies on divalent amides. Imide and nitride, into which the lanthanide (Ln/AC) deposited by impregnation of active carbon (AC) with liquid ammonia solutions of lanthanide metals were converted thermally, were studied catalytically. It was concluded that imide or imide-like species generated during the thermal degradation of lanthanide amide to nitride were very active in the hydrogenation of ethene. Lanthanide nitride was virtually inactive, but the nitride highly dispersed on active carbon was activated when subjected to evacuation treatment above about 1000 K. (orig.)

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

Energy Technology Data Exchange (ETDEWEB)

R.E. Rogers

1999-09-27

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

Development of an ELISA assay for screening inhibitors against divalent metal ion dependent alphavirus capping enzyme.

Science.gov (United States)

Kaur, Ramanjit; Mudgal, Rajat; Narwal, Manju; Tomar, Shailly

2018-06-26

Alphavirus non-structural protein, nsP1 has a distinct molecular mechanism of capping the viral RNAs than the conventional capping mechanism of host. Thus, alphavirus capping enzyme nsP1 is a potential drug target. nsP1 catalyzes the methylation of guanosine triphosphate (GTP) by transferring the methyl group from S-adenosylmethionine (SAM) to a GTP molecule at its N7 position with the help of nsP1 methyltransferase (MTase) followed by guanylylation (GT) reaction which involves the formation of m 7 GMP-nsP1 covalent complex by nsP1 guanylyltransferase (GTase). In subsequent reactions, m 7 GMP moiety is added to the 5' end of the viral ppRNA by nsP1 GTase resulting in the formation of cap0 structure. In the present study, chikungunya virus (CHIKV) nsP1 MTase and GT reactions were confirmed by an indirect non-radioactive colorimetric assay and western blot assay using an antibody specific for the m 7 G cap, respectively. The purified recombinant CHIKV nsP1 has been used for the development of a rapid and sensitive non-radioactive enzyme linked immunosorbent assay (ELISA) to identify the inhibitors of CHIKV nsP1. The MTase reaction is followed by GT reaction and resulted in m 7 GMP-nsP1 covalent complex formation. The developed ELISA nsP1 assay measures this m 7 GMP-nsP1 complex by utilizing anti-m 7 G cap monoclonal antibody. The mutation of a conserved residue Asp63 to Ala revealed its role in nsP1 enzyme reaction. Inductively coupled plasma mass spectroscopy (ICP-MS) was used to determine the presence of magnesium ions (Mg 2+ ) in the purified nsP1 protein. The divalent metal ion selectivity and investigation show preference for Mg 2+ ion by CHIKV nsP1. Additionally, using the developed ELISA nsP1 assay, the inhibitory effects of sinefungin, aurintricarboxylic acid (ATA) and ribavirin were determined and the IC 50 values were estimated to be 2.69 µM, 5.72 µM and 1.18 mM, respectively. Copyright © 2018. Published by Elsevier B.V.

Interaction of divalent minerals with liposoluble nutrients and phytochemicals during digestion and influences on their bioavailability - a review.

Science.gov (United States)

Corte-Real, Joana; Bohn, Torsten

2018-06-30

Several divalent minerals, including the macroelements calcium and magnesium, are essential nutrients for humans. However, their intake, especially via high-dose supplements, has been suspected to reduce the availability of lipophilic dietary constituents, including lipids, liposoluble vitamins, and several phytochemicals such as carotenoids. These constituents require emulsification in order to be bioavailable, and high divalent mineral concentrations may perturb this process, due to precipitations of free fatty acids or bile salt complexation, both pivotal for mixed micelle formation. Though in part based on in vitro or indirect evidence, it appears likely that high-dose supplements of divalent minerals around or even below their recommended dietary allowance perturb the availability of certain liposoluble miroconstituents, in addition to reducing absorption of dietary lipids/cholesterol. In this review, we investigate possible negative influences of divalent minerals, including trace elements (iron, zinc), on the digestion and intestinal uptake of lipophilic dietary constituents, with a focus on carotenoids. Copyright © 2018 Elsevier Ltd. All rights reserved.

TOLERANCE OF AGAVE TEQUILANA TO HIGH LEVELS OF DIVALENT METAL CATIONS

Directory of Open Access Journals (Sweden)

Elmi Roseida Cen-Cen

2015-11-01

Full Text Available Los agaves son plantas que pertenecen a un género constituido por numerosas especies, adaptadas para crecer en muy diversos hábitats, algunos con condiciones ambientales extremas. Distintas especies de agave crecen sobre distintos tipos de suelos, algunas en suelos con muy bajo contenido de nutrientes minerales y otras en suelos salinos o en suelos contaminados con iones metálicos. La relación planta-suelo ha sido escasamente estudiada en este género por lo que se desconoce, entre otras cuestiones, cuál es la capacidad de los agaves para absorber, transportar y almacenar nutrientes minerales, cuáles son los mecanismos celulares y bioquímicos que utilizan, o si poseen especial sensibilidad o tolerancia a los iones metálicos. Este estudio reporta el efecto de diversas concentraciones de sulfato de cadmio, cobalto, cobre, zinc o de manganeso sobre plántulas deAgave tequilana, bajo condiciones controladas de laboratorio; la concentración mínima de esos iones metálicos requerida para inducir un efecto tóxico visualmente detectable en tiempos cortos (ocho días; describimos los efectos tóxicos que estos metales generan sobre las plántulas de agave; y reportamos la cantidad de Cu2+, Cd2+ y Co2+ que se acumula en las hojas de plántulas de agave tratadas con altas concentraciones (milimolares de esos metales. Nuestros resultados muestran que, en experimentos de toxicidad aguda y bajo las condiciones aquí establecidas, elA. tequilanaposee una notable tolerancia a altas concentraciones de los distintos metales iónicos probados, incluyendo tanto micronutrientes como metales tóxicos, así como la capacidad de transportar en altas cantidades estos metales a tejido aéreo.

Hemolysis of human red blood cells induced by the combination of diethyldithiocarbamate (DDC) and divalent metals: modulation by anaerobiosis, certain antioxidants and oxidants.

Science.gov (United States)

Ginsburg, I; Sadovnic, M; Varani, J; Tirosh, O; Kohen, R

1999-08-01

The objective of the present communication is to describe the role played by combinations between diethydithiocarbamate (DDC) and divalent metals in hemolysis of human RBC. RBC which had been treated with DDC (10-50 microM) were moderately hemolyzed (about 50%) upon the addition of subtoxic amounts of Cu2+ (50 microM). However, a much stronger and a faster hemolysis occurred either if mixtures of RBC-DDC were immediately treated either by Co2+ (50 microM) or by a premixture of Cu2+ and Co2+ (Cu:Co) (50 microM). While Fe2+ and Ni2+, at 50 microM, initiated 30-50% hemolysis when combined with DDC (50 microM), on a molar basis, Cd2+ was at least 50 fold more efficient than any of the other metals in the initiation of hemolysis by DDC. On the other hand, neither Mn2+ nor Zn2+, had any hemolysis-initiating effects. Co2+ was the only metal which totally blocked hemolysis if added to DDC prior to the addition of the other metals. Hemolysis by mixtures of DDC + (Cu:Co) was strongly inhibited by anaerobiosis (flushing with nitrogen gas), by the reducing agents glutathione, N-acetyl cysteine, mercaptosuccinate, ascorbate, TEMPO, and alpha-tocopherol, by the PLA2 inhibitorbromophenacylbromide (BrPACBr), by tetracycline as well as by phosphatidyl choline, cholesterol and by trypan blue. However, TEMPO, BrPACBr and PC were the only agents which inhibited hemolysis induced by DDC: Cd2+ complexes. On the other hand, none of the classical scavengers of reactive oxygen species (ROS) employed e.g dimethylthiourea, catalase, histidine, mannitol, sodium benzoate, nor the metal chelators desferal and phenanthroline, had any appreciable inhibitory effects on hemolysis induced by DDC + (Cu:Co). DDC oxidized by H2O2 lost its capacity to act in concert either with Cu2+ or with Cd2+ to hemolyze RBC. While either heating RBC to temperatures greater than 37 degrees C or exposure of the cells to glucose-oxidase-generated peroxide diminished their susceptibility to hemolysis, exposure to the

Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

International Nuclear Information System (INIS)

Ho, T.C.; Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

1987-01-01

A process is described for hydrotreating a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and heating the composite at elevated temperature of at least about 150 0 C, in the presence of sulfur and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand L. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrotreat at least a portion of the feed

High-energy-density, aqueous, metal-polyiodide redox flow batteries

Science.gov (United States)

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

Electronic structure and superconductivity of divalent metals under very high pressure

International Nuclear Information System (INIS)

Bireckoven, B.

1987-05-01

A single crystal, high-pressure diamond cell has been developed for the study of superconductors under pressures to over 50 GPa. A high sensitivity AC-SQUID magnetometer has been employed to detect the diamagnetic response of the very small samples at T C . The T C (p)-dependence of the lead-manometer has been calibrated against the ruby-pressure-scale up to pressures of 30 GPa. In spite of the well-known fcc/hcp-transition at 13 GPa lead shows a smooth T C (p)-behaviour and thus is a very suitable manometer. Band structure calculations for the alkaline earth metals indicate an appreciable s-to-d transfer with increasing pressure. In fact, superconductivity was previously observed in the pressure induced d-transition metals Sr and Ba (however not yet in Ca). For the first time the author presents a quantitative investigation of T C as a function of p up to 50 GPa. Both elements turn out to be ''good'' superconductors featuring T C 's of about 7 K. The possibility of a generalized phase diagram for the alkaline earth metals will be critically discussed. At any rate, the occurrence of such high T C 's is rather strong evidence for a substantial d-transition metal character at high p. Investigations of very dilute BaEu-alloys up to 45 GPa reveal a strong monotonic increase of ΔT C = T C Ba -T C BaEu . (orig./GSCH)

Effects of mutagenesis of aspartic acid residues in the putative phosphoribosyl diphosphate binding site of Escherichia coli phosphoribosyl diphosphate synthetase on metal ion specificity and ribose-5-phosphate binding

DEFF Research Database (Denmark)

Willemoës, Martin; Nilsson, Dan; Hove-Jensen, Bjarne

1996-01-01

The three conserved aspartic acid residues of the 5-phospho-d-ribosyl a-1-diphosphate binding site (213-GRDCVLVDDMIDTGGT-228) of Escherichia coli phosphoribosyl diphosphate synthetase were studied by analysis of the mutant enzymes D220E, D220F, D221A, D224A, and D224S. The mutant enzymes showed...... enzymes were dependent on the metal ion present, suggesting a function of the investigated aspartic acid residues both in the binding of ribose 5-phosphate, possibly via a divalent metal ion, and in the interaction with a divalent metal ion during catalysis....

Precipitation of gold and silver from cyanide solutions by hydrated electrons generated by ionizing radiation

International Nuclear Information System (INIS)

Chernyak, A.S.; Zhigunov, V.A.; Shepot'ko, M.L.; Smirnov, G.I.; Dolin, P.I.; Bobrova, A.S.; Khikin, G.I.

1981-01-01

Redox reactions are widely used in chemistry and chemical engineering for the precipitation of noble metals, since this general class of reactions offers the possibility of selective recovery of these metals from solutions that are complex in composition. The classical method for precipitation of gold and silver from cyanide process solutions is reduction by metallic zinc. This process has certain advantages, and it is easy to carry out under plant conditions with high indices of efficiency. However, the precipitation of gold and silver is accompanied by contamination of the solutions with zinc ions, which makes it difficult to recycle the cyanide solutions; also, additional treatment of the precipitates is required before they are directed to the refining process. Hence, greater quantities of reagents are required, the process conversion becomes more complicated, and the cost of producing the metals is higher. All of these factors make it attractive to seek new methods for processing cyanide solutions that do not have these shortcomings. An interesting approach to the solution of this problem is the use of so-called ''reagentless'' precipitation methods, among which we may class the reduction of gold and silver to the metallic state in cyanide solutions by hydrated electrons generated by ionizing radiation. The significant advances that have been made in research on the hydrated electron, along with data indicating that it is feasible, at least in principle, to use the hydrated electron for industrial purposes, have been the stiumlus for setting up the studies that are reported here

Synthesis and characterization of divalent metal complexes with ligand derived from the reaction of 3-aminopyridine and biacetyl

Directory of Open Access Journals (Sweden)

RAMESH KUMAR

2006-09-01

Full Text Available Divalent cobalt, nickel and copper salts reacted in situ with 3-aminopyridine and biacetyl to form complexes of the type: [M(Ap2biac2X2], where Ap2biac is the ligand and X=Cl, Br, NO3 or NCS. The complexes were analysed and characterized as distorted octahedral by conductance, molecular weight, magnetic, electronic and IR spectral studies. The electronic spectra were interpreted and tentative aassignments made. The infrared spectral studies revealed that two molecules of 3-aminopyridine were joined by molecules of biacetyl through a two carbon atom bridge and that the ligand coordinated through azomethine nitrogen atoms, whereas the pyridine nitrogen does not participate in the coordination. In the far infrared spectra, various metal–ligand vibrations were observed and are discussed.

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

Science.gov (United States)

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

2005-01-01

The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

Strong Dependence of Hydration State of F-Actin on the Bound Mg(2+)/Ca(2+) Ions.

Science.gov (United States)

Suzuki, Makoto; Imao, Asato; Mogami, George; Chishima, Ryotaro; Watanabe, Takahiro; Yamaguchi, Takaya; Morimoto, Nobuyuki; Wazawa, Tetsuichi

2016-07-21

Understanding of the hydration state is an important issue in the chemomechanical energetics of versatile biological functions of polymerized actin (F-actin). In this study, hydration-state differences of F-actin by the bound divalent cations are revealed through precision microwave dielectric relaxation (DR) spectroscopy. G- and F-actin in Ca- and Mg-containing buffer solutions exhibit dual hydration components comprising restrained water with DR frequency f2 (fw). The hydration state of F-actin is strongly dependent on the ionic composition. In every buffer tested, the HMW signal Dhyme (≡ (f1 - fw)δ1/(fwδw)) of F-actin is stronger than that of G-actin, where δw is DR-amplitude of bulk solvent and δ1 is that of HMW in a fixed-volume ellipsoid containing an F-actin and surrounding water in solution. Dhyme value of F-actin in Ca2.0-buffer (containing 2 mM Ca(2+)) is markedly higher than in Mg2.0-buffer (containing 2 mM Mg(2+)). Moreover, in the presence of 2 mM Mg(2+), the hydration state of F-actin is changed by adding a small fraction of Ca(2+) (∼0.1 mM) and becomes closer to that of the Ca-bound form in Ca2.0-buffer. This is consistent with the results of the partial specific volume and the Cotton effect around 290 nm in the CD spectra, indicating a change in the tertiary structure and less apparent change in the secondary structure of actin. The number of restrained water molecules per actin (N2) is estimated to be 1600-2100 for Ca2.0- and F-buffer and ∼2500 for Mg2.0-buffer at 10-15 °C. These numbers are comparable to those estimated from the available F-actin atomic structures as in the first water layer. The number of HMW molecules is roughly explained by the volume between the equipotential surface of -kT/2e and the first water layer of the actin surface by solving the Poisson-Boltzmann equation using UCSF Chimera.

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.

Effect of illite clay and divalent cations on bitumen recovery

Energy Technology Data Exchange (ETDEWEB)

Ding, X. [SNC-Lavalin Inc., Calgary, AB (Canada); Repka, C. [Baker Petrolite Corp., Fort McMurray, AB (Canada); Xu, Z.; Masliyah, J. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

2006-12-15

Nearly 35 per cent of Canada's petroleum needs can be met from the Athabasca oil sands, particularly as conventional sources of petroleum decline. The interactions between bitumen and clay minerals play a key role in the recovery process of bitumen because they affect bitumen aeration. The 2 clays minerals found in various oil sands extraction process streams are kaolinite and illite. In this study, doping flotation tests using deionized water and electrokinetic studies were performed to examine the effect of illite clays on bitumen recovery. The effect of magnesium ions was also examined and compared with calcium ions. This paper also discussed the effects of temperature and tailings water chemistry. The negative effect of illite clay on bitumen recovery was found to be associated with its acidity. Denver flotation cell measurements indicated that the addition of calcium or magnesium ions to the flotation deionized water had only a slight effect on bitumen recovery, but the co-addition of illite clay and divalent cations resulted in a dramatic reduction in bitumen recovery. The effect was more significant at lower process temperature and low pH values. Zeta potential distributions of illite suspensions and bitumen emulsions were measured individually and as a mixture to determine the effect of divalent cations on the interaction between bitumen and illite clay. The presence of 1 mM calcium or magnesium ions in deionized water had a pronounced effect on the interactions between bitumen and illite clay. Slime coating of illite onto bitumen was not observed in zeta potential distribution measurements performed in alkaline tailings water. When tests were conducted using plant recycle water, the combination of illite clay and divalent cations did not have an adverse effect on bitumen recovery. 25 refs., 3 tabs., 15 figs.

[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.

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

Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology.

Science.gov (United States)

Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

2015-01-01

Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail.

Inter-DNA Attraction Mediated by Divalent Counterions

International Nuclear Information System (INIS)

Qiu Xiangyun; Andresen, Kurt; Kwok, Lisa W.; Lamb, Jessica S.; Park, Hye Yoon; Pollack, Lois

2007-01-01

Can nonspecifically bound divalent counterions induce attraction between DNA strands? Here, we present experimental evidence demonstrating attraction between short DNA strands mediated by Mg 2+ ions. Solution small angle x-ray scattering data collected as a function of DNA concentration enable model independent extraction of the second virial coefficient. As the [Mg 2+ ] increases, this coefficient turns from positive to negative reflecting the transition from repulsive to attractive inter-DNA interaction. This surprising observation is corroborated by independent light scattering experiments. The dependence of the observed attraction on experimental parameters including DNA length provides valuable clues to its origin

Progress in quantitative X-ray microanalysis of frozen-hydrated bulk biological samples

International Nuclear Information System (INIS)

Marshall, A.T.

1988-01-01

The analysis of bulk frozen-hydrated biological samples has developed now to a level where practical application of the technique is possible. Provided the sample is carefully coated with a conductive metal, the development of a space charge capable of causing a significant distortion of the electron diffusion volume does not seem to occur, and analytical resolution can be conveniently held to approximately 2 micron (both depth and lateral resolution). Two valid quantitative methods are available, and two methods of determining dry weight fractions are also available. An area where further research could lead to improvement in analysis of frozen-hydrated bulk samples is in the investigation of fracturing methods. If fracture planes that were flat and reproducible could be easily obtained, some of the difficulties of analysing frozen-hydrated bulk samples would be considerably reduced

Hydration water and microstructure in calcium silicate and aluminate hydrates

International Nuclear Information System (INIS)

Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

2006-01-01

Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

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

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

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

Heavy Metal Removal by Chitosan and Chitosan Composite

International Nuclear Information System (INIS)

Abdel-Mohdy, F.A.; El-Sawy, S.; Ibrahim, M.S.

2005-01-01

Radiation grafting of diethyl aminoethyl methacrylate (DEAEMA) on chitosan to impart ion exchange properties and to be used for the separation of metal ions from waste water, was carried out. The effect of experimental conditions such as monomer concentration and the radiation dose on grafting were studied. On using chitosan, grafted chitosan and some chitosan composites in metal ion removal they show high up-take capacity for Cu 2+ and lower uptake capacities for the other divalent metal ions used (Zn and Co). Competitive study, performed with solutions containing mixture of metal salts, showed high selectivity for Cu 2+ than the other metal ion. Limited grafting of DEAEMA polymer -containing specific functional groups-onto the chitosan backbone improves the sorption performance

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

Science.gov (United States)

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

2018-01-01

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

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

Science.gov (United States)

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

2007-12-01

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

Improved Design and Fabrication of Hydrated-Salt Pills

Science.gov (United States)

Shirron, Peter J.; DiPirro, Michael J.; Canavan, Edgar R.

2011-01-01

A high-performance design, and fabrication and growth processes to implement the design, have been devised for encapsulating a hydrated salt in a container that both protects the salt and provides thermal conductance between the salt and the environment surrounding the container. The unitary salt/container structure is known in the art as a salt pill. In the original application of the present design and processes, the salt is, more specifically, a hydrated paramagnetic salt, for use as a refrigerant in a very-low-temperature adiabatic demagnetization refrigerator (ADR). The design and process can also be applied, with modifications, to other hydrated salts. Hydrated paramagnetic salts have long been used in ADRs because they have the desired magnetic properties at low temperatures. They also have some properties, disadvantageous for ADRs, that dictate the kind of enclosures in which they must be housed: Being hydrated, they lose water if exposed to less than 100-percent relative humidity. Because any dehydration compromises their magnetic properties, salts used in ADRs must be sealed in hermetic containers. Because they have relatively poor thermal conductivities in the temperature range of interest (<0.1 K), integral thermal buses are needed as means of efficiently transferring heat to and from the salts during refrigeration cycles. A thermal bus is typically made from a high-thermal-conductivity met al (such as copper or gold), and the salt is configured to make intimate thermal contact with the metal. Commonly in current practice (and in the present design), the thermal bus includes a matrix of wires or rods, and the salt is grown onto this matrix. The density and spacing of the conductors depend on the heat fluxes that must be accommodated during operation.

Metallization of bacterial cellulose for electrical and electronic device manufacture

Science.gov (United States)

Evans, Barbara R [Oak Ridge, TN; O'Neill, Hugh M [Knoxville, TN; Jansen, Valerie Malyvanh [Memphis, TN; Woodward, Jonathan [Knoxville, TN

2010-09-28

A method for the deposition of metals in bacterial cellulose and for the employment of the metallized bacterial cellulose in the construction of fuel cells and other electronic devices is disclosed. The method for impregnating bacterial cellulose with a metal comprises placing a bacterial cellulose matrix in a solution of a metal salt such that the metal salt is reduced to metallic form and the metal precipitates in or on the matrix. The method for the construction of a fuel cell comprises placing a hydrated bacterial cellulose support structure in a solution of a metal salt such that the metal precipitates in or on the support structure, inserting contact wires into two pieces of the metal impregnated support structure, placing the two pieces of metal impregnated support structure on opposite sides of a layer of hydrated bacterial cellulose, and dehydrating the three layer structure to create a fuel cell.

Crystal structure and properties of tetragonal EuAg4In8 grown by metal flux technique

International Nuclear Information System (INIS)

Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C.

2015-01-01

The compound EuAg 4 In 8 has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg 4 In 8 crystallizes in the CeMn 4 Al 8 structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg 4 In 8 is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg 4 In 8 was measured in the temperature range 2–300 K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg 4 In 8 is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg 4 In 8 has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg 4 In 8 phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg 4 In 8 . • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior

Ion exchange equilibrium for some uni-univalent and uni-divalent ...

African Journals Online (AJOL)

The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well ...

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

Fluorescent Protein-Based Ca2+ Sensor Reveals Global, Divalent Cation-Dependent Conformational Changes in Cardiac Troponin C.

Directory of Open Access Journals (Sweden)

Myriam A Badr

Full Text Available Cardiac troponin C (cTnC is a key effector in cardiac muscle excitation-contraction coupling as the Ca2+ sensing subunit responsible for controlling contraction. In this study, we generated several FRET sensors for divalent cations based on cTnC flanked by a donor fluorescent protein (CFP and an acceptor fluorescent protein (YFP. The sensors report Ca2+ and Mg2+ binding, and relay global structural information about the structural relationship between cTnC's N- and C-domains. The sensors were first characterized using end point titrations to decipher the response to Ca2+ binding in the presence or absence of Mg2+. The sensor that exhibited the largest responses in end point titrations, CTV-TnC, (Cerulean, TnC, and Venus was characterized more extensively. Most of the divalent cation-dependent FRET signal originates from the high affinity C-terminal EF hands. CTV-TnC reconstitutes into skinned fiber preparations indicating proper assembly of troponin complex, with only ~0.2 pCa unit rightward shift of Ca2+-sensitive force development compared to WT-cTnC. Affinity of CTV-TnC for divalent cations is in agreement with known values for WT-cTnC. Analytical ultracentrifugation indicates that CTV-TnC undergoes compaction as divalent cations bind. C-terminal sites induce ion-specific (Ca2+ versus Mg2+ conformational changes in cTnC. Our data also provide support for the presence of additional, non-EF-hand sites on cTnC for Mg2+ binding. In conclusion, we successfully generated a novel FRET-Ca2+ sensor based on full length cTnC with a variety of cellular applications. Our sensor reveals global structural information about cTnC upon divalent cation binding.

Thermal study of monovalent-divalent phase transition in npBifc-F1TCNQ System

International Nuclear Information System (INIS)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji; Mochida, Tomoyuki

2009-01-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F 1 TCNQ) 3 , Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D + A - ) and the divalent state (D 2+ A 2- ). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (ΔS) was determined to be 22 ± 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

The modulation of TRPM7 currents by nafamostat mesilate depends directly upon extracellular concentrations of divalent cations

Directory of Open Access Journals (Sweden)

Chen Xuanmao

2010-12-01

Full Text Available Abstract Concentrations of extracellular divalent cations (Ca2+ and Mg2+ fall substantially during intensive synaptic transmission as well as during some pathophysiological conditions such as epilepsy and brain ischemia. Here we report that a synthetic serine protease inhibitor, nafamostat mesylate (NM, and several of its analogues, block recombinant TRPM7 currents expressed in HEK293T cells in inverse relationship to the concentration of extracellular divalent cations. Lowering extracellular Ca2+ and Mg2+ also evokes a divalent-sensitive non-selective cation current that is mediated by TRPM7 expression in hippocampal neurons. In cultured hippocampal neurons, NM blocked these TRPM7-mediated currents with an apparent affinity of 27 μM, as well as the paradoxical Ca2+ influx associated with lowering extracellular Ca2+. Unexpectedly, pre-exposure to NM strongly potentiated TRPM7 currents. In the presence of physiological concentrations of extracellular divalent cations, NM activates TRPM7. The stimulating effects of NM on TRPM7 currents are also inversely related to extracellular Ca2+ and Mg2+. DAPI and HSB but not netropsin, blocked and stimulated TRPM7. In contrast, mono-cationic, the metabolites of NM, p-GBA and AN, as well as protease inhibitor leupeptin and gabexate failed to substantially modulate TRPM7. NM thus provides a molecular template for the design of putative modulators of TRPM7.

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

Science.gov (United States)

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

2004-12-01

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

Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

International Nuclear Information System (INIS)

Montney, Matthew R.; Supkowski, Ronald M.; Staples, Richard J.; LaDuca, Robert L.

2009-01-01

Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)] n neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)] n chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group

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 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.

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.

Internal hydration of a metal-transporting ATPase is controlled by membrane lateral pressure

Energy Technology Data Exchange (ETDEWEB)

Fahmy, Karim [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Fischermeier, E. [Technische Univ. Dresden (Germany); Pospisil, P. [A.S.C. R., Prague (Czech Republic). J. Heyrovsky Inst. Physical Chemistry; Solioz, M. [Bern Univ. (Switzerland); Sayed, A.; Hof, M.

2017-07-01

The active transport of ions across biological mem branes requires their hydration shell to interact with the interior of membrane proteins. However, the influence of the external lipid phase on internal dielectric dynamics is hard to access by experiment. Using the octahelical transmembrane architecture of the copper-transporting P{sub 1B}-type ATPase from Legionella pneumophila (LpCopA) as a model structure, we have established the site-specific labeling of internal cysteines with a polarity-sensitive fluorophore. This enabled dipolar relaxation studies in a solubilized form of the protein and in its lipid-embedded state in nano-discs (NDs). Time-dependent fluorescence shifts revealed the site-specific hydration and dipole mobility around the conserved ion-binding motif. The spatial distribution of both features is shaped significantly and independently of each other by membrane lateral pressure.

Internal hydration of a metal-transporting ATPase is controlled by membrane lateral pressure

International Nuclear Information System (INIS)

Fahmy, Karim; Pospisil, P.; Sayed, A.; Hof, M.

2017-01-01

The active transport of ions across biological mem branes requires their hydration shell to interact with the interior of membrane proteins. However, the influence of the external lipid phase on internal dielectric dynamics is hard to access by experiment. Using the octahelical transmembrane architecture of the copper-transporting P_1_B-type ATPase from Legionella pneumophila (LpCopA) as a model structure, we have established the site-specific labeling of internal cysteines with a polarity-sensitive fluorophore. This enabled dipolar relaxation studies in a solubilized form of the protein and in its lipid-embedded state in nano-discs (NDs). Time-dependent fluorescence shifts revealed the site-specific hydration and dipole mobility around the conserved ion-binding motif. The spatial distribution of both features is shaped significantly and independently of each other by membrane lateral pressure.

Methane Hydrates: Chapter 8

Science.gov (United States)

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

2008-01-01

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

Transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

International Nuclear Information System (INIS)

Jacobson, A.J.; Chianelli, R.R.; Pecoraro, T.A.

1987-01-01

A process is described for hydrorefining a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and in the presence of hydrogen with a catalyst obtained by heating one or more precursor salts at elevated temperature of at least about 150 0 C, in the presence of sulfur or one or more sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrorefine at least a portion of the feed

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.

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.

Chemical potentials of alkaline earth metal halide aqueous electrolytes and solubility of their hydrates by molecular simulation: Application to CaCl2, antarcticite, and sinjarite

Science.gov (United States)

Moučka, Filip; Kolafa, Jiří; Lísal, Martin; Smith, William R.

2018-06-01

We present a molecular-level simulation study of CaCl2 in water and crystalline hydrates formed by CaCl2 at ambient (298.15 K, 1 bar) conditions and at a high-temperature high-pressure state (365 K, 275 bars) typical of hydraulic fracturing conditions in natural-gas extraction, at which experimental properties are poorly characterized. We focus on simulations of chemical potentials in both solution and crystalline phases and on the salt solubility, the first time to our knowledge that such properties have been investigated by molecular simulation for divalent aqueous electrolytes. We first extend our osmotic ensemble Monte Carlo simulation technique [F. Moučka et al., J. Phys. Chem. B 115, 7849-7861 (2011)] to such solutions. We then describe and apply new methodology for the simulation of the chemical potentials of the experimentally observed crystalline hydrates at ambient conditions (antarcticite, CaCl2.6H2O) and at high-temperature conditions (sinjarite, CaCl2.2H2O). We implement our methodologies using for both phases the CaCl2 transferable force field (FF) based on simple point charge-extended water developed by Mamatkulov et al. [J. Chem. Phys. 138, 024505 (2013)], based on training sets involving single-ion and ion-pair low-concentration solution properties at near-ambient conditions. We find that simulations of the solution chemical potentials at high concentrations are somewhat problematic, exhibiting densities diverging from experimental values and accompanied by dramatically decreasing particle mobility. For the solid phases, the sinjarite crystalline lattice differs from experiment only slightly, whereas the simulations of antarcticite completely fail, due to instability of the crystalline lattice. The FF thus only successfully yields the sinjarite solubility, but its value m = 8.0(7) mol kg-1H2O lies well below the experimentally observed solubility range at 1 bar pressure of (12m, 15m) in the temperature interval (320 K, 400 K). We conclude that the

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.)

Characterization of nano-porous oxides containing aqueous heavy metallic ions

International Nuclear Information System (INIS)

Louisfrema, Wilfried

2016-01-01

Porous crystalline aluminosilicates such as cationic zeolites, are widely studied because of their adsorption, ion exchange and catalytic properties, which explain their use in many industrial applications. Examples of the latter, which involve in particular multivalent cations, include detergents/softeners, catalytic cracking, or decontamination. Such industrial applications of zeolites all exploit their adsorption properties, which vary as a function of the pore size, comparable to the adsorbing molecules, or chemical composition, which results in charges within the framework, and in turn strong binding or repulsive sites. Importantly, in such applications zeolites are hydrated. Water is involved in the microscopic processes and thus influences all properties of the material. Molecular modeling is a weapon of choice to predict and understand the microscopic properties of the hydrated material, which are difficult to access experimentally. More precisely, the present modeling work deals with the behavior of multivalent cations in hydrated zeolites, in collaboration with experimentalists. Our study on zeolite Y faujasite first allowed us to clarify the migration of sodium cations upon dehydration and to predict the cation localization in the hydrated material in the presence of divalent cations. Furthermore, we rationalized the coupled migration of cations and deformation of the framework upon water adsorption. To this end, we have developed a new method for the analysis of cation localization. The good performance of a polarizable force field demonstrated here paves the way for the study of the dynamics of the whole system, following in particular the simultaneous migration of cations and deformation of the framework. Such an approach could be later extended to other multivalent ions of industrial interest (rare Earths, f-block elements,...). (author)

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

Science.gov (United States)

Camilleri, J; Sorrentino, F; Damidot, D

2015-04-01

BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited

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

A QUANTUM MECHANICAL STUDY OF THE PROTONATION AND COVALENT HYDRATION OF QUINAZOLINE IN THE PRESENCE OF METAL CATIONS

Science.gov (United States)

We have investigated the protonation and reversible covalent hydration of quinazoline in the presence of Li+, Na+, and Ca2+ ions using ab initio quantum mechanical calculations at the MP2/6-31G**//HF/6-31G*level of theory. Proton affinities, enthalpies of hydration at 298.15K (DH...

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

Fire extinction utilizing carbon dioxide hydrate

Energy Technology Data Exchange (ETDEWEB)

Hatakeyama, T.; Aida, E.; Yokomori, T.; Ohmura, R.; Ueda, T. [Keio Univ., Hiyoshi, Kohoku-ku, Yokohama (Japan)

2008-07-01

Clathrate hydrates formed with nonflammable gases may be suitable for use as fire extinguishing agents because dissociation of the hydrates results in the temperature decrease in the combustion field and the nonflammable gases released from the dissociated hydrates prevent the supply of the oxygen to the combustion field. This paper discussed experiments in which ordinary ice and dry ice were used to evaluate the performance of CO{sub 2} hydrate as a fire extinguishing agent. The paper described the apparatus and procedure for the preparation of CO{sub 2} hydrate crystals. A schematic of the reactor to form CO{sub 2} hydrate and a photograph of CO{sub 2} hydrate crystal formed in the study were also presented. Other illustrations, photographs, and tables that were presented included a schematic diagram of the experimental apparatus used for the flame extinction experiments; a photograph of CO{sub 2} hydrate powder; sequential video graphs of the flame extinction by the supply of CO{sub 2} hydrate crystals to the methanol pool flame and the relevant illustration; and heat of CO{sub 2} hydrate dissociation, water vaporization and sublimation of dry ice. It was concluded that the critical mass of the CO{sub 2} hydrate required to extinguish a flame was much less than that of ordinary ice, indicating the superiority of CO{sub 2} hydrate to the ice. In addition, the experiments also revealed that the size of the CO{sub 2} hydrate particles had a significant effect on the performance of flame extinction. 5 refs., 2 tabs., 7 figs.

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.

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…

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

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

Thermal study of monovalent-divalent phase transition in npBifc-F{sub 1}TCNQ System

Energy Technology Data Exchange (ETDEWEB)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji [Department of Physics, Faculty of Science, Toho University, Miyama 2-2-1, Funabashi, Chiba, 274-8510 (Japan); Mochida, Tomoyuki, E-mail: nishio@ph.sci.toho-u.ac.j [Department of Chemistry, Faculty of Science, Kobe University, Rokkodai, Nada, Kobe 657-8501 (Japan)

2009-03-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F{sub 1}TCNQ){sub 3}, Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D{sup +}A{sup -}) and the divalent state (D{sup 2+}A{sup 2-}). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (DELTAS) was determined to be 22 +- 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

The effects of monovalent and divalent cations on the stability of silver nanoparticles formed from direct reduction of silver ions by Suwannee River humic acid/natural organic matter

Energy Technology Data Exchange (ETDEWEB)

Akaighe, Nelson [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Depner, Sean W.; Banerjee, Sarbajit [Department of Chemistry, 410 Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 (United States); Sharma, Virender K. [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Sohn, Mary, E-mail: msohn@fit.edu [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States)

2012-12-15

The formation and characterization of AgNPs (silver nanoparticles) formed from the reduction of Ag{sup +} by SRNOM (Suwannee River natural organic matter) is reported. The images of SRNOM-formed AgNPs and the selected area electron diffraction (SAED) were captured by high resolution transmission electron microscopy (HRTEM). The colloidal and chemical stability of SRNOM- and SRHA (Suwannee River humic acid)-formed AgNPs in different ionic strength solutions of NaCl, KCl, CaCl{sub 2} and MgCl{sub 2} was investigated in an effort to evaluate the key fate and transport processes of these nanoparticles in natural aqueous environments. The aggregation state, stability and sedimentation rate of the AgNPs were monitored by Dynamic Light Scattering (DLS), zeta potential, and UV-vis measurements. The results indicate that both types of AgNPs are very unstable in high ionic strength solutions. Interestingly, the nanoparticles appeared more unstable in divalent cation solutions than in monovalent cation solutions at similar concentrations. Furthermore, the presence of SRNOM and SRHA contributed to the nanoparticle instability at high ionic strength in divalent metallic cation solutions, most likely due to intermolecular bridging with the organic matter. The results clearly suggest that changes in solution chemistry greatly affect nanoparticle long term stability and transport in natural aqueous environments. Highlights: Black-Right-Pointing-Pointer Formation of SRNOM-AgNPs under environmentally relevant conditions Black-Right-Pointing-Pointer Influence of monovalent versus divalent cations on SRHA- and SRNOM-AgNP stability Black-Right-Pointing-Pointer Effect of AgNPs on organic matter removal from water columns.

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

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

Flow assurance intervention, hydrates remediation

Energy Technology Data Exchange (ETDEWEB)

Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)

2012-07-01

This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

A dynamic model to explain hydration behaviour along the lanthanide series

International Nuclear Information System (INIS)

Duvail, M.; Spezia, R.; Vitorge, P.

2008-01-01

An understanding of the hydration structure of heavy atoms, such as transition metals, lanthanides and actinides, in aqueous solution is of fundamental importance in order to address their solvation properties and chemical reactivity. Herein we present a systematic molecular dynamics study of Ln 3+ hydration in bulk water that can be used as reference for experimental and theoretical research in this and related fields. Our study of hydration structure and dynamics along the entire Ln 3+ series provides a dynamic picture of the CN behavioural change from light (CN=9 predominating) to heavy (CN=8 predominating) lanthanides consistent with the exchange mechanism proposed by Helm, Merbach and co-workers. This scenario is summarized in this work. The hydrated light lanthanides are stable TTP structures containing two kinds of water molecules: six molecules forming the trigonal prism and three in the centre triangle. Towards the middle of the series both ionic radii and polarizabilities decrease, such that first-shell water-water repulsion increases and water-cation attraction decreases. This mainly applies for molecules of the centre triangle of the nine-fold structure. Thus, one of these molecules stay in the second hydration sphere of the lanthanide for longer average times, as one progresses along the lanthanide series. The interchange between predominantly CN=9 and CN=8 is found between Tb and Dy. Therefore, we propose a model that determines the properties governing the change in the first-shell coordination number across the series, confirming the basic hypothesis proposed by Helm and Merbach. We show that it is not a sudden change in behaviour, but rather that it results from a statistical predominance of one first hydration shell structure containing nine water molecules over one containing eight. This is observed progressively across the series. (O.M.)

Two-phase coexistence in the monovalent-to-divalent phase transition of dineopentylbiferrocene-fluorotetracyanoquinodimethane [npBifc-(F1TCNQ)3], charge-transfer salt

International Nuclear Information System (INIS)

Uruichi, Mikio; Yue, Yue; Yakushi, Kyuya; Mochida, Tomoyuki

2007-01-01

We present experimental findings showing that for npBifc-(F 1 TCNQ) 3 , two phases coexist over a wide temperature interval of 100-150 K near the monovalent-to-divalent phase transition temperature. Macroscopic domains of the high-temperature (monovalent) and low-temperature (divalent) phases were detected in the transition temperature region using X-ray diffraction and micro-Raman spectroscopy techniques. The volume fraction of the two domains continuously varied depending upon the temperature. A considerably large volume difference was found between the monovalent and divalent phases. The effect of volumetric strain due to this volume difference is discussed to understand this inhomogeneous state. (author)

Indian continental margin gas hydrate prospects : results of the Indian National Gas Hydrate Program (NGHP) expedition 01

Energy Technology Data Exchange (ETDEWEB)

Collett, T [United States Geological Survey, Denver, CO (United States); Riedel, M. [McGill Univ., Montreal, PQ (Canada). Dept. of Earth and Planetary Sciences; Cochran, J.R. [Columbia Univ., Palisades, NY (United States). Lamont Doherty Earth Observatory; Boswell, R. [United States Dept. of Energy, Morgantown, WV (United States). National Energy Technology Lab; Kumar, P. [Pushpendra Kumar Oil and Natural Gas Corp. Ltd., Mumbai (India). Inst. of Engineering and Ocean Technology; Sathe, A.V. [Oil and Natural Gas Corp. Ltd., Uttaranchal (India). KDM Inst. of Petroleum Exploration

2008-07-01

The geologic occurrence of gas hydrate deposits along the continental margins of India were investigated in the first expedition of the Indian National Gas Hydrate Program (NGHP). The objective was to determine the regional context and characteristics of the gas hydrate deposits through scientific ocean drilling, logging, and analytical activities. A research drill ship was the platform for the drilling operation. The geological and geophysical studies revealed 2 geologically distinct areas with inferred gas hydrate occurrences, notably the passive continental margins of the Indian Peninsula and along the Andaman convergent margin. The NGHP Expedition 01 focused on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these 2 diverse settings. The study established the presence of gas hydrates in Krishna-Godavari, Mahanadi and Andaman basins. Site 10 in the Krishna-Godavari Basin was discovered to be the one of the richest gas hydrate accumulations yet documented, while site 17 in the Andaman Sea had the thickest and deepest gas hydrate stability zone yet known. The existence of a fully-developed gas hydrate system in the Mahanadi Basin was also discovered. Most of the gas hydrate occurrences discovered during this expedition appeared to contain mostly methane which was generated by microbial processes. However, there was also evidence of a thermal origin for a portion of the gas within the hydrates of the Mahanadi Basin and the Andaman offshore area. Gas hydrate in the Krishna-Godavari Basin appeared to be closely associated with large scale structural features, in which the flux of gas through local fracture systems, generated by the regional stress regime, controlled the occurrence of gas hydrate. 3 refs., 1 tab., 2 figs.

Metal ion controlled self-assembly of a chemically reengineered protein drug studied by small-angle X-ray scattering

DEFF Research Database (Denmark)

Jesper, Nygaard; Munch, Henrik K.; Thulstrup, Peter W.

2012-01-01

. A small-angle X-ray scattering analysis of the bipyridine-modified insulin system confirmed an organization into a novel well-ordered structure based on insulin trimers, as induced by the addition of Fe(II). In contrast, unmodified monomeric insulin formed larger and more randomly structured assemblies......Precise control of the oligomeric state of proteins is of central importance for biological function and for the properties of biopharmaceutical drugs. Here, the self-assembly of 2,2′-bipyridine conjugated monomeric insulin analogues, induced through coordination to divalent metal ions, was studied....... This protein drug system was designed to form non-native homo-oligomers through selective coordination of two divalent metal ions, Fe(II) and Zn(II), respectively. The insulin type chosen for this study is a variant designed for a reduced tendency toward native dimer formation at physiological concentrations...

The rates measurement of methane hydrate formation and dissociation using micro-drilling system application for gas hydrate exploration

Energy Technology Data Exchange (ETDEWEB)

Bin Dou [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)]|[Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Reinicke, K.M. [Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Guosheng Jiang; Xiang Wu; Fulong Ning [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)

2006-07-01

When drilling through gas hydrate bearing formations, the energy supplied by virtue of the drilling process may lead to a destabilization of the hydrates surrounding the wellbore. Therefore, as the number of oil and gas fields being development in deepwater and onshore arctic environments increases, greater emphasis should be placed on quantifying the risks, gas hydrates pose to drilling operations. The qualification of these risks requires a comprehensive understanding of gas hydrate-formation and dissociation as a result of drilling induced processes. To develop the required understanding of gas hydrat formation and dissociation, the authors conducted laboratory experiments by using a micro-drilling system, to study the dissociation rates of methane hydrates contained in a tank reactor. The test facility used is a development of China University of Geosciences. The rates of methane hydrate formation and dissociation in the tank reactor were measured at steady-state conditions at pressures ranging from 0.1 to 25 MPa and temperatures ranging from -5 to 20 C. The experimental results show that the rate of hydrate formation is strongly influenced by the fluid system used to form the hydrates, pressure and temperature, with the influence of the temperature on methane hydrate dissociation being stronger than that of the pressure. Drilling speed, drilling fluids and hydrate dissociation inhibitors were also shown to influence hydrate dissociation rate. The derived results have been used to predict hydrate drilling stability for several drilling fluid systems.

In situ NMR studies of hydrogen storage kinetics and molecular diffusion in clathrate hydrate at elevated hydrogen pressures

Energy Technology Data Exchange (ETDEWEB)

Okuchi, T. [Okayama Univ., Misasa, Tottori (Japan); Moudrakovski, I.L.; Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

The challenge of storing high-density hydrogen into compact host media was investigated. The conventional storage scheme where an aqueous solution is frozen with hydrogen gas is too slow for practical use in a hydrogen-based society. Therefore, the authors developed a faster method whereby hydrogen was stored into gas hydrates. The hydrogen gas was directly charged into hydrogen-free, crystalline hydrate powders with partly empty lattices. The storage kinetics and hydrogen diffusion into the hydrate was observed in situ by nuclear magnetic resonance (NMR) in a pressurized tube cell. At pressures up to 20 MPa, the storage was complete within 80 minutes, as observed by growth of stored-hydrogen peak into the hydrate. Hydrogen diffusion within the crystalline hydrate media is the rate-determining step of current storage scheme. Therefore, the authors measured the diffusion coefficient of hydrogen molecules using the pulsed field gradient NMR method. The results show that the stored hydrogen is very mobile at temperatures down to 250 K. As such, the powdered hydrate media should work well even in cold environments. Compared with more prevailing hydrogen storage media such as metal hydrides, clathrate hydrates have the advantage of being free from hydrogen embrittlement, more chemically durable, more environmentally sound, and economically affordable. It was concluded that the powdered clathrate hydrate is suitable as a hydrogen storage media. 22 refs., 4 figs.

Divalent Cations Regulate the Ion Conductance Properties of Diverse Classes of Aquaporins

Directory of Open Access Journals (Sweden)

Mohamad Kourghi

2017-11-01

Full Text Available Aquaporins (AQPs are known to facilitate water and solute fluxes across barrier membranes. An increasing number of AQPs are being found to serve as ion channels. Ion and water permeability of selected plant and animal AQPs (plant Arabidopsis thaliana AtPIP2;1, AtPIP2;2, AtPIP2;7, human Homo sapiens HsAQP1, rat Rattus norvegicus RnAQP4, RnAQP5, and fly Drosophila melanogaster DmBIB were expressed in Xenopus oocytes and examined in chelator-buffered salines to evaluate the effects of divalent cations (Ca2+, Mg2+, Ba2+ and Cd2+ on ionic conductances. AtPIP2;1, AtPIP2;2, HsAQP1 and DmBIB expressing oocytes had ionic conductances, and showed differential sensitivity to block by external Ca2+. The order of potency of inhibition by Ca2+ was AtPIP2;2 > AtPIP2;1 > DmBIB > HsAQP1. Blockage of the AQP cation channels by Ba2+ and Cd2+ caused voltage-sensitive outward rectification. The channels with the highest sensitivity to Ca2+ (AtPIP2;1 and AtPIP2;2 showed a distinctive relief of the Ca2+ block by co-application of excess Ba2+, suggesting that divalent ions act at the same site. Recognizing the regulatory role of divalent cations may enable the discovery of other classes of AQP ion channels, and facilitate the development of tools for modulating AQP ion channels. Modulators of AQPs have potential value for diverse applications including improving salinity tolerance in plants, controlling vector-borne diseases, and intervening in serious clinical conditions involving AQPs, such as cancer metastasis, cardiovascular or renal dysfunction.

Thermal conductivity of hydrate-bearing sediments

Science.gov (United States)

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

2009-01-01

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

Experimental investigation of methane release from hydrate formation in sandstone through both hydrate dissociation and CO{sub 2} sequestration

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

Large amounts of natural gas trapped in hydrate reservoirs are found in Arctic regions and in deep offshore locations around the world. Natural gas production from hydrate deposits offer significant potential for future energy needs. However, research is needed in order to propose potential production schemes for natural gas hydrates. Natural gas molecules can be freed from hydrate structured cages by depressurization, by heating and by exposing the hydrate to a substance that will form a thermodynamically more stable hydrate structure. This paper provided a comparison of two approaches for releasing methane from methane hydrate in porous sandstone. The study scope covered the dissociation rate of methane hydrate in porous media through depressurization, and also referred to previous work done on producing methane from hydrates in sandstone while sequestering carbon dioxide (CO{sub 2}). The study was conducted in a laboratory setting. The paper discussed the experimental design which included the placing of a pressure- and temperature-controlled sample holder inside the bore of a magnetic resonance imager. The experimental procedures were then outlined, with reference to hydrate formation; carbon dioxide sequestration; hydrate dissociation experiments with constant volume; and hydrate dissociation experiments at constant pressure. The constant volume experiments demonstrated that in order to dissociate a large amount of hydrate, the initial depressurization had to be significantly lower than the hydrate stability pressure. 9 refs., 9 figs.

Microstructure of natural hydrate host sediments

International Nuclear Information System (INIS)

Jones, K.W.; Kerkar, P.B.; Mahajan, D.; Lindquist, W.B.; Feng, H.

2007-01-01

There is worldwide interest in the study of natural gas hydrate because of its potential impact on world energy resources, control on seafloor stability, significance as a drilling hazard and probable impact on climate as a reservoir of a major greenhouse gas. Gas hydrates can (a) be free floating in the sediment matrix (b) contact, but do not cement, existing sediment grains, or (c) actually cement and stiffen the bulk sediment. Seismic surveys, often used to prospect for hydrates over a large area, can provide knowledge of the location of large hydrate concentrations because the hydrates within the sediment pores modify seismic properties. The ability to image a sample at the grain scale and to determine the porosity, permeability and seismic profile is of great interest since these parameters can help in determining the location of hydrates with certainty. We report here on an investigation of the structure of methane hydrate sediments at the grain-size scale using the synchrotron radiation-based computed microtomography (CMT) technique. Work has started on the measurements of the changes occurring as tetrahydrofuran hydrate, a surrogate for methane hydrate, is formed in the sediment

Observed gas hydrate morphologies in marine sediment

Energy Technology Data Exchange (ETDEWEB)

Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M. [Geotek Ltd., Daventry, Northamptonshire (United Kingdom)

2008-07-01

The morphology of gas hydrate in marine sediments determines the basic physical properties of the sediment-hydrate matrix and provides information regarding the formation of gas hydrate deposits, and the nature of the disruption that will occur on dissociation. Small-scale morphology is useful in estimating the concentrations of gas hydrate from geophysical data. It is also important for predicting their response to climate change or commercial production. Many remote techniques for gas hydrate detection and quantification depend on hydrate morphology. In this study, morphology of gas hydrate was examined in HYACINTH pressure cores from recent seagoing expeditions. Visual and infrared observations from non-pressurized cores were also used. The expeditions and pressure core analysis were described in detail. This paper described the difference between two types of gas hydrate morphologies, notably pore-filling and grain-displacing. Last, the paper addressed the impact of hydrate morphology. It was concluded that a detailed morphology of gas hydrate is an essential component for a full understanding of the past, present, and future of any gas hydrate environment. 14 refs., 4 figs.

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

Science.gov (United States)

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Induction of divalent cation permeability by heterologous expression of a voltage sensor domain.

Science.gov (United States)

Arima, Hiroki; Tsutsui, Hidekazu; Sakamoto, Ayako; Yoshida, Manabu; Okamura, Yasushi

2018-01-06

The voltage sensor domain (VSD) is a protein domain that confers sensitivity to membrane potential in voltage-gated ion channels as well as the voltage-sensing phosphatase. Although VSDs have long been considered to function as regulatory units acting on adjacent effectors, recent studies have revealed the existence of direct ion permeation paths in some mutated VSDs and in the voltage-gated proton channel. In this study, we show that calcium currents are evoked upon membrane hyperpolarization in cells expressing a VSD derived from an ascidian voltage-gated ion channel superfamily. Unlike the previously reported omega-pore in the Shaker K + channel and rNav1.4, mutations are not required. From electrophysiological experiments in heterologous expression systems, we found that the conductance is directly mediated by the VSD itself and is carried by both monovalent and divalent cations. This is the first report of divalent cation permeation through a VSD-like structure. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

HYDRATE CORE DRILLING TESTS

Energy Technology Data Exchange (ETDEWEB)

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

2002-11-01

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

Direct current-induced electrogenerated chemiluminescence of hydrated and chelated Tb(III) at aluminum cathodes

International Nuclear Information System (INIS)

Hakansson, M.; Jiang, Q.; Spehar, A.-M.; Suomi, J.; Kotiranta, M.; Kulmala, S.

2005-01-01

Cathodic DC polarization of oxide-covered aluminum produces electrogenerated chemiluminescence from hydrated and chelated Tb(III) ions in aqueous electrolyte solutions. At the moment of cathodic voltage onset, a strong cathodic flash is observed, which is attributed to a tunnel emission of hot electrons into the aqueous electrolyte solution and the successive chemical reactions with the luminophores. However, within a few milliseconds the insulating oxide film is damaged and finally dissolved due to (i) indiffusion of protons or alkali metal ions into the thin oxide film, (ii) subsequent hydrogen evolution at the aluminum/oxide interface and (iii) alkalization of the electrode surface induced by hydrogen evolution reaction. When the alkalization of the electrode surface has proceeded sufficiently, chemiluminescence is generated with increasing intensity. Aluminum metal, short-lived Al(II), Al(I) or atomic hydrogen and its conjugated base form, hydrated electron, can act as highly reducing species in addition to the less energetic heterogeneously transferred electrons from the aluminum electrode. Tb(III) added as a hydrated ion in the solution probably luminesces in the form of Tb(OH) 3 or Tb(OH) 4 - by direct redox reactions of the central ion whereas multidentate aromatic ligand chelated Tb(III) probably luminesces by ligand sensitized chemiluminescence mechanism in which ligand is first excited by one-electron redox reactions, which is followed by intramolecular energy transfer to the central ion which finally emits light

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

A high yield process for hydrate formation

Energy Technology Data Exchange (ETDEWEB)

Giavarini, C.; Maccioni, F. [Univ. of Roma La Sapienza, Roma (Italy). Dept. of Chemical Engineering

2008-07-01

Due to the large quantities of natural gas stored in deep ocean hydrates, hydrate reservoirs are a substantial energy resource. Hydrates concentrate methane by as much as a factor of 164. As such, several natural gas transportation and storage systems using gas hydrates have been studied, and many of them are nearing practical use. In these systems, the hydrate is produced as a slurry by a spray process at approximately 7 megapascal (MPa), and then shaped into pellets. The use of a spray process, instead of a conventional stirred vessel is necessary in order to reach high hydrate concentrations in the hydrate-ice system. This paper presented a new procedure to produce a bulk of concentrated methane hydrate in a static traditional reactor at moderate pressure, controlling pressure and temperature in the interval between ice melting and the hydrate equilibrium curve. This paper discussed the experimental procedure which included formation of methane hydrate at approximately 5 MPa and 2 degrees Celsius in a reaction calorimeter at a volume of two liters. Results were also discussed. It was concluded that the procedure seemed suitable for the development of a gas hydrate storage and transport technology. It was found that the spray procedure took more time, but could be sped up and made continuous by using two vessels, one for hydrate formation and the other for hydrate concentration. The advantage was the production of a concentrated hydrate, using a simpler equipment and working at lower pressures respect to the spray process. 9 refs., 5 figs.

Higher cytotoxicity of divalent antibody-toxins than monovalent antibody-toxins

International Nuclear Information System (INIS)

Won, JaeSeon; Nam, PilWon; Lee, YongChan; Choe, MuHyeon

2009-01-01

Recombinant antibody-toxins are constructed via the fusion of a 'carcinoma-specific' antibody fragment to a toxin. Due to the high affinity and high selectivity of the antibody fragments, antibody-toxins can bind to surface antigens on cancer cells and kill them without harming normal cells [L.H. Pai, J.K. Batra, D.J. FitzGerald, M.C. Willingham, I. Pastan, Anti-tumor activities of immunotoxins made of monoclonal antibody B3 and various forms of Pseudomonas exotoxin, Proc. Natl. Acad. Sci. USA 88 (1991) 3358-3362]. In this study, we constructed the antibody-toxin, Fab-SWn-PE38, with SWn (n = 3, 6, 9) sequences containing n-time repeated (G 4 S) between the Fab fragment and PE38 (38 kDa truncated form of Pseudomonas exotoxin A). The SWn sequence also harbored one cysteine residue that could form a disulfide bridge between two Fab-SWn-PE38 monomers. We assessed the cytotoxicity of the monovalent (Fab-SWn-PE38), and divalent ([Fab-SWn-PE38] 2 ) antibody-toxins. The cytotoxicity of the dimer against the CRL1739 cell line was approximately 18.8-fold higher than that of the monomer on the ng/ml scale, which was approximately 37.6-fold higher on the pM scale. These results strongly indicate that divalency provides higher cytotoxicity for an antibody-toxin.

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Science.gov (United States)

Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

2013-05-01

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Characterizing heterogeneous dynamics at hydrated electrode surfaces.

Science.gov (United States)

Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

2013-05-14

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Detection and Production of Methane Hydrate

Energy Technology Data Exchange (ETDEWEB)

George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

2011-12-31

This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand

Translocation of metal phosphate via the phosphate inorganic transport system of Escherichia coli

NARCIS (Netherlands)

van Veen, H.W; Abee, T.; Kortstee, G.J J; Konings, W.N; Zehnder, A.J B

1994-01-01

P-i transport via the phosphate inorganic transport system (Pit) of Escherichia coil was studied in natural and artificial membranes. P-i uptake via Pit is dependent on the presence of divalent cations, like Mg2+, Ca2+, Co2+, or Mn2+, which form a soluble, neutral metal phosphate (MeHPO(4)) complex.

Artificial Hydration and Nutrition

Science.gov (United States)

... Crisis Situations Pets and Animals myhealthfinder Food and Nutrition Healthy Food Choices Weight Loss and Diet Plans ... Your Health Resources Healthcare Management Artificial Hydration and Nutrition Artificial Hydration and Nutrition Share Print Patients who ...

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

Hydration dependent dynamics in RNA

International Nuclear Information System (INIS)

Olsen, Greg L.; Bardaro, Michael F.; Echodu, Dorothy C.; Drobny, Gary P.; Varani, Gabriele

2009-01-01

The essential role played by local and collective motions in RNA function has led to a growing interest in the characterization of RNA dynamics. Recent investigations have revealed that even relatively simple RNAs experience complex motions over multiple time scales covering the entire ms-ps motional range. In this work, we use deuterium solid-state NMR to systematically investigate motions in HIV-1 TAR RNA as a function of hydration. We probe dynamics at three uridine residues in different structural environments ranging from helical to completely unrestrained. We observe distinct and substantial changes in 2 H solid-state relaxation times and lineshapes at each site as hydration levels increase. By comparing solid-state and solution state 13 C relaxation measurements, we establish that ns-μs motions that may be indicative of collective dynamics suddenly arise in the RNA as hydration reaches a critical point coincident with the onset of bulk hydration. Beyond that point, we observe smaller changes in relaxation rates and lineshapes in these highly hydrated solid samples, compared to the dramatic activation of motion occurring at moderate hydration

Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

Science.gov (United States)

Kitadai, Norio

2017-03-01

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters

Energy Technology Data Exchange (ETDEWEB)

Jones, Adele M.; Xue, Youjia [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Kinsela, Andrew S. [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Wilcken, Klaus M. [Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Collins, Richard N., E-mail: richard.collins@unsw.edu.au [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia)

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values < 3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with {sup 55}Fe and {sup 26}Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (> 70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO{sub 4}){sub 2}{sup −} and/or Me–NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. - Highlights: • CLASS discharge large amounts of metals and their speciation is poorly

Investigations into surfactant/gas hydrate relationship

Energy Technology Data Exchange (ETDEWEB)

Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)

2007-03-15

Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

Imaging hydrated microbial extracellular polymers: Comparative analysis by electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Dohnalkova, A.C.; Marshall, M. J.; Arey, B. W.; Williams, K. H.; Buck, E. C.; Fredrickson, J. K.

2011-01-01

Microbe-mineral and -metal interactions represent a major intersection between the biosphere and geosphere but require high-resolution imaging and analytical tools for investigating microscale associations. Electron microscopy has been used extensively for geomicrobial investigations and although used bona fide, the traditional methods of sample preparation do not preserve the native morphology of microbiological components, especially extracellular polymers. Herein, we present a direct comparative analysis of microbial interactions using conventional electron microscopy approaches of imaging at room temperature and a suite of cryogenic electron microscopy methods providing imaging in the close-to-natural hydrated state. In situ, we observed an irreversible transformation of the hydrated bacterial extracellular polymers during the traditional dehydration-based sample preparation that resulted in their collapse into filamentous structures. Dehydration-induced polymer collapse can lead to inaccurate spatial relationships and hence could subsequently affect conclusions regarding nature of interactions between microbial extracellular polymers and their environment.

Molecular cloning of a putative divalent-cation transporter gene as a new genetic marker for the identification of Lactobacillus brevis strains capable of growing in beer.

Science.gov (United States)

Hayashi, N; Ito, M; Horiike, S; Taguchi, H

2001-05-01

Random amplified polymorphic DNA (RAPD) PCR analysis of Lactobacillus brevis isolates from breweries revealed that one of the random primers could distinguish beer-spoilage strains of L. brevis from nonspoilage strains. The 1.1-kb DNA fragment amplified from all beer-spoilers included one open reading frame, termed hitA (hop-inducible cation transporter), which encodes an integral membrane protein with 11 putative trans-membrane domains and a binding protein-dependent transport signature of a non-ATP binding membrane transporter common to several prokaryotic and eukaryotic transporters. The hitA polypeptide is homologous to the natural resistance-associated macrophage protein (Nramp) family characterized as divalent-cation transport proteins in many prokaryotic and eukaryotic organisms. Northern blot analysis indicated that the hitA transcripts are expressed in cells cultivated in MRS broth supplemented with hop bitter compounds, which act as mobile-carrier ionophores, dissipating the trans-membrane pH gradient in bacteria sensitive to the hop bitter compounds by exchanging H+ for cellular divalent cations such as Mn2+. This suggests that the hitA gene products may play an important role in making the bacteria resistant to hop bitter compounds in beer by transporting metal ions such as Mn2+ into cells that no longer maintain the proton gradient.

Accelerated hydration of high silica cements

International Nuclear Information System (INIS)

Walker, Colin; Yui, Mikazu

2012-01-01

Current Japanese designs for high level radioactive waste (HLW) repositories anticipate the use of both bentonite (buffer and backfill material) and cement based materials. Using hydrated Ordinary Portland Cement (OPC) as a grouting material is undesirable because the associated high pH buffer will have an undisputed detrimental effect on the performance of the bentonite buffer and backfill and of the host rock by changing its porosity. Instead, hydrated low pH cement (LopHC) grouting materials are being developed to provide a pH inferior or equal to 11 to reduce these detrimental effects. LopHC grouting materials use mixtures of superfine OPC (SOPC) clinker and silica fume (SF), and are referred as high silica cements (HSC). The focus of the present study was to identify the development of the unhydrated and hydrated mineral assemblage and the solution chemistry during the hydration of HSC. Since hydration experiments of cementitious materials are notably slow, a ball mill was used to accelerate hydration. This was done for two reasons. Firstly, to develop a method to rapidly hydrate cement based materials without the need for higher temperatures (which can alter the mineral assemblage), and secondly, to ensure that the end point of hydration was reached in a reasonable time frame and so to realize the final mineralogy and solution chemistry of hydrated HSC

A Hydrate Database: Vital to the Technical Community

Directory of Open Access Journals (Sweden)

D Sloan

2007-06-01

Full Text Available Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML to connect various hydrate databases. The accompanying four articles on laboratory hydrate data by Smith et al., on field hydrate data by L?wner et al., on hydrate modeling by Wang et al., and on construction of a Chinese gas hydrate system by Xiao et al. provide details of GHML in their respective areas.

Treatment of Petroleum Sludge By Using Solidification/Stabilization (S/S) Method : Effect of Hydration Days to Heavy Metals Leaching and Strength

Science.gov (United States)

Murshid, N.; Kamil, N. A. F. M.; Kadir, A. A.

2018-04-01

Petroleum sludge is one of the major solid wastes generated in the petroleum industry. Generally, there are numbers of heavy metals in petroleum sludge and one treatment that is gaining prominence to treat a variety of mixed organic and inorganic waste is solidification/stabilization (S/S) method. The treatment protects human health and the environment by immobilizing contaminants within the treated material and prevents migration of the contaminants. In this study, solidification/stabilization (S/S) method has been used to treat the petroleum sludge. The comparison of hydration days, namely, 7th and 28th days in these cement-based waste materials were studied by using Synthetic Precipitate Leaching Procedure (SPLP). The results were compared to the United States Environmental Protection Agency (USEPA) standards. The results for leaching test concluded that less percentage OPC gave maximum concentration of heavy metals leaching due to deficient in Calcium Oxide (CaO), which is can caused weak solidification in the mixture. Physical and mechanical properties conducted such as compressive strength and density test. From the results, it shows addition up to of 30percentage PS give results which comply with minimum landfill dispose limit. The results shows correlation between strength and density are strong regression coefficient of 82.7%. In conclusion, S/S method can be alternative disposal method for PS in the same time complies with standard for minimum landfill disposal limit. The results for leaching test concluded the less OPC percentage gave maximum concentration of heavy metals leaching.

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the

Henry's Law vaporization studies and thermodynamics of einsteinium-253 metal dissolved in ytterbium

International Nuclear Information System (INIS)

Kleinschmidt, P.D.; Ward, J.W.; Matlack, G.M.; Haire, R.G.

1984-01-01

The cohesive energy of metallic einsteinium determines whether einsteinium is a trivalent or divalent metal. The enthalpy of sublimation, a measure of the cohesive energy, is calculated from the partial pressures of einsteinium over an alloy. The partial pressure of 253 Es has been measured over the range 470--870 K, using combined target and mass spectrometric Knudsen effusion techniques. An alloy was prepared with einsteinium dissolved in a ytterbium solvent to produce a very dilute solution. Partial pressure measurements on the alloy were amenable to the experimental technique and a data analysis using a Henry's law treatment of the data. Vapor pressure data are combined with an estimated crystal entropy S 0 298 and ΔC 0 /sub p/ for ytterbium, to produce enthalpy, entropy, and free energy functions from 298 to 1300 K. The vapor pressure of einsteinium in a dilute einsteinium--ytterbium alloy is described by the equation log P(atm) = -(6815 +- 216)/T+2.576 +- 0.337, from which we calculate for the enthalpy of sublimation of pure einsteinium ΔH 0 298 (second law) = 31.76 kcal/mol. The value of the enthalpy of sublimation is consistent with the conclusion that Es is a divalent metal

Effects of metal ions on growth, β-oxidation system, and thioesterase activity of Lactococcus lactis.

Science.gov (United States)

Li, Liang; Ma, Ying

2014-10-01

The effects of divalent metal ions (Ca(2+), Mg(2+), Fe(2+), and Cu(2+)) on the growth, β-oxidation system, and thioesterase activity of Lactococcus lactis were investigated. Different metal ions significantly influenced the growth of L. lactis: Ca(2+) and Fe(2+) accelerated growth, whereas Cu(2+) inhibited growth. Furthermore, Mg(2+) inhibited growth of L. lactis at a low concentration but stimulated growth of L. lactis at a high concentration. The divalent metal ions had significant effects on activity of the 4 key enzymes of the β-oxidation system (acyl-CoA dehydrogenase, enoyl-CoA hydratase, L-3-hydroxyacyl-CoA dehydrogenase, and thiolase) and thioesterase of L. lactis. The activity of acyl-CoA dehydrogenases increased markedly in the presence of Ca(2+) and Mg(2+), whereas it decreased with 1 mmol/L Fe(2+) or 12 mmol/L Mg(2+). All the metal ions could induce activity of enoyl-CoA hydratase. In addition, 12 mmol/L Mg(2+) significantly stimulated activity of L-3-hydroxyacyl-CoA dehydrogenase, and all metal ions could induce activity of thiolase, although thiolase activity decreased significantly when 0.05 mmol/L Cu(2+) was added into M17 broth. Inhibition of thioesterase activity by all 4 metal ions could be reversed by 2 mmol/L Ca(2+). These results help us understand the effect of metal ions on the β-oxidation system and thioesterase activity of Lactococcus lactis. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Storage capacity of hydrogen in gas hydrates

International Nuclear Information System (INIS)

Tsuda, Takaaki; Ogata, Kyohei; Hashimoto, Shunsuke; Sugahara, Takeshi; Sato, Hiroshi; Ohgaki, Kazunari

2010-01-01

The storage capacity of H 2 in the THF, THT, and furan hydrates was studied by p-V-T measurements. We confirmed that the storage and release processes of H 2 in all hydrates could be performed reversibly by pressure swing without destroying of hydrate cages. H 2 absorption in both THT and furan hydrates is much faster than THF hydrate in spite of same unit-cell structure. On the other hand, the storage amounts of H 2 are coincident in the all additive hydrates and would reach at about 1.0 mass% asymptotically.

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

Science.gov (United States)

Winters, W.J.

1999-01-01

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

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

Influence of fluorosurfactants on hydrate formation rates

Energy Technology Data Exchange (ETDEWEB)

Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

2008-07-01

Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

Physical Properties of Gas Hydrates: A Review

Energy Technology Data Exchange (ETDEWEB)

Gabitto, Jorge [Prairie View A& M University; Tsouris, Costas [ORNL

2010-01-01

Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

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.

Stabilization of heavy metals in MSWI fly ash using silica fume

Energy Technology Data Exchange (ETDEWEB)

Li, Xinying; Chen, Quanyuan [School of Environment Science and Engineering, Donghua University, Shanghai 201620 (China); State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University, Shanghai 201620 (China); Zhou, Yasu [School of Environment Science and Engineering, Donghua University, Shanghai 201620 (China); Tyrer, Mark [Mineral Industry Research Organisation, Solihull B37 7HB (United Kingdom); Yu, Yang [School of Environment Science and Engineering, Donghua University, Shanghai 201620 (China)

2014-12-15

Highlights: • The stabilization of heavy metals in MSWI fly ash was investigated. • The addition of silica fume effectively reduced the leaching of Pb and Cd. • The relation of solid phase transformation and leaching behavior of heavy metals was discussed. - Abstract: The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR ({sup 27}Al and {sup 29}Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.

Molybdenum/alkali metal/ethylene glycol complexes useful as epoxidation catalysts

International Nuclear Information System (INIS)

Marquis, E.T.; Sanderson, J.R.; Keating, K.P.

1987-01-01

This patent describes a clear, storage stable solution of a molybdenum/alkali metal/ethylene glycol complex in ethylene glycol made by the process comprising: reacting at an elevated temperature between about 25 0 and 150 0 C a solid ammonium molybdate or a hydrate thereof and a solid alkali metal molybdate or a hydrate thereof with ethylene glycol, such that the ratio of moles of ethylene glycol to total gram atoms of molybdenum in the molybdates ranges from about 7:10 to 10:1, and the ratio of gram atoms of molybdenum in the ammonium molybdate or hydrate thereof to gram atoms of molybdenum in the alkali metal molybdate is from about 1:1 to about 20:1 to thereby provide a reaction product composed of a solution of an alkali metal-containing complex of molybdenum, alkali metal and ethylene glycol and by-products, including water, in the ethylene glycol and subsequently stripping the solution at a reduced pressure to remove from about 5 to about 25% of the reaction product, as distillate, to thereby provide a storage stable solution of the complex in the ethylene glycol having a molybdenum content of about 6 wt. % to about 20 wt. %, a water concentration of about 0.1 wt. % to about 6 wt. % and an acid number of more than about 60

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...

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

Directory of Open Access Journals (Sweden)

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.

Characteristic of metallic state preperties of mendelevium and other actinoids by thermochcomatography

International Nuclear Information System (INIS)

Hubener, S.; Zvara, I.

1982-01-01

The adsorption of the heavy actinoids Cf, Es, Fm, and Md on polycrystalline titanium and molybdenum has been studied by thermochromatography in comparison with several well-known metallic elements, in trace amounts. The data lead us to suggest that Es, Fm, and Md are divalent in the metallic state and, moreover, that the position of their f energy levels relativg to the Fermi-energy is lower than in the cases of Cf and Yb. A correlation was found between the experimental enthalpies of adsorption of the heavy actinoids and their predicted enthalpies of sublimation

Methane hydrates in nature - Current knowledge and challenges

Science.gov (United States)

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

Science.gov (United States)

Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

2014-01-01

The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins.

Thermodynamic of hydration of a Wyoming montmorillonite saturated with Ca, Mg, Na and K

International Nuclear Information System (INIS)

Vieillard, P.; Blanc, P.; Gailhanou, H.; Gaboreau, S.; Giffaut, E.

2010-01-01

enthalpy of immersion, and isotherms of adsorption - desorption has been done for Wyoming montmorillonite saturated by Mg 2+ , Ca 2+ , Na + and K + . Smectite water-vapor pressure isotherms represent the total concentration of H 2 O taken up the sample which is distributed among the interlayers, the outer surfaces of particles and the open pore space in the sample. In order to retrieve standard state thermodynamic properties for smectite hydration and dehydration from such data, the amount of H 2 O in excess of that in the interlayer must be assessed and subtracted from the total amount taken up by the clay sample. Berend et al. (1995), Cases et al. (1992, 1997) provide careful measurements of recovering waters in both processes (hydration and dehydration) on Wyoming saturated by monovalent and divalent cations. Despite the fact that neither the hydration, nor the dehydration isotherm necessarily represents the equilibrium state of the system, the two isotherms together can be considered to bracket the equilibrium values of Xhs and the activity of H 2 O. Paired hydration and dehydration isotherm in the one hand and enthalpy of immersion in the other hand, which constitute the limits of these brackets can be regressed to assess standard state thermodynamic parameters (enthalpy and entropy) for the hydration- dehydration process. Experimental enthalpies of hydration are used in the determination of ΔH deg. hyd. W H1 and W H2 by the minimization technique. For the adsorption-desorption isotherms, the determination of parameters ΔS deg. hyd. W S1 and W S2 are obtained by minimizing the difference between measured sets of data (relative humidity and number of adsorbed interlayer water) and calculated ones. For each Wyoming saturated with one cation, six parameters are requested and characterize the standard state thermodynamic properties of hydration between smectite and interlayer H 2 O. Relations between hydration parameters ΔH deg. hyd. and ΔS deg. hyd. in the one hand

Toxicity of metal oxide nanoparticles in Escherichia coli correlates with conduction band and hydration energies.

Science.gov (United States)

Kaweeteerawat, Chitrada; Ivask, Angela; Liu, Rong; Zhang, Haiyuan; Chang, Chong Hyun; Low-Kam, Cecile; Fischer, Heidi; Ji, Zhaoxia; Pokhrel, Suman; Cohen, Yoram; Telesca, Donatello; Zink, Jeffrey; Mädler, Lutz; Holden, Patricia A; Nel, Andre; Godwin, Hilary

2015-01-20

Metal oxide nanoparticles (MOx NPs) are used for a host of applications, such as electronics, cosmetics, construction, and medicine, and as a result, the safety of these materials to humans and the environment is of considerable interest. A prior study of 24 MOx NPs in mammalian cells revealed that some of these materials show hazard potential. Here, we report the growth inhibitory effects of the same series of MOx NPs in the bacterium Escherichia coli and show that toxicity trends observed in E. coli parallel those seen previously in mammalian cells. Of the 24 materials studied, only ZnO, CuO, CoO, Mn2O3, Co3O4, Ni2O3, and Cr2O3 were found to exert significant growth inhibitory effects; these effects were found to relate to membrane damage and oxidative stress responses in minimal trophic media. A correlation of the toxicological data with physicochemical parameters of MOx NPs revealed that the probability of a MOx NP being toxic increases as the hydration enthalpy becomes less negative and as the conduction band energy approaches those of biological molecules. These observations are consistent with prior results observed in mammalian cells, revealing that mechanisms of toxicity of MOx NPs are consistent across two very different taxa. These results suggest that studying nanotoxicity in E. coli may help to predict toxicity patterns in higher organisms.

Salinity-Dependent Contact Angle Alteration in Oil/Brine/Silicate Systems: the Critical Role of Divalent Cations.

Science.gov (United States)

Haagh, M E J; Siretanu, I; Duits, M H G; Mugele, F

2017-04-11

The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging. Our experiments involve aqueous droplets with a variable content of chloride salts of Na + , K + , Ca 2+ , and Mg 2+ , wetting surfaces of muscovite and amorphous silica, and an environment of ambient decane containing small amounts of fatty acids to represent polar oil components. By diluting the salt content in various manners, we demonstrate that the water contact angle on muscovite, not on silica, decreases by up to 25° as the divalent cation concentration is reduced from typical concentrations in seawater to zero. Decreasing the ionic strength at a constant divalent ion concentration, however, has a negligible effect on the contact angle. We discuss the consequences for the interpretation of core flooding experiments and the identification of a microscopic mechanism of low salinity water flooding, an increasingly popular, inexpensive, and environment-friendly technique for enhanced oil recovery.

Bulk band gaps in divalent hexaborides: A soft x-ray emission study

International Nuclear Information System (INIS)

Denlinger, Jonathan D.; Gweon, Gey-Hong; Allen, James W.; Bianchi, Andrea D.; Fisk, Zachary

2001-01-01

Boron K-edge soft x-ray emission and absorption are used to address the fundamental question of whether divalent hexaborides are intrinsic semimetals or defect-doped bandgap insulators. These bulk sensitive measurements, complementary and consistent with surface-sensitive angle-resolved photoemission experiments, confirm the existence of a bulk band gap and the location of the chemical potential at the bottom of the conduction band

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

Science.gov (United States)

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

2014-05-01

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

Simulation and Characterization of Methane Hydrate Formation

Science.gov (United States)

Dhakal, S.; Gupta, I.

2017-12-01

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

Surface energy and work function of elemental metals

DEFF Research Database (Denmark)

Skriver, Hans Lomholt; Rosengaard, N. M.

1992-01-01

and noble metals, as derived from the surface tension of liquid metals. In addition, they give work functions which agree with the limited experimental data obtained from single crystals to within 15%, and explain the smooth behavior of the experimental work functions of polycrystalline samples......We have performed an ab initio study of the surface energy and the work function for six close-packed surfaces of 40 elemental metals by means of a Green’s-function technique, based on the linear-muffin-tin-orbitals method within the tight-binding and atomic-sphere approximations. The results...... are in excellent agreement with a recent full-potential, all-electron, slab-supercell calculation of surface energies and work functions for the 4d metals. The present calculations explain the trend exhibited by the surface energies of the alkali, alkaline earth, divalent rare-earth, 3d, 4d, and 5d transition...

Seismic reflections associated with submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Andreassen, K

1996-12-31

Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

Seismic reflections associated with submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Andreassen, K.

1995-12-31

Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

Divalent cations and the protein surface co-ordinate the intensity of human platelet adhesion and P-selectin surface expression.

Science.gov (United States)

Whiss, P A; Andersson, R G G

2002-07-01

At sites of blood vessel injury, platelets adhere to exposed vessel components, such as collagen, or immobilized fibrinogen derived from plasma or activated platelets. The divalent cations Mg(2+) and Ca(2+) are essential for platelet adhesion and activation, but Mg(2+) can also inhibit platelet activation. The present study evaluates, by an enzymatic method, the effects of various divalent cations on the adhesion of isolated human platelets to collagen, fibrinogen, albumin or plastic in vitro. By enzyme-linked immunosorbent assay, platelet surface expression of P-selectin was measured to estimate the state of activation on adherence. Mg(2+) increased platelet adhesion exclusively to collagen and fibrinogen at physiologically relevant concentrations. At higher concentrations, the adhesion declined. Ca(2+) induced a weak adhesion only to fibrinogen at physiological doses and a peak of increased adhesion to all protein-coated surfaces at 10 mmol/l. Mn(2+) elicited dose-dependent adhesion only to collagen and fibrinogen. Zn(2+), Ni(2+) and Cu(2+) increased the adhesion of platelets independently of the surface. Ca(2+) dose-dependently inhibited adhesion elicited by Mg(2+) to collagen and fibrinogen. No other combination of divalent cations elicited such an effect. Mg(2+)-dependent platelet adhesion to collagen and Ca(2+)-dependent adhesion to fibrinogen increased P-selectin expression. Thus, the present study shows that the outcome of the platelet adhesion depends on the surface and the access of divalent cations, which co-ordinate the intensity of platelet adhesion and P-selectin surface expression.

Study of Cd Te recrystallization by hydrated-CdCl_2 thermal treatment

International Nuclear Information System (INIS)

Hernandez V, C.; Albor A, M. L.; Galarza G, U.; Aguilar H, J. R.; Gonzalez T, M. A.; Flores M, J. M.; Jimenez O, D.

2017-01-01

Cd Te thin films solar cells are currently produced using a layer sequence of glass/FTO/CdS/Cd Te/metal contact (Cu/Ag), these films are deposited by two different techniques, chemical bath deposition (CBD) and close space vapour transport (CSVT). In order to reach reasonable conversion efficiencies, the device has to be thermally treated in a hydrated-CdCl_2 atmosphere. This study was carried out using X-ray diffraction (XRD), photoluminescence, Sem-EDS, four probe method and Sims profiling of Cd Te. These analyses confirm the presence of hydrated CdCl_2 and Cd Te phases on Cd Te surface and shown a good recrystallization morphology helping to the carriers mobility along the structure. Using the thermal treatment was possible to reduce the resistivity of Cd Te thin film; it is a result to the Cl migration along the Cd Te solar cell structure, reducing the defects between CdS and Cd Te thin films. A strong Cd Te thin film recrystallization was observed by the implementation of a hydrated-CdCl_2 treatment doing to this a good candidate to Cd Te solar cells process. (Author)

Metal chloride hydrates as Lewis acid catalysts in multicomponent synthesis of 2,4,5-triarylimidazoles or 2,4,5-triaryloxazoles

Energy Technology Data Exchange (ETDEWEB)

Marques, Marcelo V. [Departamento de Engenharia de Processos, Fundacao de Ciencia e Tecnologia, Cachoeirinha, RS (Brazil); Russowsky, Dennis, E-mail: dennis@iq.ufrgs.br [Laboratorio de Sinteses Organicas, Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS (Brazil); Ruthner, Marcelo M.; Fontoura, Luiz A.M. [Curso de Quimica, Universidade Luterana do Brasil, Canoas, RS (Brazil)

2012-07-01

A series of nine metal chloride hydrates (ZnCl{sub 2}.2H{sub 2}O, SnCl{sub 2}.2H{sub 2}O, CdCl{sub 2}.2H{sub 2}O, MnCl{sub 2}.4H{sub 2}O, CoCl{sub 2}.6H{sub 2}O, SrCl{sub 2}.6H{sub 2}O, NiCl{sub 2}.6H{sub 2}O, CrCl{sub 3}.6H{sub 2}O and CeCl{sub 3}.7H{sub 2}O) was investigated as mild and inexpensive Lewis acid catalysts to promote the multicomponent synthesis of triarylimidazoles. Reactions starting from benzil showed the best results when SnCl{sub 2}.2H{sub 2}O was used, while for benzoin as the starting material, CeCl{sub 3}.7H{sub 2}O was more efficient. All reactions were performed in EtOH as solvent. These catalysts were also successfully employed in the synthesis of triaryloxazoles. (author)

EPR of divalent manganese in non-Kramers hosts

Energy Technology Data Exchange (ETDEWEB)

Lech, J.; Slezak, A. [Institute of Physics, Technical University of Czestochowa, Czestochowa (Poland)

1997-12-31

Various interactions which lead to the observation of sharp EPR spectra of the high half-integer spin impurity Mn{sup 2+} (S=5/2) in paramagnetic hosts with integer spins S=1 and S=2 have been studied. Studies have been carried out on the basis of data extracted from experimental EPR spectra of Mn{sup 2+} in single crystal of divalent nickel Ni{sup 2+} (S=1) and Fe{sup 2+} (S=1) perchlorate hexahydrates. It has been shown that dipolar host-host and host-guest couplings broaden resonance lines of Mn{sup 2+}. Narrowing of the lines in the both crystals can be mainly attributed to the host-guest exchange interactions and quenching of the host spins. 19 refs, 3 figs, 1 tab.

Gas Hydrate Storage of Natural Gas

Energy Technology Data Exchange (ETDEWEB)

Rudy Rogers; John Etheridge

2006-03-31

Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

Crucial role of dynamic linker histone binding and divalent ions for DNA accessibility and gene regulation revealed by mesoscale modeling of oligonucleosomes

Science.gov (United States)

Collepardo-Guevara, Rosana; Schlick, Tamar

2012-01-01

Monte Carlo simulations of a mesoscale model of oligonucleosomes are analyzed to examine the role of dynamic-linker histone (LH) binding/unbinding in high monovalent salt with divalent ions, and to further interpret noted chromatin fiber softening by dynamic LH in monovalent salt conditions. We find that divalent ions produce a fiber stiffening effect that competes with, but does not overshadow, the dramatic softening triggered by dynamic-LH behavior. Indeed, we find that in typical in vivo conditions, dynamic-LH binding/unbinding reduces fiber stiffening dramatically (by a factor of almost 5, as measured by the elasticity modulus) compared with rigidly fixed LH, and also the force needed to initiate chromatin unfolding, making it consistent with those of molecular motors. Our data also show that, during unfolding, divalent ions together with LHs induce linker-DNA bending and DNA–DNA repulsion screening, which guarantee formation of heteromorphic superbeads-on-a-string structures that combine regions of loose and compact fiber independently of the characteristics of the LH–core bond. These structures might be important for gene regulation as they expose regions of the DNA selectively. Dynamic control of LH binding/unbinding, either globally or locally, in the presence of divalent ions, might constitute a mechanism for regulation of gene expression. PMID:22790986

Simultaneous spectrophotometric determination of heavy metal ions Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with Br-PADPA in primary reactor coolant system

Energy Technology Data Exchange (ETDEWEB)

Kim, Tae-Hyeong; Yun, Jong-Il [KAIST, Daejeon (Korea, Republic of)

2015-05-15

The performance with integrity of nuclear power plants is highly influenced by the presence of the corrosion products. The deposition of corrosion products in the steam generator is the one of the main concerns of power plants. The quantification of corrosion products is considered of importance. In this study, we applied the spectrophotometric method to detect metal ions such as iron, cobalt, nickel, copper, and zinc, which are major elements of structural material of the plant. In particular, the chemical complexation of those divalent metal ions with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) provides high molar absorptivity. For the simultaneous determination of metal ions, a partial least square (PLS) regression method was applied. In the present work, the complexation of Br-PADAP with divalent metal ions (iron, cobalt, nickel, copper and zinc) was studied. The PLS regression method was successfully applied for simultaneous elemental detection in multi-element systems. These results suggests that the method is very ample to detect corrosion products in nuclear power plants.

Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

NARCIS (Netherlands)

Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

2010-01-01

Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the

Chitosan metal-crosslinked beads applied for n-alkylmonoamines removal from aqueous solutions – a thermodynamic study

International Nuclear Information System (INIS)

Oliveira, Margarete; Simoni, Jose A.; Airoldi, Claudio

2014-01-01

Highlights: • Chitosan beads were successfully synthesized with divalent cations. • Well-formed bead structures containing cations act as acceptor electron sites. • n-Alkylmonoamine/bead interactions are favorably sorbed at the solid/liquid interface. • The thermodynamic data were favorably obtained from calorimetric titrations. • Crosslinked metal–chitosan beads can remove amine-like substances from an ecosystem. - Abstract: Chitosan has ability in coordinating divalent cations when immersed in crosslinked beads, after dripping: (i) chitosan gel into a copper solution, (ii) nickel chitosan gel into sodium hydroxide and (iii) chitosan/cobalt gel into sodium tripolyphosphate. The amounts of (1.82; 1.27 and 0.44) mmol · g −1 for copper, nickel and cobalt cations in these well-formed structures were determined, to give nitrogen/metal ratios of 3.52; 2.09 and 8.51, indicating the least effectiveness for cobalt in the coordination. Copper cation is well-adjusted in the coordination model through free amino and hydroxyl electron pairs, while amino and acetamino groups for nickel and cobalt were used. The chitosan–hydrogen bond breaking in bead formation caused decreases in crystallinity to yield amorphous structures for cobalt and nickel. The water mass fraction released during heating depends on the hydration of the cations, with the highest value of 0.20 for cobalt. The quantitative aspects of the interaction among cations on beads and basic n-alkylmonoamines determined via sorption batch methodology adjusted to the Langmuir isothermal model, with maximum sorption quantities to saturate nickel of (2.50; 2.38; 2.03; 1.79) mmol · g −1 and copper of (2.59; 2.29; 2.28; 1.92) mmol · g −1 for ethyl- propyl-, butyl- and pentylamines, respectively. The interaction energies quantitatively determined from isothermal titration calorimetry (ITC) at the solid/liquid interface resulted in exothermic enthalpic values. These negative enthalpy values combined to

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

Data in support of the negative influence of divalent cations on (?)-epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2)

OpenAIRE

Deb, Gauri; Batra, Sahil; Limaye, Anil M.

2015-01-01

In this data article we have provided evidence for the negative influence of divalent cations on (−)‐epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2) activity in cell-free experiments. Chelating agents, such as EDTA and sodium citrate alone, did not affect MMP-2 activity. While EDTA enhanced, excess of divalent cations interfered with EGCG-mediated inhibition of MMP-2.

THERMODYNAMIC MODEL OF GAS HYDRATES

OpenAIRE

Недоступ, В. И.; Недоступ, О. В.

2015-01-01

The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

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)

Indian National Gas Hydrate Program Expedition 01 report

Science.gov (United States)

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

2015-01-01

Gas hydrate is a naturally occurring “ice-like” combination of natural gas and water that has the potential to serve as an immense resource of natural gas from the world’s oceans and polar regions. However, gas-hydrate recovery is both a scientific and a technical challenge and much remains to be learned about the geologic, engineering, and economic factors controlling the ultimate energy resource potential of gas hydrate. The amount of natural gas contained in the world’s gas-hydrate accumulations is enormous, but these estimates are speculative and range over three orders of magnitude from about 2,800 to 8,000,000 trillion cubic meters of gas. By comparison, conventional natural gas accumulations (reserves and undiscovered, technically recoverable resources) for the world are estimated at approximately 440 trillion cubic meters. Gas recovery from gas hydrate is hindered because the gas is in a solid form and because gas hydrate commonly occurs in remote Arctic and deep marine environments. Proposed methods of gas recovery from gas hydrate generally deal with disassociating or “melting” in situ gas hydrate by heating the reservoir beyond the temperature of gas-hydrate formation, or decreasing the reservoir pressure below hydrate equilibrium. The pace of energy-related gas hydrate assessment projects has accelerated over the past several years.

Anti-Agglomerator of Tetra-n-Butyl Ammonium Bromide Hydrate and Its Effect on Hydrate-Based CO2 Capture

Directory of Open Access Journals (Sweden)

Rong Li

2018-02-01

Full Text Available Tetra-n-butyl ammonium bromide (TBAB was widely used in the research fields of cold storage and CO2 hydrate separation due to its high phase change latent heat and thermodynamic promotion for hydrate formation. Agglomeration always occurred in the process of TBAB hydrate generation, which led to the blockage in the pipeline and the separation apparatus. In this work, we screened out a kind of anti-agglomerant that can effectively solve the problem of TBAB hydrate agglomeration. The anti-agglomerant (AA is composed of 90% cocamidopropyl dimethylamine and 10% glycerol, which can keep TBAB hydrate of 19.3–29.0 wt. % in a stable state of slurry over 72 h. The microscopic observation of the morphology of the TBAB hydrate particles showed that the addition of AA can greatly reduce the size of the TBAB hydrate particles. CO2 gas separation experiments found that the addition of AA led to great improvement on gas storage capacity, CO2 split fraction and separation factor, due to the increasing of contact area between gas phase and hydrate particles. The CO2 split fraction and separation factor with AA addition reached up to 70.3% and 42.8%, respectively.

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Thomas E. Williams; Keith Millheim; Bill Liddell

2005-03-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated

Characteristics of separation of carnitine and metal ions in cheese whey model solution by loose reverse osmosis membrane

Energy Technology Data Exchange (ETDEWEB)

Xu, J.; Echizen, H.; Xing, X.; Yamamoto, S.; Unno, H. [Tokyo Institute of Technology, Tokyo (Japan)

1996-04-20

Aiming at recovering carnitine from cheese whey by using loose reverse osmosis membranes, rejection characteristics of several components in the whey were examined by using model solutions. An electroneutral membrane was found to be most effective for the separation. The rejection of carnitine was above 0.95 independent of the pH of solutions, while monovalent metal ions showed low rejections of 0.1-0.3. On the other hand, the rejections of divalent metal ions deceased with increase of the pH, and reached a minimum of about 0.5. As a result, mono-and divalent metal ions could be removed simultaneously by adjusting the pH of the feed solutions. To clarify the effect of pH on the rejection the permeate of MgCl2 aqueous solution was examined. The rejections of MgCl2 were greatly affected by the pH and showed the same tendency as the mixed station. The effect of the pH on permeation of electrolyte was considered to be caused mainly by the adsorption of ions on the membrane. 16 refs., 6 figs., 2 tabs.

Mussel-inspired histidine-based transient network metal coordination hydrogels

Science.gov (United States)

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

FY1995 molecular control technology for mining of methane-gas-hydrate; 1995 nendo methane hydrate no bunshi seigyo mining

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

The objectives of the investigation are as follows: 1) developing a method to control formation/dissociation of methane-gas-hydrate, 2) developing a technology to displace methane gas by CO{sub 2} in methane-gas-hydrate deposit, 3) developing a technology to produce methane gas from the deposit efficiently. The final purpose of the project is to create new mining industry that solves both the problems of energy and global environment. 1) Clustering of water molecules is found to play the key role in the methane gas hydrate formation. 2) Equilibrium properties and kinetics of gas hydrates formation and dissociation in bulk-scale gas-hydrate are clarified in the practical environmental conditions. 3) Particle size of hydrate deposit influences the formation and dissociation of bulk-scale gas-hydrate crystal. 4) Mass transfer between gas and liquid phase in turbulent bubbly flow is a function of bubble diameter. The mass transfer depends on interfacial dynamics. (NEDO)

Changes in structure and preferential cage occupancy of ethane hydrate and ethane-methane mixed gas hydrate under high pressure

International Nuclear Information System (INIS)

Hirai, H; Takahara, N; Kawamura, T; Yamamoto, Y; Yagi, T

2010-01-01

Structural changes and preferential cage occupancies were examined for ethane hydrate and ethane-methane mixed gas hydrates with five compositions in a pressure range of 0.2 to 2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed the following structural changes. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions, where sII and sH appeared. Above 2.1 GPa ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it was thought that ethane molecules were contained only in the large cage.

Impact of Compound Hydrate Dynamics on Phase Boundary Changes

Science.gov (United States)

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

2006-12-01

Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed

Natural gas hydrates. Experimental techniques and their applications

Energy Technology Data Exchange (ETDEWEB)

Ye, Yuguang; Liu, Changling (eds.) [Qingdao Institute of Marine Geology (China). Gas Hydrate Laboratory

2013-07-01

Focuses on gas hydrate experiment in laboratory. Intends to provide practical significant parameters for gas hydrate exploration and exploitation in the oceanic and permafrost environments. Consists of different themes that present up-to-date information on hydrate experiments. ''Natural Gas Hydrates: Experimental Techniques and Their Applications'' attempts to broadly integrate the most recent knowledge in the fields of hydrate experimental techniques in the laboratory. The book examines various experimental techniques in order to provide useful parameters for gas hydrate exploration and exploitation. It provides experimental techniques for gas hydrates, including the detection techniques, the thermo-physical properties, permeability and mechanical properties, geochemical abnormalities, stability and dissociation kinetics, exploitation conditions, as well as modern measurement technologies etc.

Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

Energy Technology Data Exchange (ETDEWEB)

Marques de Toledo Camargo, R.

2001-03-01

The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

Coloration of chromium-doped yttrium aluminum garnet single-crystal fibers using a divalent codopant

International Nuclear Information System (INIS)

Tissue, B.M.; Jia, W.; Lu, L.; Yen, W.M.

1991-01-01

We have grown single-crystal fibers of Cr:YAG and Cr,Ca:YAG under oxidizing and reducing conditions by the laser-heated-pedestal-growth method. The Cr:YAG crystals were light green due to Cr 3+ in octahedral sites, while the Cr,Ca:YAG crystals were brown. The presence of the divalent codopant was the dominant factor determining the coloration in these single-crystal fibers, while the oxidizing power of the growth atmosphere had little effect on the coloration. The Cr,Ca:YAG had a broad absorption band centered at 1.03 μm and fluoresced from 1.1 to 1.7 μm, with a room-temperature lifetime of 3.5 μs. The presence of both chromium and a divalent codopant were necessary to create the optically-active center which produces the near-infrared emission. Doping with only Ca 2+ created a different coloration with absorption in the blue and ultraviolet. The coloration in the Cr,Ca:YAG is attributed to Cr 4+ and is produced in as-grown crystals without irradiation or annealing, as has been necessary in previous work

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...

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

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.

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

Energy Technology Data Exchange (ETDEWEB)

Myers, Greg [Consortium for Ocean Leadership, Washington, DC (United States)

2014-02-01

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Project Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.

Study of Cd Te recrystallization by hydrated-CdCl{sub 2} thermal treatment

Energy Technology Data Exchange (ETDEWEB)

Hernandez V, C.; Albor A, M. L.; Galarza G, U.; Aguilar H, J. R. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Fisica, San Pedro Zacatenco, 07738 Ciudad de Mexico (Mexico); Gonzalez T, M. A. [IPN, Escuela Superior de Computo, Nueva Industrial Vallejo, 07738 Ciudad de Mexico (Mexico); Flores M, J. M. [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Departamento de Ingenieria en Metalurgia y Materiales, Nueva Industrial Vallejo, 07738 Ciudad de Mexico (Mexico); Jimenez O, D. [IPN, Escuela Superior de Ingenieria Mecanica y Electrica, SEPI, Nueva Industrial Vallejo, 07738 Ciudad de Mexico (Mexico)

2017-11-01

Cd Te thin films solar cells are currently produced using a layer sequence of glass/FTO/CdS/Cd Te/metal contact (Cu/Ag), these films are deposited by two different techniques, chemical bath deposition (CBD) and close space vapour transport (CSVT). In order to reach reasonable conversion efficiencies, the device has to be thermally treated in a hydrated-CdCl{sub 2} atmosphere. This study was carried out using X-ray diffraction (XRD), photoluminescence, Sem-EDS, four probe method and Sims profiling of Cd Te. These analyses confirm the presence of hydrated CdCl{sub 2} and Cd Te phases on Cd Te surface and shown a good recrystallization morphology helping to the carriers mobility along the structure. Using the thermal treatment was possible to reduce the resistivity of Cd Te thin film; it is a result to the Cl migration along the Cd Te solar cell structure, reducing the defects between CdS and Cd Te thin films. A strong Cd Te thin film recrystallization was observed by the implementation of a hydrated-CdCl{sub 2} treatment doing to this a good candidate to Cd Te solar cells process. (Author)

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

Science.gov (United States)

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

2006-01-01

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

Morphology studies on gas hydrates interacting with silica gel

Energy Technology Data Exchange (ETDEWEB)

Beltran, J.; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering

2008-07-01

Clathrate hydrates or gas hydrates are non-stoichiometric, crystalline compounds that form when small molecules come in contact with water at certain temperatures and pressures. Natural gas hydrates are found in the ocean bottom and in permafrost regions. It is thought that the amount of energy stored in natural hydrates is at least twice that of all other fossil fuels combined. In addition, trapping carbon dioxide as a hydrate in the bottom of the ocean has been suggested as an alternative means of reducing atmospheric carbon dioxide levels. Naturally occurring clathrates are found in close interaction with fine grained particles of very small mean pore diameters. Even though an increasing amount of hydrate equilibrium data for small diameter porous media has become available, the morphological behavior of hydrates subject to such conditions is yet to be explored. This paper presented a study that visually examined hydrate formation and decomposition of gas hydrates while interacting with fine grains of silica gel. The study showed still frames from high-resolution video recordings for hydrate formation and decomposition. The paper discussed the experiment including the apparatus as well as the results of hydrate formation and hydrate dissociation. This study enabled for the first time to observe clathrate morphology while hydrates interacted closely with fine grain particles with small mean pore diameters. 9 refs., 8 figs.

Ab Initio Assessment of the Bonding in Disulfonates Containing Divalent Nitrogen and Phosphorus Atoms

DEFF Research Database (Denmark)

Andersen, Vinca Bonde; Berg, Rolf W.; Shim, Irene

2017-01-01

The iminodisulfonate, [N(SO3)2]3–, and phosphinodisulfonate, [P(SO3)2]3–, ions have been investigated by performing ab initio MP2/6-311+G**calculations. The nitrogen and phosphorus atoms as part of the ions are shown to be divalent with a negative charge and two lone pairs on the nitrogen...

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.

Effect of mass concentration of composite phase change material CA-DE on HCFC-141b hydrate induction time and system stability

Science.gov (United States)

Li, Juan; Sun, Zhigao; Liu, Chenggang; Zhu, Minggui

2018-03-01

HCFC-141b hydrate is a new type of environment-friendly cold storage medium which may be adopted to balance energy supply and demand, achieve peak load shifting and energy saving, wherein the hydrate induction time and system stability are key factors to promote and realize its application in industrial practice. Based on step cooling curve measurement, two kinds of aliphatic hydrocarbon organics, n-capric acid (CA) and lauryl alcohol (DE), were selected to form composite phase change material and to promote the generation of HCFC-141b hydrate. Five kinds of CA-DE mass concentration were chosen to compare the induction time and hydration system stability. In order to accelerate temperature reduction rate, the metal Cu with high heat conductivity performance was adopted to conduct out the heat generated during phase change. Instability index was introduced to appraise system stability. Experimental results show that phase change temperature and sub-cooling degree of CA-DE is 11.1°C and 3.0°C respectively, which means it is a preferable medium for HCFC-141b hydrate formation. For the experimental hydration systems, segmented emulsification is achieved by special titration manner to avoid rapid layering under static condition. Induction time can achieve up to 23.3min with the densest HCFC-141b hydrate and the lowest instability index, wherein CA-DE mass concentration is 3%.

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

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.

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.

Gas hydrate exploration activities in Korea

Energy Technology Data Exchange (ETDEWEB)

Keun-Pil Park, K.P. [Korea Inst. of Geoscience and Mineral Resources, Gas Hydrate R and D Organization, Ministry of Knowledge Economy, Yuseong-gu, Daejeon (Korea, Republic of)

2008-07-01

Korea's first gas hydrate research project was launched in 1996 to study the gas hydrate potential in the Ulleung Basin of the East Sea. It involved a series of laboratory experiments followed by a preliminary offshore seismic survey and regional reconnaissance geophysical and marine geological surveys. The bottom simulating reflector (BSR) was interpreted to show wide area distribution in the southern part of the Ulleung Basin, and its average burial depth was 187 m below the sea floor in the East Sea. A three-phase 10-year National Gas Hydrate Development Program was launched in 2004 to estimate the potential reserves in the East Sea. It will involve drilling to identify natural gas hydrates and to determine the most optimized production methods. Drilling sites were proposed based on five indicators that imply gas hydrate occurrence, notably BSR, gas vent, enhanced seismic reflection, acoustic blanking and gas seeping structure. The UBGH-X-01 gas hydrate expedition in the East Sea Ulleung Basin involved 5 logging while drilling (LWD) surveys at three high priority sites. One wire line logging was implemented at the site of the UBGH09. A total 334 m of non-pressurized conventional cores and 16 pressure cores were obtained in late 2007. The UBGH-X-01 was successfully completed, recovering many natural samples of gas hydrate from 3 coring sites in the East Sea. 7 refs., 12 figs.

Seismic-Scale Rock Physics of Methane Hydrate

Energy Technology Data Exchange (ETDEWEB)

Amos Nur

2009-01-08

We quantify natural methane hydrate reservoirs by generating synthetic seismic traces and comparing them to real seismic data: if the synthetic matches the observed data, then the reservoir properties and conditions used in synthetic modeling might be the same as the actual, in-situ reservoir conditions. This approach is model-based: it uses rock physics equations that link the porosity and mineralogy of the host sediment, pressure, and hydrate saturation, and the resulting elastic-wave velocity and density. One result of such seismic forward modeling is a catalogue of seismic reflections of methane hydrate which can serve as a field guide to hydrate identification from real seismic data. We verify this approach using field data from known hydrate deposits.

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

Energy Technology Data Exchange (ETDEWEB)

Collett, Tim [U.S. Geological Survey, Boulder, CO (United States); Bahk, Jang-Jun [Korea Inst. of Geoscience and Mineral Resources, Daejeon (Korea); Frye, Matt [U.S. Bureau of Ocean Energy Management, Sterling, VA (United States); Goldberg, Dave [Lamont-Doherty Earth Observatory, Palisades, NY (United States); Husebo, Jarle [Statoil ASA, Stavenger (Norway); Koh, Carolyn [Colorado School of Mines, Golden, CO (United States); Malone, Mitch [Texas A & M Univ., College Station, TX (United States); Shipp, Craig [Shell International Exploration and Production Inc., Anchorage, AK (United States); Torres, Marta [Oregon State Univ., Corvallis, OR (United States); Myers, Greg [Consortium For Ocean Leadership Inc., Washington, DC (United States); Divins, David [Consortium For Ocean Leadership Inc., Washington, DC (United States); Morell, Margo [Consortium For Ocean Leadership Inc., Washington, DC (United States)

2013-12-31

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

Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

Science.gov (United States)

Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

2016-06-01

The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions.

Energy from gas hydrates - assessing the opportunities and challenges for Canada: report of the expert panel on gas hydrates

International Nuclear Information System (INIS)

2008-09-01

Gas hydrates form when water and natural gas combine at low temperatures and high pressures in regions of permafrost and in marine subseafloor sediments. Estimates suggest that the total amount of natural gas bound in hydrate form may exceed all conventional gas resources, or even the amount of all combined hydrocarbon energy. Gas from gas hydrate could provide a potentially vast new source of energy to offset declining supplies of conventional natural gas in North America and to provide greater energy security for countries such as Japan and India that have limited domestic sources. However, complex issues would need to be addressed if gas hydrate were to become a large part of the energy future of Canada. Natural Resources Canada asked the Council of Canadian Academies to assemble a panel of experts to examine the challenges for an acceptable operational extraction of gas hydrates in Canada. This report presented an overview of relevant contextual background, including some basic science; the medium-term outlook for supply and demand in markets for natural gas; broad environmental issues related to gas hydrate in its natural state and as a fuel; and an overview of Canada's contribution to knowledge about gas hydrate in the context of ongoing international research activity. The report also presented current information on the subject and what would be required to delineate and quantify the resource. Techniques for extracting gas from gas hydrate were also outlined. The report also addressed safety issues related to gas hydrate dissociation during drilling operations or release into the atmosphere; the environmental issues associated with potential leakage of methane into the atmosphere and with the large volumes of water produced during gas hydrate dissociation; and jurisdictional and local community issues that would need to be resolved in order to proceed with the commercial exploitation of gas hydrate. It was concluded that there does not appear to be

Gas Hydrates Research Programs: An International Review

Energy Technology Data Exchange (ETDEWEB)

Jorge Gabitto; Maria Barrufet

2009-12-09

Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

Obsidian hydration dates glacial loading?

Science.gov (United States)

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

1973-05-18

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

Effects of Nanosilica on Early Age Stages of Cement Hydration

Directory of Open Access Journals (Sweden)

Forood Torabian Isfahani

2017-01-01

Full Text Available Effects of nanosilica on cement hydration have been broadly investigated in the literature and early age cement hydration, as a whole, has been mainly considered, disregarding the substages of the hydration. The hydration of cement is characterized by different substages and nanosilica effect on the hydration could be a result of diverse, even contradictory, behavior of nanosilica in individual stages of the hydration. In this study, effects of nanosilica on different substages of cement hydration are investigated. Isothermal calorimetry results show that at early ages (initial 72 hours the effects of nanosilica depend on the phenomenon by which the hydration is governed: when the hydration is chemically controlled, that is, during initial reaction, dormant period, and acceleratory period, the hydration rate is accelerated by adding nanosilica; when the hydration is governed by diffusion process, that is, during postacceleratory period, the hydration rate is decelerated by adding nanosilica. The Thermal Gravimetric Analysis on the samples at the hardened state (after 28 days of curing reveals that, after adding nanosilica, the hydration degree slightly increased compared to the plain paste.

Molecular simulation of a model of dissolved organic matter.

Science.gov (United States)

Sutton, Rebecca; Sposito, Garrison; Diallo, Mamadou S; Schulten, Hans-Rolf

2005-08-01

A series of atomistic simulations was performed to assess the ability of the Schulten dissolved organic matter (DOM) molecule, a well-established model humic molecule, to reproduce the physical and chemical behavior of natural humic substances. The unhydrated DOM molecule had a bulk density value appropriate to humic matter, but its Hildebrand solubility parameter was lower than the range of current experimental estimates. Under hydrated conditions, the DOM molecule went through conformational adjustments that resulted in disruption of intramolecular hydrogen bonds (H-bonds), although few water molecules penetrated the organic interior. The radius of gyration of the hydrated DOM molecule was similar to those measured for aquatic humic substances. To simulate humic materials under aqueous conditions with varying pH levels, carboxyl groups were deprotonated, and hydrated Na+ or Ca2+ were added to balance the resulting negative charge. Because of intrusion of the cation hydrates, the model metal-humic structures were more porous, had greater solvent-accessible surface areas, and formed more H-bonds with water than the protonated, hydrated DOM molecule. Relative to Na+, Ca2+ was both more strongly bound to carboxylate groups and more fully hydrated. This difference was attributed to the higher charge of the divalent cation. The Ca-DOM hydrate, however, featured fewer H-bonds than the Na-DOM hydrate, perhaps because of the reduced orientational freedom of organic moieties and water molecules imposed by Ca2+. The present work is, to our knowledge, the first rigorous computational exploration regarding the behavior of a model humic molecule under a range of physical conditions typical of soil and water systems.

A unified approach for description of gas hydrate formation kinetics in the presence of kinetic promoters in gas hydrate converters

International Nuclear Information System (INIS)

ZareNezhad, Bahman; Varaminian, Farshad

2013-01-01

Highlights: • A unified kinetic model for description of promoted and non-promoted gas hydrate formation processes is presented. • Effects of impeller speed, promoter concentration and different kinetic promoters are investigated. • A unique region of gas hydrate formation is identified regarding gas hydrate formation processes. • The proposed model is useful for understanding the behavior of gas hydrate formation processes and design of GTH converters. - Abstract: The kinetic promoters have found wide applications in enhancing the rate of energy conversion and storage via gas hydrate formation processes. Effects of different kinetic promoters such as anionic surfactants sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBSA), and sodium dodecyl benzene sulfonate (SDBS); cationic surfactants, Cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide (DTAB) and non-ionic surfactants, alkylpolyglucoside (APG), dodecyl polysaccharide glycoside (DPG), TritonX-100 (TX100) on methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ) gas hydrate formation processes are investigated in this work. A macroscopic kinetic model based on the time variations of reaction chemical potential is also presented for global description of gas hydrate formation processes. Experimental gas hydrate formation data are employed to validate the proposed kinetic model. Effects of promoter’s concentrations and agitation intensities on the gas consumption profiles are also investigated. A universal correlation and a unified kinetic map have been proposed for macroscopic description of gas hydrate formation kinetics in the presence or absence of kinetic promoters. According to the presented unified kinetic map, a unique region of gas hydrate formation is identified for the first time. For negligible amounts of kinetic promoters, the presented region disappears and approaches to a unique path at high agitation intensities. The presented unified approach is

Protein Hydration Thermodynamics: The Influence of Flexibility and Salt on Hydrophobin II Hydration.

Science.gov (United States)

Remsing, Richard C; Xi, Erte; Patel, Amish J

2018-04-05

The solubility of proteins and other macromolecular solutes plays an important role in numerous biological, chemical, and medicinal processes. An important determinant of protein solubility is the solvation free energy of the protein, which quantifies the overall strength of the interactions between the protein and the aqueous solution that surrounds it. Here we present an all-atom explicit-solvent computational framework for the rapid estimation of protein solvation free energies. Using this framework, we estimate the hydration free energy of hydrophobin II, an amphiphilic fungal protein, in a computationally efficient manner. We further explore how the protein hydration free energy is influenced by enhancing flexibility and by the addition of sodium chloride, and find that it increases in both cases, making protein hydration less favorable.

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

Science.gov (United States)

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

2010-01-01

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

Standardization and software infrastructure for gas hydrate data communications

Energy Technology Data Exchange (ETDEWEB)

Kroenlein, K.; Chirico, R.D.; Kazakov, A.; Frenkel, M. [National Inst. of Standards and Technology, Boulder, CO (United States). Physical and Chemical Properties Div.; Lowner, R. [GeoForschungsZentrum Potsdam (Germany); Wang, W. [Chinese Academy of Science, Beijing (China). Computer Network Information Center; Smith, T. [MIT Systems, Flushing, NY (United States); Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Centre for Hydrate Research

2008-07-01

The perceived value of gas hydrates as an energy resource for the future has led to extensive hydrate research studies and experiments. The hydrate deposits are widely dispersed throughout the world, and many countries are now investigating methods of extracting gas hydrate resources. This paper described a gas hydrates markup language (GHML) developed as an international standard for data transfer and storage within the gas hydrates community. The language is related to a hydrates database developed to facilitate a greater understanding of naturally occurring hydrate interactions with geophysical processes, and aid in the development of hydrate technologies for resource recovery and storage. Recent updates to the GHML included the addition of ThermoML, a communication standard for thermodynamic data into the GHML schema. The standard will be used to represent all gas hydrates thermodynamic data. A new element for the description of crystal structures has also been developed, as well as a guided data capture tool. The tool is available free of charge and is publicly licensed for use by gas hydrate data producers. A web service has also been provided to ensure that access to GHML files for gas hydrates and data files are available for users. It was concluded that the tool will help to ensure data quality assurance for the conversion of data and meta-data within the database. 28 refs., 9 figs.

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 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

"Rocking-Chair"-Type Metal Hybrid Supercapacitors.

Science.gov (United States)

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D; Gewirth, Andrew A; Genorio, Bostjan; Rajput, Nav Nidhi; Persson, Kristin A; Burrell, Anthony K; Cabana, Jordi

2016-11-16

Hybrid supercapacitors that follow a "rocking-chair"-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative "rocking-chair"-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts, made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the "rocking-chair"-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.

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.

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

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

Science.gov (United States)

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

2009-10-22

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

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

Science.gov (United States)

Ruppel, Carolyn D.

2018-01-17

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

Hydration behaviors of calcium silicate-based biomaterials.

Science.gov (United States)

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

Cryogenic-SEM investigation of CO{sub 2} hydrate morphologies

Energy Technology Data Exchange (ETDEWEB)

Camps, A.P.; Milodowski, A.; Rochelle, C.; Williams, J.F.; Jackson, P. D. [British Geological Survey, Keyworth, Nottinghamshire (United Kingdom); Camps, A.P; Lovell, M.; Williams, J.F. [Leicester Univ., Leicester (United Kingdom). Dept. of Geology

2008-07-01

Gas hydrates occur naturally around the world in the shallow-marine geosphere, and are seen as a drilling hazard in the petroleum industry due to their role in the carbon cycle, and their possible contribution in past and present climate change. Hydrates are ice-like structures composed of cages of water molecules containing one or more guest molecules, such as methane and carbon dioxide (CO{sub 2}). CO{sub 2} hydrates also occur naturally on earth and are being investigated for their potential to store large volumes of CO{sub 2} to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. However, the mineralogy and formation processes of hydrates are relatively poorly understood. Different imaging techniques have been utilized to study gas hydrates, such as nuclear magnetic resonance, magnetic resonance imaging, and x-ray computed tomography. Scanning Electron Microscopy (SEM) at cryogenic temperatures is another technique to study hydrates, and has been used successfully for investigation of methane and CO{sub 2} hydrates. This paper presented a study that investigated CO{sub 2} hydrates formed in laboratories, using a cryogenic-SEM. The paper presented the study methods and observations, including euhedral crystalline carbon dioxide hydrate; acicular carbon dioxide hydrate; granoblastic carbon dioxide hydrate; and gas rich carbon dioxide hydrate. It was concluded that the investigation produced various different hydrate morphologies resulting from different formation conditions. Morphologies ranged from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. 22 refs., 6 figs., 1 appendix.

Gas Hydrates | Alaska Division of Geological & Geophysical Surveys

Science.gov (United States)

Preliminary Report - Cascadia Margin Gas Hydrates, Volume 204 Initial Report Mallik 2002 GSC Bulletin 585 : Scientific results from the Mallik 2002 gas hydrate production well program Offshore gas hydrate sample

Comparative Assessment of Advanced Gay Hydrate Production Methods

Energy Technology Data Exchange (ETDEWEB)

M. D. White; B. P. McGrail; S. K. Wurstner

2009-06-30

Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

DEFF Research Database (Denmark)

Takeya, Kei; Zhang, Caihong; Kawayama, Iwao

2009-01-01

For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has...... a characteristic broad absorption peak at 0.5 THz corresponding to the dipole moment of THF molecules. The refractive indices of THF and propane hydrates are 1.725 and 1.775 at 1 THz, respectively, and show a slight but clear difference from the refractive index of ice (1.79). THz-TDS is a potentially useful...... technique for the ondestructive inspection of gas hydrates. # 2009 The Japan Society of Applied Physics...

Mitochondrial membranes with mono- and divalent salt: Changes induced by salt ions on structure and dynamics

NARCIS (Netherlands)

Pöyry, S.; Róg, T.; Karttunen, M.E.J.; Vattulainen, I.

2009-01-01

We employ atomistic simulations to consider how mono- (NaCl) and divalent (CaCl2) salt affects properties of inner and outer membranes of mitochondria. We find that the influence of salt on structural properties is rather minute, only weakly affecting lipid packing, conformational ordering, and

Hydrate Control for Gas Storage Operations

Energy Technology Data Exchange (ETDEWEB)

Jeffrey Savidge

2008-10-31

The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

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

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

Energy Technology Data Exchange (ETDEWEB)

McConnell, Daniel

2017-12-30

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production.

A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Leg II in 2009 and recently confirmed with coring in 2017.

A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.

Experimental Setup to Characterize Bentonite Hydration Processes

International Nuclear Information System (INIS)

Bru, A.; Casero, D.; Pastor, J. M.

2001-01-01

We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

Marine Gas Hydrates - An Untapped Non-conventional Energy ...

Indian Academy of Sciences (India)

Table of contents. Marine Gas Hydrates - An Untapped Non-conventional Energy Resource · Slide 2 · Slide 3 · Slide 4 · Gas Hydrate Stability Zone · Slide 6 · Slide 7 · Exploration of gas hydrates (seismic) · Characteristics of BSR · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Distribution of Gas Hydrates in KG ...

The structure of hydrate bearing fine grained marine sediments

Energy Technology Data Exchange (ETDEWEB)

Priest, J.; Kingston, E.; Clayton, C. [Southampton Univ., Highfield (United Kingdom). School of Civil Engineering and the Environment; Schultheiss, P.; Druce, M. [Geotek Ltd., Daventry (United Kingdom)

2008-07-01

This paper discussed the structure of naturally occurring methane gas hydrates in fine-grained sediments from core samples recovered using in situ pressures from the eastern margin of the Indian Ocean. High resolution X-ray computed tomography (CT) images were taken of gas hydrate cores. The hydrate structure was examined and comparisons were made between low resolution X-ray images obtained on the cores prior to sub-sectioning and depressurization procedures. The X-ray images showed the presence of high-angle, sub-parallel veins within the recovered sediments. The scans indicated that the hydrates occurred as fracture filing veins throughout the core. Fracture orientation was predominantly sub-vertical. Thick millimetric hydrate veins were composed of sub-millimetric veins with variations in fracture angle. The analysis indicated that hydrate formation was episodic in nature and subject to changes in the stress regime. Results of the study showed that depressurization and subsequent freezing alter the structure of the sediment even when the gas hydrate has not been altered. A large proportion of the hydrate survived when outside of its stability region. The self-preserving behaviour of the hydrate was attributed to the endothermic nature of gas hydrate dissociation. It was concluded that the accurate physical characterization of gas hydrates can only be conducted when the core section remains under in situ stress conditions. 13 refs., 9 figs.

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.

TOUGH+Hydrate v1.0 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

Energy Technology Data Exchange (ETDEWEB)

Moridis, George; Moridis, George J.; Kowalsky, Michael B.; Pruess, Karsten

2008-03-01

TOUGH+HYDRATE v1.0 is a new code for the simulation of the behavior of hydrate-bearing geologic systems. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH{sub 4}-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.0 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH{sub 4}, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is the first member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

Heavy metal extraction from PCB wastewater treatment sludge by sulfuric acid

International Nuclear Information System (INIS)

Kuan, Yu-Chung; Lee, I-Hsien; Chern, Jia-Ming

2010-01-01

Heavy metals contaminated wastewater sludge is classified as hazardous solid waste and needs to be properly treated to prevent releasing heavy metals to the environment. In this study, the wastewater treatment sludge from a printed circuit board manufacturing plant was treated in a batch reactor by sulfuric acid to remove the contained heavy metals. The effects of sulfuric acid concentration and solid to liquid ratio on the heavy metal removal efficiencies were investigated. The experimental results showed that the total and individual heavy metal removal efficiencies increased with increasing sulfuric acid concentration, but decreased with increasing solid to liquid ratio. A mathematical model was developed to predict the residual sludge weights at varying sulfuric concentrations and solid to liquid ratios. The trivalent heavy metal ions, iron and chromium were more difficult to be removed than the divalent ions, copper, zinc, nickel, and cadmium. For 5 g/L solid to liquid ratio, more than 99.9% of heavy metals can be removed from the sludge by treating with 0.5 M sulfuric acid in 2 h.

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

Science.gov (United States)

Lorenson, T.D.

1999-01-01

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

Hydration shells exchange charge with their protein

DEFF Research Database (Denmark)

Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert

2010-01-01

. In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity......Investigation of the interaction between a protein and its hydration shells is an experimental and theoretical challenge. Here, we used ultrasonic pressure waves in aqueous solutions of a protein to explore the conformational states of the protein and its interaction with its hydration shells...... the presence of an ultrasonic pressure, a protein and its hydration shells are in thermodynamic and charge equilibrium, i.e. a protein and its hydration shells exchange charges. The ultrasonic wave disrupts these equilibria which are regained within 30–45 min after the ultrasonic pressure is shut off....

Oceanic hydrates: more questions than answers

International Nuclear Information System (INIS)

Laherrere, Jean

2000-01-01

Methane hydrates create problems by blocking pipelines and casing; they are also accused of contributing to environmental problems (e.g. global warming). Methane hydrates are also found in permafrost areas and in oceanic sediments where the necessary temperature and pressure for stability occur. Claims for the widespread occurrence in thick oceanic deposits are unfounded: apparently indirect evidence from seismic reflectors, seismic hydrocarbon indicators, logs and free samples is unreliable. At one time, hydrate was seen as a static, biogenic, continuous, huge resource but that view is changing to one of a dynamic, overpressurised, discontinuous and unreliable resource. Only Japan and India are currently showing any serious interest in hydrates. Academic research has raised more questions than answers. It is suggested that more hard exploratory evidence rather than theoretical study is required

Chloral Hydrate

Science.gov (United States)

... if you are allergic to chloral hydrate, aspirin, tartrazine (a yellow dye in some processed foods and ... in, tightly closed, and out of reach of children. Store it at room temperature, away from excess ...

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

Carbon dioxide hydrate formation in a fixed-bed reactor

Energy Technology Data Exchange (ETDEWEB)

Fan, S.; Lang, X. [South China Univ. of Technology, Guangzhou (China). Key Laboratory of Enhanced Heat Transfer and Energy Conservation; Wang, Y.; Liang, D. [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion and Guangzhou Center of Natural Gas Hydrate; Sun, X.; Jurcik, B. [Air Liquide Laboratories, Tsukuba (Japan)

2008-07-01

Gas hydrates are thermodynamically stable at high pressures and near the freezing temperature of pure water. Methane hydrates occur naturally in sediments in the deep oceans and permafrost regions and constitute an extensive hydrocarbon reservoir. Carbon dioxide (CO{sub 2}) hydrates are of interest as a medium for marine sequestration of anthropogenic carbon dioxide. Sequestering CO{sub 2} as hydrate has potential advantages over most methods proposed for marine CO{sub 2} sequestration. Because this technique requires a shallower depth of injection when compared with other ocean sequestration methods, the costs of CO{sub 2} hydrate sequestration may be lower. Many studies have successfully used different continuous reactor designs to produce CO{sub 2} hydrates in both laboratory and field settings. This paper discussed a study that involved the design and construction of a fixed-bed reactor for simulation of hydrate formation system. Water, river sands and carbon dioxide were used to simulate the seep kind of hydrate formation. Carbon dioxide gas was distributed as small bubbles to enter from the bottom of the fixed-bed reactor. The paper discussed the experimental data and presented a diagram of the gas hydrate reactor system. The morphology as well as the reaction characters of CO{sub 2} hydrate was presented in detail. The results were discussed in terms of experimental phenomena and hydrate formation rate. A mathematical model was proposed for describing the process. 17 refs., 7 figs.

Structural and hydration properties of amorphous tricalcium silicate

International Nuclear Information System (INIS)

Mori, K.; Fukunaga, T.; Shiraishi, Y.; Iwase, K.; Xu, Q.; Oishi, K.; Yatsuyanagi, K.; Yonemura, M.; Itoh, K.; Sugiyama, M.; Ishigaki, T.; Kamiyama, T.; Kawai, M.

2006-01-01

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca 3 SiO 5 ) sample, where Ca 3 SiO 5 is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca 3 SiO 5 . The hydration of the milled Ca 3 SiO 5 with D 2 O proceeds as follows: the formation of hydration products such as Ca(OD) 2 rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca 3 SiO 5 is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca 3 SiO 5 for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage

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.

CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

Science.gov (United States)

Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

2013-04-01

In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with

Investigating the Metastability of Clathrate Hydrates for Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Koh, Carolyn Ann [Colorado School of Mines, Golden, CO (United States)

2014-11-18

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

The impact of permafrost-associated microorganisms on hydrate formation kinetics

Science.gov (United States)

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

2016-04-01

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

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

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

Zinc is the metal cofactor of Borrelia burgdorferi peptide deformylase.

Science.gov (United States)

Nguyen, Kiet T; Wu, Jen-Chieh; Boylan, Julie A; Gherardini, Frank C; Pei, Dehua

2007-12-15

Peptide deformylase (PDF, E.C. 3.5.1.88) catalyzes the removal of N-terminal formyl groups from nascent ribosome-synthesized polypeptides. PDF contains a catalytically essential divalent metal ion, which is tetrahedrally coordinated by three protein ligands (His, His, and Cys) and a water molecule. Previous studies revealed that the metal cofactor is a Fe2+ ion in Escherichia coli and many other bacterial PDFs. In this work, we found that PDFs from two iron-deficient bacteria, Borrelia burgdorferi and Lactobacillus plantarum, are stable and highly active under aerobic conditions. The native B. burgdorferi PDF (BbPDF) was purified 1200-fold and metal analysis revealed that it contains approximately 1.1 Zn2+ ion/polypeptide but no iron. Our studies suggest that PDF utilizes different metal ions in different organisms. These data have important implications in designing PDF inhibitors and should help address some of the unresolved issues regarding PDF structure and catalytic function.

Novel DOTA-based prochelator for divalent peptide vectorization: synthesis of dimeric bombesin analogues for multimodality tumor imaging and therapy.

Science.gov (United States)

Abiraj, Keelara; Jaccard, Hugues; Kretzschmar, Martin; Helm, Lothar; Maecke, Helmut R

2008-07-28

Dimeric peptidic vectors, obtained by the divalent grafting of bombesin analogues on a newly synthesized DOTA-based prochelator, showed improved qualities as tumor targeted imaging probes in comparison to their monomeric analogues.

Understanding the resistivity and absolute thermoelectric power of disordered metals and alloys

International Nuclear Information System (INIS)

Gasser, Jean-Georges

2008-01-01

We recall definitions of the electronic transport properties, direct coefficients like electrical and thermal transport conductivities and crossed thermoelectric coefficients like the Seebeck, Peltier and Thomson coefficients. We discuss the links between the different electronic transport coefficients and the experimental problems in measuring these properties in liquid metals. The electronic transport properties are interpreted in terms of the scattering of electrons by 'pseudo-atoms'. The absolute thermoelectric power (ATP), thermopower or Seebeck coefficient is known as the derivative of the electrical resistivity versus energy. The key is to understand the concept of resistivity versus energy. We show that the resistivity follows approximately a 1/E curve. The structure factor modulates this curve and, for a Fermi energy corresponding to noble and divalent metals, induces a positive thermopower when the free electron theory predicts a negative one. A second modulation is introduced by the pseudopotential squared form factor or equivalently by the squared t matrix of the scattering potential. This term sometimes introduces an anti-resonance (divalent metals) which lowers the resistivity, and sometimes a resonance having an important effect on the transition metals. Following the position of the Fermi energy, the thermopower can be positive or negative. For heavy semi-metals, the density of states splits into an s and a p band, themselves different from a free electron E 0.5 curve. The electrons available to be scattered enter the Ziman formula. Thus if the density of states is not a free electron one, a third modulation of the ρ ≅ 1/E curve is needed, which also can change the sign of the thermopower. For alloys, different contributions weighted by the concentrations are needed to explain the concentration dependent resistivity or thermopower. The formalism is the same for amorphous metals. It is possible that this mechanism can be extended to high

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.

Sequence of ligand binding and structure change in the diphtheria toxin repressor upon activation by divalent transition metals.

Science.gov (United States)

Rangachari, Vijayaraghavan; Marin, Vedrana; Bienkiewicz, Ewa A; Semavina, Maria; Guerrero, Luis; Love, John F; Murphy, John R; Logan, Timothy M

2005-04-19

The diphtheria toxin repressor (DtxR) is an Fe(II)-activated transcriptional regulator of iron homeostatic and virulence genes in Corynebacterium diphtheriae. DtxR is a two-domain protein that contains two structurally and functionally distinct metal binding sites. Here, we investigate the molecular steps associated with activation by Ni(II)Cl(2) and Cd(II)Cl(2). Equilibrium binding energetics for Ni(II) were obtained from isothermal titration calorimetry, indicating apparent metal dissociation constants of 0.2 and 1.7 microM for two independent sites. The binding isotherms for Ni(II) and Cd(II) exhibited a characteristic exothermic-endothermic pattern that was used to infer the metal binding sequence by comparing the wild-type isotherm with those of several binding site mutants. These data were complemented by measuring the distance between specific backbone amide nitrogens and the first equivalent of metal through heteronuclear NMR relaxation measurements. Previous studies indicated that metal binding affects a disordered to ordered transition in the metal binding domain. The coupling between metal binding and structure change was investigated using near-UV circular dichroism spectroscopy. Together, the data show that the first equivalent of metal is bound by the primary metal binding site. This binding orients the DNA binding helices and begins to fold the N-terminal domain. Subsequent binding at the ancillary site completes the folding of this domain and formation of the dimer interface. This model is used to explain the behavior of several mutants.

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

New approach in modeling Cr(VI) sorption onto biomass from metal binary mixtures solutions

Energy Technology Data Exchange (ETDEWEB)

Liu, Chang [College of Environmental Science and Engineering, Anhui Normal University, South Jiuhua Road, 189, 241002 Wuhu (China); Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Fiol, Núria [Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Villaescusa, Isabel, E-mail: Isabel.Villaescusa@udg.edu [Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Poch, Jordi [Applied Mathematics Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain)

2016-01-15

In the last decades Cr(VI) sorption equilibrium and kinetic studies have been carried out using several types of biomasses. However there are few researchers that consider all the simultaneous processes that take place during Cr(VI) sorption (i.e., sorption/reduction of Cr(VI) and simultaneous formation and binding of reduced Cr(III)) when formulating a model that describes the overall sorption process. On the other hand Cr(VI) scarcely exists alone in wastewaters, it is usually found in mixtures with divalent metals. Therefore, the simultaneous removal of Cr(VI) and divalent metals in binary mixtures and the interactive mechanism governing Cr(VI) elimination have gained more and more attention. In the present work, kinetics of Cr(VI) sorption onto exhausted coffee from Cr(VI)–Cu(II) binary mixtures has been studied in a stirred batch reactor. A model including Cr(VI) sorption and reduction, Cr(III) sorption and the effect of the presence of Cu(II) in these processes has been developed and validated. This study constitutes an important advance in modeling Cr(VI) sorption kinetics especially when chromium sorption is in part based on the sorbent capacity of reducing hexavalent chromium and a metal cation is present in the binary mixture. - Highlights: • A kinetic model including Cr(VI) reduction, Cr(VI) and Cr(III) sorption/desorption • Synergistic effect of Cu(II) on Cr(VI) elimination included in the model • Model validation by checking it against independent sets of data.

New approach in modeling Cr(VI) sorption onto biomass from metal binary mixtures solutions

International Nuclear Information System (INIS)

Liu, Chang; Fiol, Núria; Villaescusa, Isabel; Poch, Jordi

2016-01-01

In the last decades Cr(VI) sorption equilibrium and kinetic studies have been carried out using several types of biomasses. However there are few researchers that consider all the simultaneous processes that take place during Cr(VI) sorption (i.e., sorption/reduction of Cr(VI) and simultaneous formation and binding of reduced Cr(III)) when formulating a model that describes the overall sorption process. On the other hand Cr(VI) scarcely exists alone in wastewaters, it is usually found in mixtures with divalent metals. Therefore, the simultaneous removal of Cr(VI) and divalent metals in binary mixtures and the interactive mechanism governing Cr(VI) elimination have gained more and more attention. In the present work, kinetics of Cr(VI) sorption onto exhausted coffee from Cr(VI)–Cu(II) binary mixtures has been studied in a stirred batch reactor. A model including Cr(VI) sorption and reduction, Cr(III) sorption and the effect of the presence of Cu(II) in these processes has been developed and validated. This study constitutes an important advance in modeling Cr(VI) sorption kinetics especially when chromium sorption is in part based on the sorbent capacity of reducing hexavalent chromium and a metal cation is present in the binary mixture. - Highlights: • A kinetic model including Cr(VI) reduction, Cr(VI) and Cr(III) sorption/desorption • Synergistic effect of Cu(II) on Cr(VI) elimination included in the model • Model validation by checking it against independent sets of data

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.

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

Prospects of gas hydrate presence in the Chukchi sea

Directory of Open Access Journals (Sweden)

Т. В. Матвеева

2017-08-01

Full Text Available The purpose of this study is to forecast the scale and distribution character of gas hydrate stability zone in the Chukchi Sea under simulated natural conditions and basing on these results to estimate resource potential of gas hydrates within this area. Three types of stability zone have been identified. A forecast map of gas hydrate environment and potentially gas hydrate-bearing water areas in the Chukchi Sea has been plotted to a scale of 1:5 000 000. Mapping of gas hydrate stability zone allowed to give a justified forecast based on currently available data on geologic, fluid dynamic, cryogenic, geothermal and pressure-temperature conditions of gas hydrate formation in the Chukchi Sea. It is the first forecast of such kind that focuses on formation conditions for hydrates of various types and compositions in the Arctic seas offshore Russia. Potential amount of gas, stored beneath the Chukchi Sea in the form of hydrates, is estimated based on mapping of their stability zone and falls into the interval of 7·1011-11.8·1013 m3.

Modeling dissociation behaviour of methane hydrate in porous soil media

Energy Technology Data Exchange (ETDEWEB)

Jayasinghe, A.G.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

2008-07-01

Gas hydrates, or clathrates, exist in the form of crystalline solid structures of hydrogen bonded water molecules where the lattice cages are occupied by guest gas molecules. Methane gas hydrates are the most common. As such, hydrate bearing sediments are considered to be a potential future energy resource. Gas hydrates also function as a source or sink for atmospheric methane, which may influence global warming. The authors emphasized that an understanding of the behaviour of soils containing gas hydrates is necessary in order to develop ways of recovering the vast gas resources that exist in the form of hydrates, particularly since hydrates are also suspected to be a potential factor in the initiation and propagation of submarine slope failures. Gas hydrate dissociation occurs when water and gas are released, resulting in an increase in pore fluid pressure, thereby causing significant reductions in effective stress leading to sediment failure. Dissociation may occur as a result of pressure reductions or increases in temperature. This study focused on the strength and deformation behaviour of hydrate bearing soils associated with temperature induced dissociation. Modeling the dissociation behavior of hydrates in porous soil media involves an understanding of the geomechanics of hydrate dissociation. This paper addressed the issue of coupling the hydrate dissociation problem with the soil deformation problem. A mathematical framework was constructed in which the thermally stimulated hydrate dissociation process in porous soil media under undrained conditions was considered with conduction heat transfer. It was concluded that a knowledge of geomechanical response of hydrate bearing sediments will enable better estimates of benefits and risks associated with the recovery process, thereby ensuring safe and economical exploration. 20 refs., 1 fig., 1 appendix.

Constraining gas hydrate occurrence in the northern Gulf of Mexico continental slope : fine scale analysis of grain-size in hydrate-bearing sediments

Energy Technology Data Exchange (ETDEWEB)

Hangsterfer, A.; Driscoll, N.; Kastner, M. [Scripps Inst. of Oceanography, La Jolla, CA (United States). Geosciences Research Division

2008-07-01

Methane hydrates can form within the gas hydrate stability zone (GHSZ) in sea beds. The Gulf of Mexico (GOM) contains an underlying petroleum system and deeply buried, yet dynamic salt deposits. Salt tectonics and fluid expulsion upward through the sediment column result in the formation of fractures, through which high salinity brines migrate into the GHSZ, destabilizing gas hydrates. Thermogenic and biogenic hydrocarbons also migrate to the seafloor along the GOMs northern slope, originating from the thermal and biogenic degradation of organic matter. Gas hydrate occurrence can be controlled by either primary permeability, forming in coarse-grained sediment layers, or by secondary permeability, forming in areas where hydrofracture and faulting generate conduits through which hydrocarbon-saturated fluids flow. This paper presented a study that attempted to determine the relationship between grain-size, permeability, and gas hydrate distribution. Grain-size analyses were performed on cores taken from Keathley Canyon and Atwater Valley in the GOM, on sections of cores that both contained and lacked gas hydrate. Using thermal anomalies as proxies for the occurrence of methane hydrate within the cores, samples of sediment were taken and the grain-size distributions were measured to see if there was a correlation between gas hydrate distribution and grain-size. The paper described the methods, including determination of hydrate occurrence and core analysis. It was concluded that gas hydrate occurrence in Keathley Canyon and Atwater Valley was constrained by secondary permeability and was structurally controlled by hydrofractures and faulting that acted as conduits through which methane-rich fluids flowed. 11 refs., 2 tabs., 5 figs.

TOUGH+HYDRATE v1.2 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

Energy Technology Data Exchange (ETDEWEB)

Moridis, George J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kowalsky, Michael B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pruess, Karsten [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2012-08-01

TOUGH+HYDRATE v1.2 is a code for the simulation of the behavior of hydratebearing geologic systems, and represents the second update of the code since its first release [Moridis et al., 2008]. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH4-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy’s law is valid. TOUGH+HYDRATE v1.2 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is a member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95/2003, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

Science.gov (United States)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with

Basics of development of gas hydrate deposits

Energy Technology Data Exchange (ETDEWEB)

Makogon, Yuri F.; Holditch, Stephen A.; Makogon, Taras Y.

2005-07-01

Natural gas hydrate deposits could possibly be an important energy resource during this century. However, many problems associated with producing these deposits must first be solved. The industry must develop new technologies to produce the gas, to forecast possible tectonic cataclysms in regions of gas hydrate accumulations, and to prevent damage to the environment. These global issues must be addressed by every company or country who wants to produce gas hydrate deposits. Cooperative research between industry and universities can lead to technology breakthroughs in coming years. This paper reviews the Messoyakha field and the Blake Ridge and Nankai areas to explain a methodology for estimating how much gas might be producible from gas hydrate deposits (GHDs) under various conditions. The Messoyakha field is located on land, while the Blake Ridge and Nankai areas are offshore. Messoyakha is the first and the only GHD where gas production from hydrates has reached commercial flow rates. The Blake Ridge GHD has been studied for 20 years and 11 wells have been drilled to collect gas-hydrate samples. The potential resources of gas (gas in place) from Blake Ridge is estimated at 37.7Oe10{sup 12} m{sup 3} (1.330 Tcf) in hydrate form and 19.3Oe10{sup 12}m{sup 3} (681 Bcf) [5] in free gas. To estimate how much of the potential resource can be produced we need a thorough understanding of both the geologic and the thermodynamic characteristics of the formations. (Author)

CLATHRATE HYDRATES FORMATION IN SHORT-PERIOD COMETS

International Nuclear Information System (INIS)

Marboeuf, Ulysse; Mousis, Olivier; Petit, Jean-Marc; Schmitt, Bernard

2010-01-01

The initial composition of current models of cometary nuclei is only based on two forms of ice: crystalline ice for long-period comets and amorphous ice for short-period comets. A third form of ice, i.e., clathrate hydrate, could exist within the short-period cometary nuclei, but the area of formation of this crystalline structure in these objects has never been studied. Here, we show that the thermodynamic conditions in the interior of short-period comets allow the existence of clathrate hydrates in Halley-type comets. We show that their existence is viable in the Jupiter family comets only when the equilibrium pressure of CO clathrate hydrate is at least 1 order of magnitude lower than the usually assumed theoretical value. We calculate that the amount of volatiles that could be trapped in the clathrate hydrate layer may be orders of magnitude greater than the daily amount of gas released at the surface of the nucleus at perihelion. The formation and the destruction of the clathrate hydrate cages could then explain the diversity of composition of volatiles observed in comets, as well as some pre-perihelion outbursts. We finally show that the potential clathrate hydrate layer in comet 67P/Churyumov-Gerasimenko would, unfortunately, be deep inside the nucleus, out of reach of the Rosetta lander. However, such a clathrate hydrate layer would show up by the gas composition of the coma.

Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

Directory of Open Access Journals (Sweden)

Jianzhong Zhao

2015-01-01

Full Text Available The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower temperature and higher pressure can promote hydrate formation, but they can increase production cost. So these factors should be considered synthetically. The investigation will promote the advance of gas storage technology in hydrates.

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

Science.gov (United States)

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

2016-11-01

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

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.

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.

Effect of Gemini-type surfactant on methane hydrate formation

Energy Technology Data Exchange (ETDEWEB)

Jeong, K.E.; Park, J.M.; Kim, C.U.; Chae, H.J.; Jeong, S.Y. [Korea Research Inst. of Chemical Technology, Jang-Dong, Yuseong-Gu, Daejeon (Korea, Republic of)

2008-07-01

Natural gas hydrates are formed from water and natural gas molecules at particular temperatures and pressures that become ice-like inclusion compounds. Gas hydrates offer several benefits such as energy resource potential and high storage capacity of natural gas in the form of hydrates. However, the application of natural gas hydrates has been deterred by its low formation rate and low conversion ratio of water into hydrate resulting in low actual storage capacity. This paper presented an experimental study to determine the effect of adding a novel Gemini-type surfactant on methane hydrate formation. The experimental study was described with reference to the properties of prepared diols and properties of prepared disulfonates. Gemini surfactant is the family of surfactant molecules possessing more than one hydrophobic tail and hydrophilic head group. They generally have better surface-active properties than conventional surfactants of equal chain length. The paper presented the results of the study in terms of the reactions of diols with propane sultone; storage capacity of hydrate formed with and without surfactant; and methane hydrate formation with and without disulfonate. It was concluded that the methane hydrate formation was accelerated by the addition of novel anionic Gemini-type surfactants and that hydrate formation was influenced by the surfactant concentration and alkyl chain length. For a given concentration, the surfactant with the highest chain length demonstrated the highest formation rate and storage capacity. 5 refs., 3 tabs., 4 figs.

Volume of hydration in terminal cancer patients.

Science.gov (United States)

Bruera, E; Belzile, M; Watanabe, S; Fainsinger, R L

1996-03-01

In this retrospective study we reviewed the volume and modality of hydration of consecutive series of terminal cancer patients in two different settings. In a palliative care unit 203/290 admitted patients received subcutaneous hydration for 12 +/- 8 days at a daily volume of 1015 +/- 135 ml/day. At the cancer center, 30 consecutive similar patients received intravenous hydration for 11.5 +/- 5 days (P > 0.2) but at a daily volume of 2080 +/- 720 ml/day (P palliative care unit patients required discontinuation of hydration because of complications. Hypodermoclysis was administered mainly as a continuous infusion, an overnight infusion, or in one to three 1-h boluses in 62 (31%), 98 (48%) and 43 (21%) patients, respectively. Our findings suggest that, in some settings, patients may be receiving excessive volumes of hydration by less comfortable routes such as the intravenous route. Increased education and research in this area are badly needed.

Geomechanical Performance of Hydrate-Bearing Sediment in Offshore Environments

Energy Technology Data Exchange (ETDEWEB)

Stephen Holditch; Tad Patzek; Jonny Rutqvist; George Moridis; Richard Plumb

2008-03-31

The objective of this multi-year, multi-institutional research project was to develop the knowledge base and quantitative predictive capability for the description of geomechanical performance of hydrate-bearing sediments (hereafter referred to as HBS) in oceanic environments. The focus was on the determination of the envelope of hydrate stability under conditions typical of those related to the construction and operation of offshore platforms. We have developed a robust numerical simulator of hydrate behavior in geologic media by coupling a reservoir model with a commercial geomechanical code. We also investigated the geomechanical behavior of oceanic HBS using pore-scale models (conceptual and mathematical) of fluid flow, stress analysis, and damage propagation. The objective of the UC Berkeley work was to develop a grain-scale model of hydrate-bearing sediments. Hydrate dissociation alters the strength of HBS. In particular, transformation of hydrate clusters into gas and liquid water weakens the skeleton and, simultaneously, reduces the effective stress by increasing the pore pressure. The large-scale objective of the study is evaluation of geomechanical stability of offshore oil and gas production infrastructure. At Lawrence Berkeley National Laboratory (LBNL), we have developed the numerical model TOUGH + Hydrate + FLAC3D to evaluate how the formation and disassociation of hydrates in seafloor sediments affects seafloor stability. Several technical papers were published using results from this model. LBNL also developed laboratory equipment and methods to produce realistic laboratory samples of sediments containing gas hydrates so that mechanical properties could be measured in the laboratory. These properties are required to run TOUGH + Hydrate + FLAC3D to evaluate seafloor stability issues. At Texas A&M University we performed a detailed literature review to determine what gas hydrate formation properties had been measured and reported in the literature. We

Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRH-Theory): three-dimensional PC validation

Science.gov (United States)

Kadyshevich, E. A.; Dzyabchenko, A. V.; Ostrovskii, V. E.

2014-04-01

Size compatibility of the CH4-hydrate structure II and multi-component DNA fragments is confirmed by three-dimensional simulation; it is validation of the Life Origination Hydrate Theory (LOH-Theory).

Androgen Receptor Antagonism By Divalent Ethisterone Conjugates In Castrate-Resistant Prostate Cancer Cells

Science.gov (United States)

Levine, Paul M.; Lee, Eugine; Greenfield, Alex; Bonneau, Richard; Logan, Susan K.; Garabedian, Michael J.; Kirshenbaum, Kent

2013-01-01

Sustained treatment of prostate cancer with Androgen Receptor (AR) antagonists can evoke drug resistance, leading to castrate-resistant disease. Elevated activity of the AR is often associated with this highly aggressive disease state. Therefore, new therapeutic regimens that target and modulate AR activity could prove beneficial. We previously introduced a versatile chemical platform to generate competitive and non-competitive multivalent peptoid oligomer conjugates that modulate AR activity. In particular, we identified a linear and a cyclic divalent ethisterone conjugate that exhibit potent anti-proliferative properties in LNCaP-abl cells, a model of castrate-resistant prostate cancer. Here, we characterize the mechanism of action of these compounds utilizing confocal microscopy, time-resolved fluorescence resonance energy transfer, chromatin immunoprecipitation, flow cytometry, and microarray analysis. The linear conjugate competitively blocks AR action by inhibiting DNA binding. In addition, the linear conjugate does not promote AR nuclear localization or co-activator binding. In contrast, the cyclic conjugate promotes AR nuclear localization and induces cell-cycle arrest, despite its inability to compete against endogenous ligand for binding to AR in vitro. Genome-wide expression analysis reveals that gene transcripts are differentially affected by treatment with the linear or cyclic conjugate. Although the divalent ethisterone conjugates share extensive chemical similarities, we illustrate that they can antagonize the AR via distinct mechanisms of action, establishing new therapeutic strategies for potential applications in AR pharmacology. PMID:22871957

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

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Richard Sigal; Kent Newsham; Thomas Williams; Barry Freifeld; Timothy Kneafsey; Carl Sondergeld; Shandra Rai; Jonathan Kwan; Stephen Kirby; Robert Kleinberg; Doug Griffin

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. The work scope drilled and cored a well The Hot Ice No. 1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report. The Hot Ice No. 1 well was drilled from the surface to a measured depth of 2300 ft. There was almost 100% core recovery from the bottom of surface casing at 107 ft to total depth. Based on the best estimate of the bottom of the methane hydrate stability zone (which used new data obtained from Hot Ice No. 1 and new analysis of data from adjacent wells), core was recovered over its complete range. Approximately 580 ft of porous, mostly frozen, sandstone and 155 of conglomerate were recovered in the Ugnu Formation and approximately 215 ft of porous sandstone were recovered in the West Sak Formation. There were gas shows in the bottom

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.)

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...

Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

Energy Technology Data Exchange (ETDEWEB)

McConnell, Dan

2018-02-25

Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydrates and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.

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.

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.

Enhanced desorption of cesium from collapsed interlayer regions in vermiculite by hydrothermal treatment with divalent cations

Energy Technology Data Exchange (ETDEWEB)

Yin, Xiangbiao, E-mail: yin.x.aa@m.titech.ac.jp [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Wang, Xinpeng [College of Resources and Metallurgy, Guangxi University, 100 Daxue East Road, Nanning 530004 (China); Wu, Hao; Ohnuki, Toshihiko; Takeshita, Kenji [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2017-03-15

Highlights: • Desorption of Cs{sup +} fixed in collapsed interlayer region of vermiculite was studied. • Monovalent cations readily induced interlayer collapse inhibiting Cs{sup +} desorption. • Larger hydrous ionic radii of divalent cations greatly prevented Cs{sup +} desorption. • Effect of divalent cation on Cs{sup +} desorption changes depending on thermal treatment. • ∼100% removal of saturated Cs{sup +} was achieved by hydrothermal treatment at 250 °C. - Abstract: Adsorption of cesium (Cs) on phyllosilicates has been intensively investigated because natural soils have strong ability of immobilizing Cs within clay minerals resulting in difficulty of decontamination. The objectives of present study are to clarify how Cs fixation on vermiculite is influenced by structure change caused by Cs sorption at different loading levels and how Cs desorption is affected by various replacing cations induced at different treating temperature. As a result, more than 80% of Cs was readily desorbed from vermiculite with loading amount of 2% saturated Cs (5.49 × 10{sup −3} mmol g{sup −1}) after four cycles of treatment of 0.01 M Mg{sup 2+}/Ca{sup 2+} at room temperature, but less than 20% of Cs was desorbed from saturated vermiculite. These distinct desorption patterns were attributed to inhibition of Cs desorption by interlayer collapse of vermiculite, especially at high Cs loadings. In contrast, elevated temperature significantly facilitated divalent cations to efficiently desorb Cs from collapsed regions. After five cycles of treatment at 250 °C with 0.01 M Mg{sup 2+}, ∼100% removal of saturated Cs was achieved. X-ray diffraction analysis results suggested that Cs desorption was completed through enhanced diffusion of Mg{sup 2+} cations into collapsed interlayer space under hydrothermal condition resulting in subsequent interlayer decollapse and readily release of Cs{sup +}.

Influence of Lithium Carbonate on C3A Hydration

Directory of Open Access Journals (Sweden)

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.

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.

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.

Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

Energy Technology Data Exchange (ETDEWEB)

Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

2008-07-01

Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

Clinker mineral hydration at reduced relative humidities

DEFF Research Database (Denmark)

Jensen, Ole Mejlhede

1998-01-01

This report deals with gas phase hydration of pure cement clinker minerals at reduced relative humidities. This is an important subject in relation to modern high performance concrete which may self-desiccate during hydration. In addition the subject has relevance to storage stability where...... prehydration may occur. In the report both theoretical considerations and experimental data are presented. It is suggested that the initiation of hydration during water vapour exposure is nucleation controlled....

Impact of welan gum on tricalcium aluminate–gypsum hydration

International Nuclear Information System (INIS)

Ma Lei; Zhao Qinglin; Yao Chukang; Zhou Mingkai

2012-01-01

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

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.

Behaviour of gas production from type 3 hydrate reservoirs

Energy Technology Data Exchange (ETDEWEB)

Pooladi-Darvish, M. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering]|[Fekete Associates Inc., Calgary, AB (Canada); Zatsepina, O. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering; Hong, H. [Fekete Associates Inc., Calgary, AB (Canada)

2008-07-01

The possible role of gas hydrates as a potential energy resource was discussed with particular reference to methods for estimating the rate of gas production from hydrate reservoirs under different operating conditions. This paper presented several numerical simulations studies of gas production from type 3 hydrate reservoirs in 1-D and 2-D geometries. Type 3 reservoirs include gas production from hydrate-reservoirs that lie totally within the hydrate stability zone and are sandwiched by impermeable layers on top and bottom. The purpose of this study was to better understand hydrate decomposition by depressurization. The study questioned whether 1-D modeling of type 3 hydrate reservoirs is a reasonable approximation. It also determined whether gas rate increases or decreases with time. The important reservoir characteristics for determining the rate of gas production were identified. Last, the study determined how competition between fluid and heat flow affects hydrate decomposition. This paper also described the relation and interaction between the heat and fluid flow mechanisms in depressurization of type 3 hydrate reservoirs. All results of 1-D and 2-D numerical simulation and analyses were generated using the STARS simulator. It was shown that the rate of gas production depends on the initial pressure/temperature conditions and permeability of the hydrate bearing formation. A high peak rate may be achieved under favourable conditions, but this peak rate is obtained after an initial period where the rate of gas production increases with time. The heat transfer in the direction perpendicular to the direction of fluid flow is significant, requiring 2D modeling. The hydraulic diffusivity is low because of the low permeability of hydrate-bearing formations. This could result in competition between heat and fluid flow, thereby influencing the behaviour of decomposition. 6 refs., 3 tabs., 12 figs.

Hydrate Evolution in Response to Ongoing Environmental Shifts

Energy Technology Data Exchange (ETDEWEB)

Rempel, Alan [Univ. of Oregon, Eugene, OR (United States)

2015-12-31

Natural gas hydrates have the potential to become a vital domestic clean-burning energy source. However, past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. This project was designed to fill critical gaps in our understanding of domestic hydrate resources and improve forecasts for their response to environmental shifts. Project work can be separated into three interrelated components, each involving the development of predictive mathematical models. The first project component concerns the role of sediment properties on the development and dissociation of concentrated hydrate anomalies. To this end, we developed numerical models to predict equilibrium solubility of methane in twophase equilibrium with hydrate as a function of measureable porous medium characteristics. The second project component concerned the evolution of hydrate distribution in heterogeneous reservoirs. To this end, we developed numerical models to predict the growth and decay of anomalies in representative physical environments. The third project component concerned the stability of hydrate-bearing slopes under changing environmental conditions. To this end, we developed numerical treatments of pore pressure evolution and consolidation, then used "infinite-slope" analysis to approximate the landslide potential in representative physical environments, and developed a "rate-and-state" frictional formulation to assess the stability of finite slip patches that are hypothesized to develop in response to the dissociation of hydrate anomalies. The increased predictive capabilities that result from this work provide a framework for interpreting field observations of hydrate anomalies in terms of the history of environmental forcing that led to their development. Moreover

An international effort to compare gas hydrate reservoir simulators

Energy Technology Data Exchange (ETDEWEB)

Wilder, J.W. [Akron Univ., Akron, OH (United States). Dept. of Theoretical and Applied Math; Moridis, G.J. [California Univ., Berkely, CA (United States). Earth Sciences Div., Lawrence Berkely National Lab.; Wilson, S.J. [Ryder Scott Co., Denver, CO (United States); Kurihara, M. [Japan Oil Engineering Co. Ltd., Tokyo (Japan); White, M.D. [Pacific Northwest National Laboratory Hydrology Group, Richland, WA (United States); Masuda, Y. [Tokyo Univ., Tokyo (Japan). Dept. of Geosystem Engineering; Anderson, B.J. [National Energy Technology Lab., Morgantown, WV (United States)]|[West Virginia Univ., Morgantown, WV (United States). Dept. of Chemical Engineering; Collett, T.S. [United States Geological Survey, Denver, CO (United States); Hunter, R.B. [ASRC Energy Services, Anchorage, AK (United States); Narita, H. [National Inst. of Advanced Industrial Science and Technology, MEthane hydrate Research Lab., Sapporo (Japan); Pooladi-Darvish, M. [Fekete Associates Inc., Calgary, AB (Canada); Rose, K.; Boswell, R. [National Energy Technology Lab., Morgantown, WV (United States)

2008-07-01

In this study, 5 different gas hydrate production scenarios were modeled by the CMG STARS, HydateResSim, MH-21 HYDRES, STOMP-HYD and the TOUGH+HYDRATE reservoir simulators for comparative purposes. The 5 problems ranged in complexity from 1 to 3 dimensional with radial symmetry, and in horizontal dimensions of 20 meters to 1 kilometer. The scenarios included (1) a base case with non-isothermal multi-fluid transition to equilibrium, (2) a base case with gas hydrate (closed-domain hydrate dissociation), (3) dissociation in a 1-D open domain, (4) gas hydrate dissociation in a one-dimensional radial domain, similarity solutions, (5) gas hydrate dissociation in a two-dimensional radial domain. The purpose of the study was to compare the world's leading gas hydrate reservoir simulators in an effort to improve the simulation capability of experimental and naturally occurring gas hydrate accumulations. The problem description and simulation results were presented for each scenario. The results of the first scenario indicated very close agreement among the simulators, suggesting that all address the basics of mass and heat transfer, as well as overall process of gas hydrate dissociation. The third scenario produced the initial divergence among the simulators. Other differences were noted in both scenario 4 and 5, resulting in significant corrections to algorithms within several of the simulators. The authors noted that it is unlikely that these improvements would have been identified without this comparative study due to a lack of real world data for validation purposes. It was concluded that the solution for gas hydrate production involves a combination of highly coupled fluid, heat and mass transport equations combined with the potential for formation or disappearance of multiple solid phases in the system. The physical and chemical properties of the rocks containing the gas hydrate depend on the amount of gas hydrate present in the system. Each modeling and

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

Science.gov (United States)

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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

Science.gov (United States)

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

2015-11-01

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

Composite anion-exchangers modified with nanoparticles of hydrated oxides of multivalent metals

Science.gov (United States)

Maltseva, T. V.; Kolomiets, E. O.; Dzyazko, Yu. S.; Scherbakov, S.

2018-02-01

Organic-inorganic composite ion-exchangers based on anion exchange resins have been obtained. Particles of one-component and two-component modifier were embedded using the approach, which allows us to realize purposeful control of a size of the embedded particles. The approach is based on Ostwald-Freundlich equation, which was adapted to deposition in ion exchange matrix. The equation was obtained experimentally. Hydrated oxides of zirconium and iron were applied to modification, concentration of the reagents were varied. The embedded particles accelerate sorption, the rate of which is fitted by the model equation of chemical reactions of pseudo-second order. When sorption of arsenate ions from very diluted solution (50 µg dm-3) occurs, the composites show higher distribution coefficients comparing with the pristine resin.

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.

Steric congestion at, and proximity to, a ferrous center leads to hydration of α-nitrile substituents forming coordinated carboxamides.

Science.gov (United States)

Thallaj, Nasser K; Orain, Pierre-Yves; Thibon, Aurore; Sandroni, Martina; Welter, Richard; Mandon, Dominique

2014-08-04

The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

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.

Geologic and porous media factors affecting the 2007 production response characteristics of the JOGMEC/NRCan/AURORA Mallik gas hydrate production research well

Energy Technology Data Exchange (ETDEWEB)

Dallimore, S. R.; Wright, J. F.; Nixon, F. M. [Natural Resources Canada, Sidney, BC (Canada). Geological Survey of Canada; Kurihara, M. [Japan Oil Engineering, Tokyo (Japan); Yamamoto, K.; Fujii, T.; Fujii, K.; Numasawa, M.; Yasuda, M. [Japan Oil, Gas, Metals National Corp., Chiba (Japan). Technical Research Centre; Imasato, Y. [Schlumberger K.K., Fuchinombe (Japan)

2008-07-01

The joint research project between Japan Oil, Gas and Metals National Corporation (JOGMEC), Natural Resources Canada (NRCan) and the Aurora Research Institute was conducted in an effort to measure and monitor the response of a terrestrial gas hydrate reservoir to pressure draw down. This paper reviewed the geologic setting and porous media conditions of a concentrated gas hydrate production interval between 1093 and 1105 m. The short-duration production test was conducted at the Mallik site in Canada's Mackenzie Delta in April 2007. The production interval consists of a sand-dominated succession with occasional silty sand interbeds. Gas hydrate occurs primarily within the sediment pore spaces, with concentrations ranging between 50-90 per cent. Experiments on pore water salinity and porous media conditions on pressure-temperature stability suggest that the partition between gas hydrate stability and instability should be considered as a phase boundary zone rather than a discrete threshold. The experiment revealed that there are significant changes to the physical properties following gas hydrate dissociation, with sediments containing no hydrate behaving as unconsolidated sands. A strong reservoir response to pressure draw down was observed with increasing gas flow during the testing period. Sand inflow to the well during the test may be attributed to loss of sediment strength during gas hydrate dissociation, with the sediment behaving as a gasified slurry. It was concluded that the gas flow response observed during the 2007 production test at Mallik was highly influenced by porous media properties and by the geological heterogeneities which may initiate high permeability conduits in sediments within the production interval of the Mallik gas hydrate reservoir. 18 refs., 6 figs.

Carbon dioxide gas hydrates accumulation in freezing and frozen sediments

Energy Technology Data Exchange (ETDEWEB)

Chuvilin, E.; Guryeva, O. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology

2008-07-01

Carbon dioxide (CO{sub 2}) hydrates and methane hydrates can be formed, and exist under natural conditions. The permafrost area has been considered as an environment for the potential disposal of CO{sub 2}. The favorable factors for preserving CO{sub 2} in liquid and gas hydrate states in frozen sediments and under permafrost horizons are great thickness of frozen sediments; low permeability in comparison with thawed sediments; and favourable conditions for hydrates formation. Therefore, research on the formation and existence conditions of CO{sub 2} gas hydrates in permafrost and under permafrost sediments are of great importance for estimation of CO{sub 2} disposal conditions in permafrost, and for working out specific sequestration schemes. This paper presented the results of an experimental study on the process of carbon dioxide (CO{sub 2}) gas hydrates formation in the porous media of sediments under positive and negative temperatures. Sediment samples of various compositions including those selected in the permafrost area were used. The research was conducted in a special pressure chamber, which allowed to monitor pressure and temperature. The study used the monitoring results in order to make quantitative estimation of the kinetics of CO{sub 2} hydrates accumulation in the model sediments. Results were presented in terms of kinetics of CO{sub 2} hydrates accumulation in the porous media at positive and negative temperatures; kinetics of CO{sub 2} hydrates accumulation in various porous media; gas hydrate-former influence on kinetics of hydrates accumulation in frozen sediments; and influence of freezing on CO{sub 2} hydrates accumulation in porous media. It was concluded that hydrate accumulation took an active place in porous media not only under positive, but also under high negative temperatures, when the water was mainly in the form of ice in porous media. 27 refs., 3 tabs., 5 figs.

Ion exchange equilibrium for some uni-univalent and uni-divalent reaction systems using strongly basic anion exchange resin Duolite A-102 D

Directory of Open Access Journals (Sweden)

R.S. Lokhande

2008-04-01

Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems was observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 13.7, 38.0, 23.9, 22.9 kJ/mol, respectively.

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

Science.gov (United States)

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

2011-01-01

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

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

Science.gov (United States)

Lee, M.W.

1999-01-01

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

A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl2 hydrates and MgCl2 hydrates for seasonal heat storage

NARCIS (Netherlands)

Pathak, A.D.; Gaastra-Nedea, S.V.; Zondag, H.A.; Rindt, C.C.M.; Smeulders, D.M.J.

2016-01-01

Salt hydrates store solar energy in chemical form via a reversible dehydration–hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The

Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

International Nuclear Information System (INIS)

Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

2017-01-01

Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.

Skin Hydration Assessment through Modern Non-Invasive Bioengineering Technologies.

Science.gov (United States)

Constantin, Maria-Magdalena; Poenaru, Elena; Poenaru, Calin; Constantin, Traian

2014-03-01

Non-invasive bioengineering technologies continuously discovered and developed in recent decades provide a significant input to research development and remarkably contribute to the improvement of medical education and care to our patients. Assessing skin hydration by using the capacitance method for a group of patients with allergic contact dermatitis versus healthy subjects, before and after applying a moisturiser (assessing the immediate and long-term effectiveness of hydration). For both groups, but especially for the patients with dry skin, there was a clear improvement of hydration, statistically significant after applying the moisturiser. In the case of the patients with allergic contact dermatitis, hydration was at a maximum immediately after the first application, and then maintained an increased level after 7 and 28 days, respectively. In the healthy subjects, the increase in hydration was lower, but progressive. The moisturiser determined an increase in hydration for all age groups, but those who showed the most obvious effect were the young adults (18-29 years old) with an increase of 19.9%.The maintenance effect of hydration lasted for 28 days, while the improvement was important for allergic skin (17.1%) and significant for healthy skin (10.9%). The assessment of epidermal hydration performed by using the corneometer showed very good hydration of the stratum corneum for both groups studied, with immediate and long-term effect. This study also showed that the degree of skin hydration was inversely proportional with age. The corneometer is easy to use, efficient and widely utilised in international studies for measurements in healthy or pathological conditions, for quantitative assessment of the effectiveness of various preparations intended for application to the skin surface, under well-controlled and standardised conditions.

Multisite Ion Model in Concentrated Solutions of Divalent Cations (MgCl2 and CaCl2): Osmotic Pressure Calculations

Science.gov (United States)

2015-01-01

Accurate force field parameters for ions are essential for meaningful simulation studies of proteins and nucleic acids. Currently accepted models of ions, especially for divalent ions, do not necessarily reproduce the right physiological behavior of Ca2+ and Mg2+ ions. Saxena and Sept (J. Chem. Theor. Comput.2013, 9, 3538–3542) described a model, called the multisite-ion model, where instead of treating the ions as an isolated sphere, the charge was split into multiple sites with partial charge. This model provided accurate inner shell coordination of the ion with biomolecules and predicted better free energies for proteins and nucleic acids. Here, we expand and refine the multisite model to describe the behavior of divalent ions in concentrated MgCl2 and CaCl2 electrolyte solutions, eliminating the unusual ion–ion pairing and clustering of ions which occurred in the original model. We calibrate and improve the parameters of the multisite model by matching the osmotic pressure of concentrated solutions of MgCl2 to the experimental values and then use these parameters to test the behavior of CaCl2 solutions. We find that the concentrated solutions of both divalent ions exhibit the experimentally observed behavior with correct osmotic pressure, the presence of solvent separated ion pairs instead of direct ion pairs, and no aggregation of ions. The improved multisite model for (Mg2+ and Ca2+) can be used in classical simulations of biomolecules at physiologically relevant salt concentrations. PMID:25482831

Precise structural analysis of methane hydrate by neutron diffraction

International Nuclear Information System (INIS)

Igawa, Naoki; Hoshikawa, Akinori; Ishii, Yoshinobu

2006-01-01

Methane hydrate has attracted great interest as an energy resource to replace natural gas since this material is deposited in the seafloor and the deposits are estimated to exceed those of natural gas. Understanding the physical proprieties, such as the temperature dependence of the crystal structure, helps to specify the optimum environmental temperature and pressure during drilling, transport, and storage of methane hydrate. Clathrate hydrates consisted of encaging atomic and/or molecular species as a guest and host water formed by a hydrogen bonding. Although many studies on the clathrate hydrate including methane hydrate were reported, no detailed crystallographic property has yet been cleared. We focused on the motion of methane in the clathrate hydrate by the neutron diffraction. The crystal structure of the methane hydrate was analyzed by the applying the combination of the Rietveld refinement and the maximum entropy method (MEM) to neutron powder diffraction. Temperature dependence of the scattering-length density distribution maps revealed that the motion of methane molecules differs between the shapes of dodecahedron and tetrakaidecahedron. (author)

National Gas Hydrate Program Expedition 01 offshore India; gas hydrate systems as revealed by hydrocarbon gas geochemistry

Science.gov (United States)

Lorenson, Thomas; Collett, Timothy S.

2018-01-01

The National Gas Hydrate Program Expedition 01 (NGHP-01) targeted gas hydrate accumulations offshore of the Indian Peninsula and along the Andaman convergent margin. The primary objectives of coring were to understand the geologic and geochemical controls on the accumulation of methane hydrate and their linkages to underlying petroleum systems. Four areas were investigated: 1) the Kerala-Konkan Basin in the eastern Arabian Sea, 2) the Mahanadi and 3) Krishna-Godavari Basins in the western Bay of Bengal, and 4) the Andaman forearc Basin in the Andaman Sea.Upward flux of methane at three of the four of the sites cored during NGHP-01 is apparent from the presence of seafloor mounds, seismic evidence for upward gas migration, shallow sub-seafloor geochemical evidence of methane oxidation, and near-seafloor gas composition that resembles gas from depth.The Kerala-Konkan Basin well contained only CO2 with no detectable hydrocarbons suggesting there is no gas hydrate system here. Gas and gas hydrate from the Krishna-Godavari Basin is mainly microbial methane with δ13C values ranging from −58.9 to −78.9‰, with small contributions from microbial ethane (−52.1‰) and CO2. Gas from the Mahanadi Basin was mainly methane with lower concentrations of C2-C5 hydrocarbons (C1/C2 ratios typically >1000) and CO2. Carbon isotopic compositions that ranged from −70.7 to −86.6‰ for methane and −62.9 to −63.7‰ for ethane are consistent with a microbial gas source; however deeper cores contained higher molecular weight hydrocarbon gases suggesting a small contribution from a thermogenic gas source. Gas composition in the Andaman Basin was mainly methane with lower concentrations of ethane to isopentane and CO2, C1/C2 ratios were mainly >1000 although deeper samples were compositions range from −65.2 to −80.7‰ for methane, −53.1 to −55.2‰ for ethane is consistent with mainly microbial gas sources, although one value recorded of −35.4‰ for propane

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

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.

Isotherms of ion exchange on titanates of alkaline metals

International Nuclear Information System (INIS)

Fillina, L.P.; Belinskaya, F.A.

1986-01-01

Present article is devoted to isotherms of ion exchange on titanates of alkaline metals. Therefore, finely dispersed hydrated titanates of alkaline metals (lithium, sodium, potassium) with ion exchange properties are obtained by means of alkaline hydrolysis of titanium chloride at high ph rates. Sorption of cations from salts solution of Li 2 SO 4 , NaNO 3 , Ca(NO 3 ) 2 , AgNO 3 by titanates is studied.

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

Science.gov (United States)

Lee, Myung W.; Waite, William F.

2008-07-01

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

Dehydration behaviour of hydrates

Energy Technology Data Exchange (ETDEWEB)

Dette, S.S.; Stelzer, T.; Jones, M.J.; Ulrich, J. [Martin-Luther-Universitaet Halle-Wittenberg, Zentrum fuer Ingenieurwissenschaften, Verfahrenstechnik/TVT, 06099 Halle (Germany)

2010-07-15

Immersing a crystalline solvate in a suitable anti-solvent can induce phase transformation to solvent-free solid phase. In certain cases the solvent-mediated phase transition results in the generation of hollow, tubular structures. Both the tube dimensions of sodium-2-keto-L-gulonate anhydrate (skga) and the dehydration kinetics of sodium-2-keto-L-gulonate monohydrate (skgm) can be modified by the antisolvent employed. An explanation for the variable dehydration behaviour of skgm in the antisolvents is presented here. Furthermore, other crystalline hydrates were dehydrated in dry methanol. Providing an operational window can be found, any hydrate material could possibly find use in the production of tubes (micro- or nanotubes for different applications). The experimental conditions selected (dry methanol as antisolvent, dehydration temperature at 25 C) for the dehydration did not lead to the anhydrate tube growth for all hydrates investigated. Based upon the results presented here a first hypothesis is presented to explain this effect. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Methane hydrates in quaternary climate change

International Nuclear Information System (INIS)

Kennett, J. P.; Hill, T. M.; Behl, R. J.

2005-01-01

The hydrate reservoir in marine sediments is known to contain a large volume of exchangeable carbon stored as solid methane hydrate and associated free gas. This reservoir has been shown to be potentially unstable in response to changing intermediate water temperature and sea level (pressure). Evidence continues to grow for past episodes of major methane release at times of climatic warming. Yet few studies of late Quaternary climate change include methane hydrates as an integral part of the global climate system, in spite of the largest known oscillations at this time in sea level and upper ocean temperature changes for the Cenozoic or earlier, conditions that favor instability of the methane hydrate reservoir. Abrupt increases in atmospheric methane recorded in polar ice cores are widely believed to have resulted, not from ocean-floor methane degassing, but instead from continental wetland activation, a hypothesis thus far unsupported by geological data. Furthermore, as part of this Wetland Methane Hypothesis, the abrupt methane increases have been seen as a response to climatic warming rather than contributing significantly to the change. An alternative view (formulated as the Clathrate Gun Hypothesis) is that the speed, magnitude and timing of abrupt climate change in the recent geologic past are consistent with the process of major degassing of methane hydrates. We summarize aspects of this hypothesis here and needs to test this hypothesis. (Author)

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

India National Gas Hydrate Program Expedition 02 Technical Contributions

Science.gov (United States)

Collett, T. S.; Kumar, P.; Shukla, K. M.; Nagalingam, J.; Lall, M. V.; Yamada, Y.; Schultheiss, P. J.; Holland, M.; Waite, W. F.

2017-12-01

The National Gas Hydrate Program Expedition 02 (NGHP-02) was conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India. The primary objective of this expedition was the exploration and discovery of highly saturated gas hydrate occurrences in sand reservoirs that would be targets of future production testing. The first 2 months of the expedition were dedicated to logging while drilling (LWD) operations with a total of 25 holes being drilled and logged. The next 3 months were dedicated to coring operations at 10 of the most promising sites. NGHP-02 downhole logging, coring and formation pressure testing have confirmed the presence of large, highly saturated, gas hydrate accumulations in coarse-grained sand-rich depositional systems throughout the Krishna-Godavari Basin within the regions defined during NGHP-02 as Area-B, Area-C, and Area-E. The nature of the discovered gas hydrate occurrences closely matched pre-drill predictions, confirming the project developed depositional models for the sand-rich depositional facies in the Krishna-Godavari and Mahanadi Basins. The existence of a fully developed gas hydrate petroleum system was established in Area-C of the Krishna-Godavari Basin with the discovery of a large slope-basin interconnected depositional system, including a sand-rich, gas-hydrate-bearing channel-levee prospect at Sites NGHP-02-08 and -09. The acquisition of closely spaced LWD and core holes in the Area-B L1 Block gas hydrate accumulation have provided one of the most complete three-dimensional petrophysical-based views of any known gas hydrate reservoir system in the world. It was concluded that Area-B and Area-C in the area of the greater Krishna-Godavari Basin contain important world-class gas hydrate accumulations and represent ideal sites for consideration of future gas hydrate production testing.

Experimental Investigation into the Combustion Characteristics of Propane Hydrates in Porous Media

Directory of Open Access Journals (Sweden)

Xiang-Ru Chen

2015-02-01

Full Text Available The combustion characteristics of both pure propane hydrates and the mixtures of hydrates and quartz sands were investigated by combustion experiments. The flame propagation, flame appearance, burning time and temperature in different hydrate layers were studied. For pure propane hydrate combustion, the initial flame falls in the “premixed” category. The flame propagates very rapidly, mainly as a result of burnt gas expansion. The flame finally self-extinguishes with some proportion of hydrates remaining unburned. For the hydrate-sand mixture combustion, the flame takes the form of many tiny discontinuous flames appearing and disappearing at different locations. The burn lasts for a much shorter amount of time than pure hydrate combustion. High porosity and high hydrate saturation is beneficial to the combustion. The hydrate combustion is the combustion of propane gas resulting from the dissociation of the hydrates. In both combustion test scenarios, the hydrate-dissociated water plays a key role in the fire extinction, because it is the main resistance that restrains the heat transfer from the flame to the hydrates and that prevents the hydrate-dissociated gas from releasing into the combustion zone.

SURVEY OF THE SPECTRA OF THE DIVALENT RARE EARTH IONS IN CUBIC CRYSTALS

Energy Technology Data Exchange (ETDEWEB)

McClure, Donald S. [Univ. of Chicago, IL (United States); Kiss, Zoltan J. [RCA Laboratories, Princeton, NJ (United States)

1963-04-15

The rare earth ions may exist in the divalent state in suitable host crystals such as CaF/sub 2/. All of the trivalent ions from La to Yb are reduced in situ to the divalent state in CaF/sub 2/ by gamma irradiation. The spectra of most of these ions show that the ground and first few excited states derive from f/sup n/ configurations, but the wesk absorption due to these is masked at higher energies by strong broad bands of the parity permitted f/sup n/ yields f/sup n-1/ d transitions. The excitation energy of these spectra have been calculated in a first approximation as the energy difference between the Hund Rule'' single determinant states of the configurations f/sup n -1/d and f/sup n/. This procedure satisfactorily accounts for the remarkable variations in the excitation energy in passing from one ion to the next in the series with the exception of Ge/ sup 2+/ Ce/sup 2+/, and Tb/sup 2+/, Ge/sup 2+/ probably has f/sup 7/d for its ground con figuration, while Ce/sup 2+/ and Tb/sup 2+/ are borderline cases. The spectral structure probably arises chiefly from the crystal field splitting of the d-orbital, since each ion in CaF/sub 2/ has a similar spectrum, and the spectra change drastically in sites of other than cubic symmetry. (auth)

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

International Nuclear Information System (INIS)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-01-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function. (paper)

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

Science.gov (United States)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-02-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

Science.gov (United States)

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Kinetic Hydration Heat Modeling for High-Performance Concrete Containing Limestone Powder

Directory of Open Access Journals (Sweden)

Xiao-Yong Wang

2017-01-01

Full Text Available Limestone powder is increasingly used in producing high-performance concrete in the modern concrete industry. Limestone powder blended concrete has many advantages, such as increasing the early-age strength, reducing the setting time, improving the workability, and reducing the heat of hydration. This study presents a kinetic model for modeling the hydration heat of limestone blended concrete. First, an improved hydration model is proposed which considers the dilution effect and nucleation effect due to limestone powder addition. A degree of hydration is calculated using this improved hydration model. Second, hydration heat is calculated using the degree of hydration. The effects of water to binder ratio and limestone replacement ratio on hydration heat are clarified. Third, the temperature history and temperature distribution of hardening limestone blended concrete are calculated by combining hydration model with finite element method. The analysis results generally agree with experimental results of high-performance concrete with various mixing proportions.

Natural gas storage in hydrates with the presence of promoters

International Nuclear Information System (INIS)

Sun Zhigao; Wang Ruzhu; Ma Rongsheng; Guo Kaihua; Fan Shuanshi

2003-01-01

Hydrate technology is being developed for the storage and transport of natural gas. Micellar surfectant solutions were found to increase the gas hydrate formation rate and storage capacity. An anionic surfactant, a nonionic surfactant, their mixtures and cyclopentane were used to improve the hydrate formation of a synthetic natural gas (methane=92.05 mol%, ethane=4.96 mol%, propane=2.99 mol%) in a quiescent system in this work. The effect of an anionic surfactant (sodium dodecyl sulfate) on natural gas storage in hydrates is more pronounced compared to the effect of a nonionic surfactant (dodecyl polysaccharide glycoside). Cyclopentane could reduce hydrate formation induction time but could not improve the hydrate formation rate and storage capacity

Methane Production and Carbon Capture by Hydrate Swapping

DEFF Research Database (Denmark)

Mu, Liang; von Solms, Nicolas

2017-01-01

There are essentially two different approaches to producing methane from natural gas hydrate reservoirs, either bring the hydrate out of its thermodynamic stability region or expose the hydrate to a substance that will form a more stable hydrate structure, forcing an in situ swapping of the trapped...... experimental runs were performed to examine the influence of operating conditions on methane production by CO2/(CO2 + N2) injection in the temperature range of 274.15–277.15 K and 7.039–10.107 MPa pressure. Our results show that the use of the (CO2 + N2) binary gas mixture is advantageous compared to the use...

Irrigation port hydration in phacoemulsification surgery

Directory of Open Access Journals (Sweden)

Suzuki H

2018-01-01

Full Text Available Hisaharu Suzuki,1 Yoichiro Masuda,2 Yuki Hamajima,1 Hiroshi Takahashi3 1Department of Ophthalmology, Nippon Medical School Musashikosugi Hospital, Kawasaki City, Kanagawa, 2Department of Ophthalmology, The Jikei University, Katsushika Medical Center, Tokyo, 3Department of Ophthalmology, Nippon Medical School, Tokyo, Japan Background: In most cases, hydration is performed by water injection into the stromal tissue with a needle. The technique is simple, however it is sometimes troublesome.Purpose: We describe a simple technique for hydrating the corneal stroma in cataract surgery using an irrigation port.Patients and methods: The technique began by pushing the irrigation port against the corneal stroma for a few seconds during phacoemulsification, which generated edema in the corneal incision that subsequently prevented leakage. This procedure is called the hydration using irrigation port (HYUIP technique. A total of 60 eyes were randomized and placed in two groups, 30 eyes underwent surgeries using the HYUIP technique (HYUIP group and 30 eyes underwent surgeries without the HYUIP technique (control. The three points evaluated during each surgery included 1 the occurrence of anterior chamber collapse during the pulling out of the I/A tip after inserting the intraocular lens, 2 the need for conventional hydration, and 3 watertight completion at the end stage of surgery.Results: The anterior chamber collapse and the need for conventional hydration were significantly smaller in the HYUIP group compared to the control group. Regarding the self-sealing completion, no significant difference was observed between the two groups.Conclusion: The HYUIP technique is an effective method for creating self-sealing wound. In addition, this technique helps to prevent anterior chamber collapse. Keywords: cataract surgery, hydration, irrigation and aspiration, phacoemulsification, wound, self-sealing 

Metal-Chelate Immobilization of Lipase onto Polyethylenimine Coated MCM-41 for Apple Flavor Synthesis.

Science.gov (United States)

Sadighi, Armin; Motevalizadeh, Seyed Farshad; Hosseini, Morteza; Ramazani, Ali; Gorgannezhad, Lena; Nadri, Hamid; Deiham, Behnaz; Ganjali, Mohammad Reza; Shafiee, Abbas; Faramarzi, Mohammad Ali; Khoobi, Mehdi

2017-08-01

An enzyme immobilized on a mesoporous silica nanoparticle can serve as a multiple catalyst for the synthesis of industrially useful chemicals. In this work, MCM-41 nanoparticles were coated with polyethylenimine (MCM-41@PEI) and further modified by chelation of divalent metal ions (M = Co 2+ , Cu 2+ , or Pd 2+ ) to produce metal-chelated silica nanoparticles (MCM-41@PEI-M). Thermomyces lanuginosa lipase (TLL) was immobilized onto MCM-41, MCM-41@PEI, and MCM-41@PEI-M by physical adsorption. Maximum immobilization yield and efficiency of 75 ± 3.5 and 65 ± 2.7% were obtained for MCM@PEI-Co, respectively. The highest biocatalytic activity at extremely acidic and basic pH (pH = 3 and 10) values were achieved for MCM-PEI-Co and MCM-PEI-Cu, respectively. Optimum enzymatic activity was observed for MCM-41@PEI-Co at 75 °C, while immobilized lipase on the Co-chelated support retained 70% of its initial activity after 14 days of storage at room temperature. Due to its efficient catalytic performance, MCM-41@PEI-Co was selected for the synthesis of ethyl valerate in the presence of valeric acid and ethanol. The enzymatic esterification yield for immobilized lipase onto MCM-41@PEI-Co was 60 and 53%, respectively, after 24 h of incubation in n-hexane and dimethyl sulfoxide media. Graphical Abstract Divalent metal chelated polyethylenimine coated MCM-41 (MCM-41@PEI-M) was used for immobilization of Thermomyces lanuginosa lipase catalyzing green apple flavor preparation.

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

Energy Technology Data Exchange (ETDEWEB)

Dai, Sheng [Georgia Tech Research Corporation, Atlanta, GA (United States); Santamarina, J. Carlos [King Abdulaziz Univ., Jeddah (Saudi Arabia)

2017-12-30

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