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Sample records for alkaline hydrothermal solutions

  1. Direct Hydrothermal Precipitation of Pyrochlore-Type Tungsten Trioxide Hemihydrate from Alkaline Sodium Tungstate Solution

    NASA Astrophysics Data System (ADS)

    Li, Xiaobin; Li, Jianpu; Zhou, Qiusheng; Peng, Zhihong; Liu, Guihua; Qi, Tiangui

    2012-04-01

    Pyrochlore-type tungsten trioxide hemihydrate (WO3·0.5H2O) powder with the average particle size of 0.5 μm was prepared successfully from the weak alkaline sodium tungstate solution by using organic substances of sucrose or cisbutenedioic acid as the acidification agent. The influences of solution pH and acidification agents on the precipitation process were investigated. The results showed that organic acidification agents such as sucrose and cisbutenedioic acid could improve the precipitation of pyrochlore WO3·0.5H2O greatly from sodium tungstate solution compared with the traditional acidification agent of hydrochloric acid. In addition, the pH value of the hydrothermal system played a critical role in the precipitation process of WO3·0.5H2O, and WO3·0.5H2O precipitation mainly occured in the pH range of 7.0 to 8.5. The precipitation rate of tungsten species in the sodium tungstate solution could reach up to 98 pct under the optimized hydrothermal conditions. This article proposed also the hydrothermal precipitation mechanism of WO3·0.5H2O from the weak alkaline sodium tungstate solution. The novel method reported in this study has a great potential to improve the efficiency of advanced tungsten trioxide-based functional material preparation, as well as for the pollution-reducing and energy-saving tungsten extractive metallurgy.

  2. Adsorption of tungsten onto zeolite fly ash produced by hydrothermally treating fly ash in alkaline solution.

    PubMed

    Ogata, Fumihiko; Iwata, Yuka; Kawasaki, Naohito

    2014-01-01

    Fly ash (FA) was hydrothermally treated in an alkaline solution to produce zeolite fly ash (Z-FA). The properties of the FA and Z-FA were investigated. The amounts of tungsten (W) adsorbed onto the FA and Z-FA surfaces were evaluated. Z-FA was produced by hydrothermally treating FA in an alkaline solution. The specific surface area and pore volume of the Z-FA were greater than those of the FA. More W was adsorbed onto the Z-FA surface than onto the FA surface. The adsorption isotherms for W were fitted using both the Freundlich and Langmuir equations. The equilibrium concentrations of W adsorbed onto the FA and Z-FA surfaces were subsequently reached within 20 h. The pseudo-second-order model more accurately described the data than did the pseudo-first-order model. Sodium hydroxide solutions (1-50 mmol/L) were used to easily recover W from Z-FA, indicating that Z-FA was useful for recovering W from aqueous solutions.

  3. Prebiotic Synthesis of Glycine from Ethanolamine in Simulated Archean Alkaline Hydrothermal Vents.

    PubMed

    Zhang, Xianlong; Tian, Ge; Gao, Jing; Han, Mei; Su, Rui; Wang, Yanxiang; Feng, Shouhua

    2016-09-23

    Submarine hydrothermal vents are generally considered as the likely habitats for the origin and evolution of early life on Earth. In recent years, a novel hydrothermal system in Archean subseafloor has been proposed. In this model, highly alkaline and high temperature hydrothermal fluids were generated in basalt-hosted hydrothermal vents, where H2 and CO2 could be abundantly provided. These extreme conditions could have played an irreplaceable role in the early evolution of life. Nevertheless, sufficient information has not yet been obtained for the abiotic synthesis of amino acids, which are indispensable components of life, at high temperature and alkaline condition. This study aims to propose a new method for the synthesis of glycine in simulated Archean submarine alkaline vent systems. We investigated the formation of glycine from ethanolamine under conditions of high temperature (80-160 °C) and highly alkaline solutions (pH = 9.70). Experiments were performed in an anaerobic environment under mild pressure (0.1-8.0 MPa) at the same time. The results suggested that the formation of glycine from ethanolamine occurred rapidly and efficiently in the presence of metal powders, and was favored by high temperatures and high pressures. The experiment provides a new pathway for prebiotic glycine formation and points out the phenomenal influence of high-temperature alkaline hydrothermal vents in origin of life in the early ocean.

  4. Prebiotic Synthesis of Glycine from Ethanolamine in Simulated Archean Alkaline Hydrothermal Vents

    NASA Astrophysics Data System (ADS)

    Zhang, Xianlong; Tian, Ge; Gao, Jing; Han, Mei; Su, Rui; Wang, Yanxiang; Feng, Shouhua

    2016-09-01

    Submarine hydrothermal vents are generally considered as the likely habitats for the origin and evolution of early life on Earth. In recent years, a novel hydrothermal system in Archean subseafloor has been proposed. In this model, highly alkaline and high temperature hydrothermal fluids were generated in basalt-hosted hydrothermal vents, where H2 and CO2 could be abundantly provided. These extreme conditions could have played an irreplaceable role in the early evolution of life. Nevertheless, sufficient information has not yet been obtained for the abiotic synthesis of amino acids, which are indispensable components of life, at high temperature and alkaline condition. This study aims to propose a new method for the synthesis of glycine in simulated Archean submarine alkaline vent systems. We investigated the formation of glycine from ethanolamine under conditions of high temperature (80-160 °C) and highly alkaline solutions (pH = 9.70). Experiments were performed in an anaerobic environment under mild pressure (0.1-8.0 MPa) at the same time. The results suggested that the formation of glycine from ethanolamine occurred rapidly and efficiently in the presence of metal powders, and was favored by high temperatures and high pressures. The experiment provides a new pathway for prebiotic glycine formation and points out the phenomenal influence of high-temperature alkaline hydrothermal vents in origin of life in the early ocean.

  5. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments.

    PubMed

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  6. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  7. Catalytic Diversity in Alkaline Hydrothermal Vent Systems on Ocean Worlds

    NASA Astrophysics Data System (ADS)

    Cameron, Ryan D.; Barge, Laura; Chin, Keith B.; Doloboff, Ivria J.; Flores, Erika; Hammer, Arden C.; Sobron, Pablo; Russell, Michael J.; Kanik, Isik

    2016-10-01

    Hydrothermal systems formed by serpentinization can create moderate-temperature, alkaline systems and it is possible that this type of vent could exist on icy worlds such as Europa which have water-rock interfaces. It has been proposed that some prebiotic chemistry responsible for the emergence of life on Earth and possibly other wet and icy worlds could occur as a result ofredox potential and pH gradients in submarine alkaline hydrothermal vents (Russell et al., 2014). Hydrothermal chimneys formed in laboratory simulations of alkaline vents under early Earth conditions have precipitate membranes that contain minerals such as iron sulfides, which are hypothesized to catalyze reduction of CO2 (Yamaguchi et al. 2014, Roldan et al. 2014) leading to further organic synthesis. This CO2 reduction process may be affected by other trace components in the chimney, e.g. nickel or organic molecules. We have conducted experiments to investigate catalytic properties of iron and iron-nickel sulfides containing organic dopants in slightly acidic ocean simulants relevant to early Earth or possibly ocean worlds. We find that the electrochemical properties of the chimney as well as the morphology/chemistry of the precipitate are affected by the concentration and type of organics present. These results imply that synthesis of organics in water-rock systems on ocean worlds may lead to hydrothermal precipitates which can incorporate these organic into the mineral matrix and may affect the role of gradients in alkaline vent systems.Therefore, further understanding on the electroactive roles of various organic species within hydrothermal chimneys will have important implications for habitability as well as prebiotic chemistry. This work is funded by NASA Astrobiology Institute JPL Icy Worlds Team and a NAI Director's Discretionary Fund award.Yamaguchi A. et al. (2014) Electrochimica Acta, 141, 311-318.Russell, M. J. et al. (2014), Astrobiology, 14, 308-43.Roldan, A. (2014) Chem. Comm. 51

  8. RNA Oligomerization in Laboratory Analogues of Alkaline Hydrothermal Vent Systems.

    PubMed

    Burcar, Bradley T; Barge, Laura M; Trail, Dustin; Watson, E Bruce; Russell, Michael J; McGown, Linda B

    2015-07-01

    Discovering pathways leading to long-chain RNA formation under feasible prebiotic conditions is an essential step toward demonstrating the viability of the RNA World hypothesis. Intensive research efforts have provided evidence of RNA oligomerization by using circular ribonucleotides, imidazole-activated ribonucleotides with montmorillonite catalyst, and ribonucleotides in the presence of lipids. Additionally, mineral surfaces such as borates, apatite, and calcite have been shown to catalyze the formation of small organic compounds from inorganic precursors (Cleaves, 2008 ), pointing to possible geological sites for the origins of life. Indeed, the catalytic properties of these particular minerals provide compelling evidence for alkaline hydrothermal vents as a potential site for the origins of life since, at these vents, large metal-rich chimney structures can form that have been shown to be energetically favorable to diverse forms of life. Here, we test the ability of iron- and sulfur-rich chimneys to support RNA oligomerization reactions using imidazole-activated and non-activated ribonucleotides. The chimneys were synthesized in the laboratory in aqueous "ocean" solutions under conditions consistent with current understanding of early Earth. Effects of elemental composition, pH, inclusion of catalytic montmorillonite clay, doping of chimneys with small organic compounds, and in situ ribonucleotide activation on RNA polymerization were investigated. These experiments, under certain conditions, showed successful dimerization by using unmodified ribonucleotides, with the generation of RNA oligomers up to 4 units in length when imidazole-activated ribonucleotides were used instead. Elemental analysis of the chimney precipitates and the reaction solutions showed that most of the metal cations that were determined were preferentially partitioned into the chimneys.

  9. Technetium recovery from high alkaline solution

    DOEpatents

    Nash, Charles A.

    2016-07-12

    Disclosed are methods for recovering technetium from a highly alkaline solution. The highly alkaline solution can be a liquid waste solution from a nuclear waste processing system. Methods can include combining the solution with a reductant capable of reducing technetium at the high pH of the solution and adding to or forming in the solution an adsorbent capable of adsorbing the precipitated technetium at the high pH of the solution.

  10. The Origin of Life in Alkaline Hydrothermal Vents.

    PubMed

    Sojo, Victor; Herschy, Barry; Whicher, Alexandra; Camprubí, Eloi; Lane, Nick

    2016-02-01

    Over the last 70 years, prebiotic chemists have been very successful in synthesizing the molecules of life, from amino acids to nucleotides. Yet there is strikingly little resemblance between much of this chemistry and the metabolic pathways of cells, in terms of substrates, catalysts, and synthetic pathways. In contrast, alkaline hydrothermal vents offer conditions similar to those harnessed by modern autotrophs, but there has been limited experimental evidence that such conditions could drive prebiotic chemistry. In the Hadean, in the absence of oxygen, alkaline vents are proposed to have acted as electrochemical flow reactors, in which alkaline fluids saturated in H2 mixed with relatively acidic ocean waters rich in CO2, through a labyrinth of interconnected micropores with thin inorganic walls containing catalytic Fe(Ni)S minerals. The difference in pH across these thin barriers produced natural proton gradients with equivalent magnitude and polarity to the proton-motive force required for carbon fixation in extant bacteria and archaea. How such gradients could have powered carbon reduction or energy flux before the advent of organic protocells with genes and proteins is unknown. Work over the last decade suggests several possible hypotheses that are currently being tested in laboratory experiments, field observations, and phylogenetic reconstructions of ancestral metabolism. We analyze the perplexing differences in carbon and energy metabolism in methanogenic archaea and acetogenic bacteria to propose a possible ancestral mechanism of CO2 reduction in alkaline hydrothermal vents. Based on this mechanism, we show that the evolution of active ion pumping could have driven the deep divergence of bacteria and archaea.

  11. Effect of hydrothermal reaction time and alkaline conditions on the electrochemical properties of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Giannouri, M.; Boukos, N.; Lei, C.; Lekakou, C.; Trapalis, C.

    2015-12-01

    Reduced graphene oxide sheets (rGO) were prepared by hydrothermal treatment of aqueous dispersions of graphite oxide (GtO) applied for short (4 h) and prolonged reaction times (19-24 h). The effect of process duration as well as the alkaline conditions (pH ∼10) by addition of K2CO3 on the quality characteristics of the produced rGO materials was investigated. Both reduction and exfoliation occurred during this process as it was evidenced by FTIR and XRD data. SEM, TEM and HRTEM microscopy displayed highly exfoliated rGO materials. XPS verified that the re-establishment of the conjugated graphene network is more extensive for prolonged times of hydrothermal processing in accordance to Raman spectroscopy measurements. The sample produced under alkaline conditions bore fewer defects and almost 5 times higher BET surface area (∼181 m2/g) than the sample with no pH adjustment (∼34 m2/g) for the same hydrothermal reaction time (19 h), attributed to the developed microporosity. The specific capacitance of this material estimated by electrochemical impedance using three-electrode cell and KCl aqueous solution as an electrolyte was ∼400-500 F/g. When EDLC capacitors were fabricated from rGO materials the electrochemical testing in organic electrolyte i.e. TEABF4 in PC, revealed that the shortest hydrothermal reaction time (4 h) was more efficient resulting in capacitance around 60 F/g.

  12. Process for extracting technetium from alkaline solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

    1995-01-01

    A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

  13. Mackinawite and greigite in ancient alkaline hydrothermal chimneys: Identifying potential key catalysts for emergent life

    NASA Astrophysics Data System (ADS)

    White, Lauren M.; Bhartia, Rohit; Stucky, Galen D.; Kanik, Isik; Russell, Michael J.

    2015-11-01

    One model for the emergence of life posits that ancient, low temperature, submarine alkaline hydrothermal vents, partly composed of iron-sulfides, were capable of catalyzing the synthesis of prebiotic organic molecules from CO2, H2 and CH4. Specifically, hydrothermal mackinawite (FeIIS) and greigite (FeIIFeIII2S4) have been highlighted in previous studies as analogs of the active centers of hydrogenase, ferredoxin, acetyl coenzyme-A synthase and carbon monoxide dehydrogenase featured in the biochemistry of certain autotrophic prokaryotes that occupy the base of the evolutionary tree. Despite the proposed importance of iron sulfide minerals and clusters in the synthesis of abiotic organic molecules, the mechanisms for the formation of these sulfides from solution and their preservation under the anoxic and low temperature (below 100 °C) conditions expected in off-axis submarine alkaline vent systems is not well understood (Bourdoiseau et al., 2011; Rickard and Luther, 2007). To rectify this, single hydrothermal chimneys were precipitated using a unique apparatus to simulate growth at hydrothermal vents of moderate temperature under supposed Hadean ocean-bottom conditions. Iron sulfide phases were observed through Raman spectroscopy at growth temperatures ranging from 40° to 80 °C. Fe(III)-containing mackinawite is confirmed to be present with mackinawite and greigite, supporting an FeIII-mackinawite intermediate mechanism for the transformation of mackinawite to greigite below 100 °C. Raman spectroscopy of the chimneys revealed a maximum yield of greigite at 75 °C. These results suggest abiotic production of catalytically active mackinawite and greigite are possible under early Earth hydrothermal conditions as well as on other wet, rocky worlds geochemically similar to the Earth.

  14. [Chemical structure of bioethanol lignin by low-temperature alkaline catalytic hydrothermal treatment].

    PubMed

    Liu, Xiao-Huan; Zhang, Ming-Ming; Wang, Ji-Fu; Xu, Yu-Zhi; Wang, Chun-Peng; Chu, Fu-Xiang

    2013-11-01

    In order to improve the reaction activity of bioethanol lignin, we investigated the activation of bioethanol lignin by a hydrothermal treatment method. Catalytic hydrothermal treatment of bioethanol lignin was performed at 180 degrees C for 3 h in the presence of alkaline solutions (NaOH, Na2 CO3, KOH and K2 CO3), the change in bioethanol lignin structures was studied comparatively by FTIR, 1H NMR,GPC and elemental analysis. FTIR spectra showed that after alkali hydrothermal treatment, the band at 1 375 cm(-1) attributed to the phenolic hydroxyl groups increased, and the band intensity at 1 116 cm(-1) attributed to the ether bond decreased. On the other hand, the band at 1 597 and 1 511 cm(-1) attributed to aromatic skeletal vibration remained almost unchanged. 1H NMR spectra showed that after alkali hydrothermal treatment, the number of aromatic methoxyl is increased, and based on the increment of the content of phenolic hydroxyl, the catalytic activity can be ranked as follows: KOH > NaOH > K2 CO3 > Na2 CO3. Especially for KOH, the increment of the content of phenolic hydroxyl was 170%, because the ion radius of potassium cation is bigger than sodium cation, so the potassium cations more easily formed cation adducts with lignin. GPC results showed that the molecular weight of alkali hydrothermal treatment lignin decreased and the molecular distribution got wider. Elemental analysis showed that hydrothermal treatment could break the interlinkage between lignin and protein, which can reduce the protein content and increase the purity of lignin, meanwhile, the content of O and H both decreased,while C fell, indicating that the bioethanol lignin had suffered a decarbonylation reaction. This is the most benefit of the lignin as a substitute for phenol.

  15. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil

    SciTech Connect

    Zheng, Ji-Lu Zhu, Ming-Qiang; Wu, Hai-tang

    2015-09-15

    Highlights: • Swine carcasses can be converted to bio-oil by alkaline hydrothermal liquefaction. • It seems that the use of the bio-oil for heat or CHP is technically suitable. • Some valuable chemicals were found in the bio-oils. • The bio-oil and the solid residue constituted an energy efficiency of 93.63% for the feedstock. • The solid residue can be used as a soil amendment, to sequester C and for preparing activated carbon. - Abstract: It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2 wt% bio-oil, having a high heating value of 32.35 MJ/kg and a viscosity of 305cp, and 22 wt% solid residue were realized at a liquefaction temperature of 250 °C, a reaction time of 60 min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels.

  16. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil.

    PubMed

    Zheng, Ji-Lu; Zhu, Ming-Qiang; Wu, Hai-tang

    2015-09-01

    It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2wt% bio-oil, having a high heating value of 32.35MJ/kg and a viscosity of 305cp, and 22wt% solid residue were realized at a liquefaction temperature of 250°C, a reaction time of 60min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels.

  17. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  18. Pyrite Recrystallization Experiments With Circulating Hydrothermal Solution

    NASA Astrophysics Data System (ADS)

    Isobe, H.; Abe, A.; Tanaka, K.

    2007-12-01

    Pyrite is one of the most common sulfide minerals found in hydrothermal deposits and sea-floor sediments from hydrothermal fumaroles. Hydrothermal fluid flow plays an important role in crystallization of sulfide minerals. In this study, we tried to reproduce pyrite crystallization with one-way flowing hydrothermal fluid. We designed a circuit circulating hydrothermal fluid by thermal convection. A rectangular circuit (42.6 cm by 17.3 cm) of SUS316 pressure tubes with 5 mm in inner diameter was used as a reaction vessel. In the circuit, pyrite dissolves to acidic fluid in upstream region. Then, pyrite will crystallize again in downstream region as temperature decreases. The rectangular plane was held to be 20 degrees inclination to generate thermal convection. One of the long sides of the rectangular was heated by an electric furnace. Starting materials were put in a tube to be heated. Upper half, approximately 20 cm, of the tube was filled with quartz sand. Next quarter was filled with equivalent mass mixture of quartz sand and powdered pyrite crystals. The lowest quarter was filled with mixture of quartz sand, pyrite, anhydrite and sulfur, those mass are equivalent. The solution was a mixture of 0.5mol/l HCl and 3.0mol/l NaCl. Maximum temperature was controlled to approximately 350°C at the center of the heated tube. Experimental durations were up to 9 days. Fluid pressure increased to approximately 6 MPa as heating. After the experiments, the run products were fixed with resin in a sample tube, and vertical sections were observed by SEM. In the run products, pyrite dissolved at the lower part of the starting material. In the upper half of the sample tube, pyrite crystals precipitated on quartz surface. Crystallization density depends on temperature gradient of the fluid. Predominant morphology of the pyrite crystals consists (100) plains. Tiny framboidal aggregates and crystals with (210) plains also occur. In the run products of longer than 3 days run durations

  19. From Geochemistry to Biochemistry: Simulating Prebiotic Chemistry Driven by Geochemical Gradients in Alkaline Hydrothermal Vents

    NASA Astrophysics Data System (ADS)

    Barge, Laurie

    2016-07-01

    Planetary water-rock interfaces generate energy in the form of redox, pH, and thermal gradients, and these disequilibria are particularly focused in hydrothermal vent systems where the reducing, heated hydrothermal fluid feeds back into the more oxidizing ocean. Alkaline hydrothermal vents have been proposed as a likely location for the origin of life on the early Earth due to various factors: including the hydrothermal pH / Eh gradients that resemble the ubiquitous electrical / proton gradients in biology, the catalytic hydrothermal precipitates that resemble inorganic catalysts in enzymes, and the presence of electron donors and acceptors in hydrothermal systems (e.g. H2 + CH4 and CO2) that are thought to have been utilized in the earliest metabolisms. Of particular importance for the emergence of metabolism are the mineral "chimneys" that precipitate at the vent fluid / seawater interface. Hydrothermal chimneys are flow-through chemical reactors that form porous and permeable inorganic membranes transecting geochemical gradients; in some ways similar to biological membranes that transect proton / ion gradients and harness these disequilibria to drive metabolism. These emergent chimney structures in the far-from-equilibrium system of the alkaline vent have many properties of interest to the origin of life that can be simulated in the laboratory: for example, they can generate electrical energy and drive redox reactions, and produce catalytic minerals (in particular the metal sulfides and iron oxyhydroxides - "green rust") that can facilitate chemical reactions towards proto-metabolic cycles and biosynthesis. Many of the factors prompting interest in alkaline hydrothermal vents on Earth may also have been present on early Mars, or even presently within icy worlds such as Europa or Enceladus - thus, understanding the disequilibria and resulting prebiotic chemistry in these systems can be of great use in assessing the potential for other environments in the Solar

  20. Solubility of pllutonium in alkaline salt solutions

    SciTech Connect

    Hobbs, D.T.; Edwards, T.B.

    1993-02-26

    Plutonium solubility data from several studies have been evaluated. For each data set, a predictive model has been developed where appropriate. In addition, a statistical model and corresponding prediction intervals for plutonium solubility as a quadratic function of the hydroxide concentration have been developed. Because of the wide range of solution compositions, the solubility of plutonium can vary by as much as three orders of magnitude for any given hydroxide concentration and still remain within the prediction interval. Any nuclear safety assessments that depend on the maximum amount of plutonium dissolved in alkaline salt solutions should use concentrations at least as great as the upper prediction limits developed in this study. To increase the confidence in the prediction model, it is recommended that additional solubility tests be conducted at low hydroxide concentrations and with all of the other solution components involved. To validate the model for application to actual waste solutions, it is recommended that the plutonium solubilities in actual waste solutions be determined and compared to the values predicted by the quadratic model.

  1. Investigation on phase transformation mechanism of zeolite NaY under alkaline hydrothermal conditions

    SciTech Connect

    Li, Peng Ding, Tian Liu, Liping Xiong, Guang

    2013-12-15

    The phase transformation mechanism of zeolite NaY under alkaline hydrothermal conditions was investigated by UV Raman spectroscopy, X-ray diffraction, X-ray fluorescence and scanning electron microscopy techniques. The results revealed that the products and transformation rate are dependent on the alkalinities. All of the starting and resulting zeolites are constructed with the 4-ring and 6-ring secondary building units. The products have lower Si/Al ratio, higher framework density and smaller pore size, which are more stable under alkaline hydrothermal condition. During the phase transformation the fragments of faujasite are formed, then the fragments combine to form different zeolites depending on basicity. Zeolite NaY crystals are consumed as the reservoir for the transformation products during the recrystallization process. For the first time, a 4-membered ring intermediate was found at the early stage of the recrystallization process. A cooperative interaction of liquid and solid phases is required for inducing the phase transformation. - Graphical Abstract: Phase transformation of NaY zeolite under alkaline hydrothermal condition is achieved by the cooperative interaction of the liquid and solid phases. A 4-membered ring species is an intermediate for recrystallization process. Highlights: • The products and transformation rate are dependent on the alkalinity. • A 4-membered ring species is an intermediate for recrystallization process. • A cooperative interaction of liquid and solid phases is required.

  2. Removal of plutonium and americium from alkaline waste solutions

    DOEpatents

    Schulz, Wallace W.

    1979-01-01

    High salt content, alkaline waste solutions containing plutonium and americium are contacted with a sodium titanate compound to effect removal of the plutonium and americium from the alkaline waste solution onto the sodium titanate and provide an effluent having a radiation level of less than 10 nCi per gram alpha emitters.

  3. Chemistry of hydrothermal solutions from Pele's Vents, Loihi Seamount, Hawaii

    SciTech Connect

    Sedwick, P.N.; McMurtry, G.M. ); Macdougall, J.D. )

    1992-10-01

    Hydrothermal fluids were sampled from Pele's Vents on the summit of Loihi Seamount, an intraplate, hotspot volcano, on four occasions from February 1987 to September 1990. The warm ([le]31C) vent solutions are enriched in dissolved Si, CO[sub 2], H[sub 2]S, alkalinity, K[sup +], Li[sup +], Rb[sup +], Ca[sup 2+], Ba[sup 2+], Fe[sup 2+], Mn[sup 2+], NH[sup +][sub 4], and possibly Ni[sup 2+], and depleted in SO[sup 2-][sub 4], O[sub 2], Mg[sup 2+], [sup 87]Sr/[sup 86]Sr, NO[sup -][sub 3], and sometimes Cl[sup -] and Na[sup +] (calculated), relative to ambient seawater. Dissolved Si correlates linearly with sample temperature, suggesting that the solutions sampled from numerous vents in the [approximately]20 m diameter field have a common source and that Si can be used as a conservative tracer for mixing of the vent fluids with ambient seawater. These juvenile inputs likely reflect the shallow, hotspot setting of this hydrothermal system. A simple quantitative fluid-history model is considered and shown to be consistent with mass-balance constraints and saturation-state calculations, which suggest that the Si concentration of the fluids may be controlled by amorphous silica saturation at [approximately]31C. Observed temporal variations in fluid composition between expeditions - specifically, in Cl[sup -], A[sub T], C[sub T], Na[sup +] (calculated), Mg[sup 2+], Ca[sup 2+], Sr[sup 2+], [sup 87]Sr/[sup 86]Sr, Fe[sup 2+], Mn[sup 2+] and perhaps NH[sup +][sub 4], relative to Si - are, excepting Mg[sup 2+], [sup 87]Sr/[sup 86]Sr, and Mn[sup 2+], consistent with the effects of variable phase segregation at the proposed high-temperature endmember.

  4. Resolving the Richat enigma: Doming and hydrothermal karstification above an alkaline complex

    NASA Astrophysics Data System (ADS)

    Matton, Guillaume; Jébrak, Michel; Lee, James K. W.

    2005-08-01

    The Richat structure (Sahara, Mauritania) appears as a large dome at least 40 km in diameter within a Late Proterozoic to Ordovician sequence. Erosion has created circular cuestas represented by three nested rings dipping outward from the structure. The center of the structure consists of a limestone-dolomite shelf that encloses a kilometer-scale siliceous breccia and is intruded by basaltic ring dikes, kimberlitic intrusions, and alkaline volcanic rocks. Several hypotheses have been presented to explain the spectacular Richat structure and breccia, but their origin remains enigmatic. The breccia body is lenticular in shape and irregularly thins at its extremities to only a few meters. The breccia was created during karst dissolution and collapse. Internal sediments fill the centimeter- to meter-scale cavities. Alkaline enrichment and the presence of Cretaceous automorphous neoformed K-feldspar demonstrate the hydrothermal origin of these internal sediments and their contemporaneity with magmatism. A model is proposed in which doming and the production of hydrothermal fluids were instrumental in creating a favorable setting for dissolution. The circular Richat structure and its breccia core thus represent the superficial expression of a Cretaceous alkaline complex with an exceptionally well preserved hydrothermal karst infilling at its summit.

  5. Hydrothermal and alkaline hydrothermal pretreatments plus anaerobic digestion of sewage sludge for dewatering and biogas production: Bench-scale research and pilot-scale verification.

    PubMed

    Li, Chunxing; Wang, Xingdong; Zhang, Guangyi; Yu, Guangwei; Lin, Jingjiang; Wang, Yin

    2017-03-25

    To test the feasibility and practicability of the process combing hydrothermal pretreatment for dewatering with biogas production for full utilization of sewage sludge, hydrothermal/alkaline hydrothermal pretreatments and in turn anaerobic digestion of the filtrates obtained after dewatering the pretreated sludge were performed at bench- and pilot-scales. The hydrothermal temperature fell within the range of 140 °C-220 °C and the pretreatment time varied from 30 min to 120 min. For the alkaline hydrothermal pretreatment the pH value of the sludge was adjusted to 9.0-11.0 by adding Ca(OH)2. The results showed that the dewaterability of the sewage sludge was improved with increasing pretreatment temperature but the impact of the pretreatment time was not significant. The addition of Ca(OH)2 gave better performance on the subsequent mechanical dewatering of the pretreated sludge compared to pure hydrothermal pretreatment, and the higher the pH value was, the better the dewaterability of the pretreated sludge was. The conditions of 180 °C/30 min and 160 °C/60 min/pH = 10.0 (for hydrothermal and alkaline hydrothermal pretreatments, respectively) resulted in relatively good results in the theoretical energy balance, which were verified in the pilot-scale tests. Based on the data from the pilot tests, the alkaline hydrothermal process realized self-sufficiency in energy at the cost of a proper amount of CaO.

  6. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions

    NASA Astrophysics Data System (ADS)

    Shibuya, Takazo; Russell, Michael J.; Takai, Ken

    2016-02-01

    Thermodynamic calculations of mixing between hypothetical seawater and hydrothermal fluid in the Hadean deep ocean were carried out to predict saturation states of mineral precipitates and redox reactions that could occur in Hadean submarine alkaline hydrothermal systems associated with the serpentinization of ultramafic rocks. In the calculations, the seawater was assumed to be weakly acidic (pH = 5.5) and to include carbon dioxide, ferrous iron and silica, with or without nitrate, while the Hadean hydrothermal fluid was assumed to be highly alkaline (pH = 11) and to contain abundant molecular hydrogen, methane and bisulfide, based on the Archean geologic record, the modern low-temperature alkaline hydrothermal vent fluid (Lost City field), and experimental and theoretical considerations. The modeling indicates that potential mineral precipitates in the mixing zone (hydrothermal chimney structures) could consist mainly of iron sulfides but also of ferrous serpentine and brucite, siderite, and ferric iron-bearing minerals such as goethite, hematite and/or magnetite as minor phases. The precipitation of ferric iron-bearing minerals suggests that chemical iron oxidation would be made possible by pH shift even under anoxic condition. In the mixing zone, comprising an inorganic barrier precipitated at the interface of the two contrasting solutions, various redox reactions release free energy with the potential to drive endergonic reactions, assuming the involvement of coupling inorganic protoenzymes. Hydrogenotrophic methanogenesis and acetogenesis - long considered the most ancient forms of biological energy metabolisms - are able to achieve higher maximum energy yield (>0.5 kJ/kg hydrothermal fluid) than those in the modern serpentinization-associated seafloor hydrothermal systems (e.g., Kairei field). Furthermore, the recently proposed methanotrophic acetogenesis pathway was also thermodynamically investigated. It is known that methanotrophic acetogenesis would

  7. Alkaline solution/binder ratio as a determining factor in the alkaline activation of aluminosilicates

    SciTech Connect

    Ruiz-Santaquiteria, C.; Fernandez-Jimenez, A.; Palomo, A.

    2012-09-15

    This study investigates the effect of the alkaline solution/binder (S/B) ratio on the composition and nanostructure of the reaction products generated in the alkaline activation of aluminosilicates. The experiments used two mixtures of fly ash and dehydroxylated white clay and for each of these, varying proportions of the solution components. The alkali activator was an 8 M NaOH solution (with and without sodium silicate) used at three S/B ratios: 0.50, 0.75 and 1.25. The {sup 29}Si, {sup 27}Al MAS NMR and XRD characterisation of the reaction products reveal that for ratios nearest the value delivering suitable paste workability, the reaction-product composition and structure depend primarily on the nature and composition of the starting materials and the alkaline activator used. However, when an excess alkaline activator is present in the system, the reaction products tend to exhibit SiO{sub 2}/Al{sub 2}O{sub 3} ratios of approximately 1, irrespective of the composition of the starting binder or the alkaline activator.

  8. Alkaline solution absorption of carbon dioxide method and apparatus

    DOEpatents

    Hobbs, D.T.

    1991-01-01

    Disclosed is a method for measuring the concentration of hydroxides (or pH) in alkaline solutions, using the tendency of hydroxides to adsorb CO{sub 2}. The method comprises passing CO{sub 2} over the surface of an alkaline solution in a remote tank before and after measurements of the CO{sub 2} concentration. Comparison of the measurements yields the adsorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to adsorption fraction. A schematic is given of a process system according to a preferred embodiment of the invention. 2 figs.

  9. Alkaline hydrothermal conversion of fly ash filtrates into zeolites 2: utilization in wastewater treatment.

    PubMed

    Somerset, Vernon; Petrik, Leslie; Iwuoha, Emmanuel

    2005-01-01

    Filtrates were collected using a codisposal reaction wherein fly ash was reacted with acid mine drainage. These codisposal filtrates were then analyzed by X-ray Fluorescence spectrometry for quantitative determination of the SiO2 and Al2O3 content. Alkaline hydrothermal zeolite synthesis was then applied to the filtrates to convert the fly ash material into zeolites. The zeolites formed under the experimental conditions were faujasite, sodalite, and zeolite A. The use of the fly ash-derived zeolites and a commercial zeolite was explored in wastewater decontamination experiments as it was applied to acid mine drainage in different dosages. The concentrations of Ni, Zn, Cd, As, and Pb metal ions in the treated wastewater were investigated. The results of the treatment of the acid mine drainage with the prepared fly ash zeolites showed that the concentrations of Ni, Zn, Cd, and Hg were decreased as the zeolite dosages of the fly ash zeolite (FAZ1) increased.

  10. An origin-of-life reactor to simulate alkaline hydrothermal vents.

    PubMed

    Herschy, Barry; Whicher, Alexandra; Camprubi, Eloi; Watson, Cameron; Dartnell, Lewis; Ward, John; Evans, Julian R G; Lane, Nick

    2014-12-01

    Chemiosmotic coupling is universal: practically all cells harness electrochemical proton gradients across membranes to drive ATP synthesis, powering biochemistry. Autotrophic cells, including phototrophs and chemolithotrophs, also use proton gradients to power carbon fixation directly. The universality of chemiosmotic coupling suggests that it arose very early in evolution, but its origins are obscure. Alkaline hydrothermal systems sustain natural proton gradients across the thin inorganic barriers of interconnected micropores within deep-sea vents. In Hadean oceans, these inorganic barriers should have contained catalytic Fe(Ni)S minerals similar in structure to cofactors in modern metabolic enzymes, suggesting a possible abiotic origin of chemiosmotic coupling. The continuous supply of H2 and CO2 from vent fluids and early oceans, respectively, offers further parallels with the biochemistry of ancient autotrophic cells, notably the acetyl CoA pathway in archaea and bacteria. However, the precise mechanisms by which natural proton gradients, H2, CO2 and metal sulphides could have driven organic synthesis are uncertain, and theoretical ideas lack empirical support. We have built a simple electrochemical reactor to simulate conditions in alkaline hydrothermal vents, allowing investigation of the possibility that abiotic vent chemistry could prefigure the origins of biochemistry. We discuss the construction and testing of the reactor, describing the precipitation of thin-walled, inorganic structures containing nickel-doped mackinawite, a catalytic Fe(Ni)S mineral, under prebiotic ocean conditions. These simulated vent structures appear to generate low yields of simple organics. Synthetic microporous matrices can concentrate organics by thermophoresis over several orders of magnitude under continuous open-flow vent conditions.

  11. The production of glucose from corn stalk using hydrothermal process with pre-treatment ultrasound assisted alkaline

    NASA Astrophysics Data System (ADS)

    Yolanda, Dora; Prasutiyo, Indry; Trisanti, P. N.; Sumarno

    2015-12-01

    The production of glucose from corn stalk by using subcritical hydrothermal technology is studied in this work. Ultrasound-assisted alkaline delignification methods are used as pre-treatment. The corn stalk powder were pretreated with ultrasound-assisted alkaline (NaOH 2% w/w, solid to liquid ratio 1:22 w/v) at room temperature and 30 minutes. After pre-treatment, solid residue and liquid fractions are separated by filtration. Pretreated solids are further submitted to hydrothermal process for glucose production. Hydrothermal process was carried out at 100 Bar and 120°C in various times. The solid product was characterized by SEM and XRD. And liquid product was analysis using DNS method to determine percentage of glucose. From XRD analysis showed that crystallinity of material was lower than delignification product.

  12. Dynamic formation of zeolite synthesized from fly ash by alkaline hydrothermal conversion.

    PubMed

    Zhang, ZhiJian; Li, Jiangli; Li, Hongyi; Wang, Hang; Zhu, Jun; He, Qiang

    2013-11-01

    This study was designed to characterize the dynamic formation of zeolite synthesized from fly ash (ZFA) and to identify the zeolitization mechanisms during a 160-h-long hydrothermal alkaline conversion at 95°C by using fly ash (FA) samples collected from four typical thermoelectric power plants in China, with the purpose of improving ZFA quality. The process of synthesizing ZFA can be fundamentally divided into five stages: induction stage (0-0.5 h), accelerating dissolution stage (0.5-12 h), nucleation and/or crystallization stage (12-24 h), crystal growth stage (24-72 h) and crystal transformation stage (72-160 h). The crystal growth stage determined the quality of zeolite crystallization, coupled with functions of re-assembling the silicon-aluminium tetrahedral network and developing submicro- and/or nanometer microstructure. A 48-h-long hydrothermal conversion generated ZFAs that had a greater specific surface area (26.0-89.4 times) and cation exchange capacity (29.6-71.0 times) than FA, which successfully sequestrated 41-95% of ammonium and 75-98% of phosphate from swine manure. However, over-reaction resulted in more stable hydroxysodalite and/or sodalite, surface agglomeration and cracking, and energy wasting. This work suggests that the reuse of recycled synthesis materials should occur during the fourth step (24-72 h).

  13. Structural elucidation of sorghum lignins from an integrated biorefinery process based on hydrothermal and alkaline treatments.

    PubMed

    Sun, Shao-Long; Wen, Jia-Long; Ma, Ming-Guo; Sun, Run-Cang

    2014-08-13

    An integrated process based on hydrothermal pretreatment (HTP) (i.e., 110-230 °C, 0.5-2.0 h) and alkaline post-treatment (2% NaOH at 90 °C for 2.0 h) has been performed for the production of xylooligosaccharide, lignin, and digestible substrate from sweet sorghum stems. The yield, purity, dissociation mechanisms, structural features, and structural transformations of alkali lignins obtained from the integrated process were investigated. It was found that the HTP process facilitated the subsequent alkaline delignification, releasing lignin with the highest yield (79.3%) and purity from the HTP residue obtained at 190 °C for 0.5 h. All of the results indicated that the cleavage of the β-O-4 linkages and degradation of β-β and β-5 linkages occurred under the harsh HTP conditions. Depolymerization and condensation reactions simultaneously occurred at higher temperatures (≥ 170 °C). Moreover, the thermostability of lignin was positively related to its molecular weight, but was also affected by the inherent structures, such as β-O-4 linkages and condensed units. These findings will enhance the understanding of structural transformations of the lignins during the integrated process and maximize the potential utilizations of the lignins in a current biorefinery process.

  14. Solubility of plutonium and uranium in alkaline salt solutions

    SciTech Connect

    Hobbs, D.T.; Edwards, T.B.; Fleischman, S.D.

    1993-02-12

    The solubility of plutonium and uranium in alkaline salt solutions, which will be processed in the In-Tank Precipitation (ITP) process, was investigated to screen for significant factors and interactions among the factors comprising the salt solutions. The factors included in the study were hydroxide, nitrate, nitrite, aluminate, sulfate, carbonate, and temperature. Over the range of factor concentrations studied, the level of hydroxide in the solution is not sufficient alone to predict the resulting concentration of plutonium and uranium in the solution. Other constituents of the salt solution play an important role in determining the amount of plutonium and uranium in solution. Statistical models predicting the plutonium and uranium concentrations over the range of salt solutions investigated are provided.

  15. Improved spectrophotometric cell for hydrothermal solutions

    USGS Publications Warehouse

    Susak, N.J.; Crerar, D.A.; Forseman, T.C.; Haas, J.L.

    1981-01-01

    A simple, inexpensive spectrophotometric cell was designed for use with aqueous solutions for which temperature is a maximum of 325??C and pressure, 28 MPa. The cell has an internal volume of 5 ml and a path length of 1.31 cm. Each furnace assembly is 120 mm in diameter ?? 150 mm high and will fit into most commercial spectrophotometers. Temperature is controlled by a standard set-point controller and a balancing circuit that is used to maintain the temperature of the sample and reference cell within 1??C of each other at any temperature.

  16. Thiomethylation of ketones by sulphide-alkaline solutions and formaldehyde

    SciTech Connect

    Ulendeyeva, A.D.; Samigullin, I.I.; Nasteka, V.I.

    1993-12-31

    An investigation has been made of the thiomethylation of ketones by formaldehyde with mercaptides, sodium sulphide and their mixture. It is possible to regenerate 78-100 rel.% of the sulphide-alkaline solutions under mild conditions (20-50{degrees}C, atmospheric pressure) without feeding a catalyst, with the simultaneous production of ketosulphide concentrate - a less toxic product with properties of practical benefit. 7 refs., 2 figs., 2 tabs.

  17. Alkaline hydrothermal conversion of fly ash precipitates into zeolites 3: the removal of mercury and lead ions from wastewater.

    PubMed

    Somerset, Vernon; Petrik, Leslie; Iwuoha, Emmanuel

    2008-04-01

    In this paper, the utilisation of zeolites synthesised from fly ash (FA) and related co-disposal filtrates as low-cost adsorbent material were investigated. When raw FA and co-disposal filtrates were subjected to alkaline hydrothermal zeolite synthesis, the zeolites faujasite, sodalite and zeolite A were formed. The synthesised zeolites were explored to establish its ability to remove lead and mercury ions from aqueous solution in batch experiments, to which various dosages of the synthesised zeolites were added. The test results indicated that when increasing synthesised zeolite dosages of 5-20 g/L were added to the acid mine drainage (AMD) wastewater, the concentrations of lead and mercury in the wastewater were reduced accordingly. The lead concentrations were reduced from 3.23 to 0.38 and 0.17 microg/kg, respectively, at an average pH of 4.5, after the addition of raw FA zeolite and co-disposal filtrate zeolite to the AMD wastewater. On the other hand, the mercury concentration was reduced from 0.47 to 0.17 microg/kg at pH=4.5 when increasing amounts of co-disposal filtrate zeolite were added to the wastewater. The experimental results had shown that the zeolites synthesised from the co-disposal filtrates were effective in reducing the lead and mercury concentrations in the AMD wastewater by 95% and 30%, respectively.

  18. Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

    PubMed

    Chi, Quan; Chen, Wanying; He, Zhike

    2015-11-01

    The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution.

  19. Mobilization of Manufactured Gas Plant Tar with Alkaline Flushing Solutions

    PubMed Central

    Hauswirth, Scott C.; Birak, Pamela Schultz; Rylander, Seth C.; Miller, Cass T.

    2011-01-01

    This experimental study investigates the use of alkaline and alkaline-polymer solutions for the mobilization of former manufactured gas plant (FMGP) tars. Tar-aqueous interfacial tensions (IFTs) and contact angles were measured, and column flushing experiments were conducted. NaOH solutions (0.01–1 wt.%) were found to significantly reduce tar-aqueous IFT. Contact angles indicated a shift to strongly water-wet, then to tar-wet conditions as NaOH concentration increased. Column experiments were conducted with flushing solutions containing 0.2, 0.35, and 0.5% NaOH, both with and without xanthan gum (XG). Between 10 and 44% of the residual tar was removed by solutions containing only NaOH, while solutions containing both NaOH and XG removed 81–93% of the tar with final tar saturations as low as 0.018. The mechanism responsible for the tar removal is likely a combination of reduced IFT, a favorable viscosity ratio, and tar bank formation. Such an approach may have practical applications and would be significantly less expensive than surfactant-based methods. PMID:22091957

  20. Low-temperature hydrothermal synthesis of ZnO nanorods: Effects of zinc salt concentration, various solvents and alkaline mineralizers

    SciTech Connect

    Edalati, Khatereh; Shakiba, Atefeh; Vahdati-Khaki, Jalil; Zebarjad, Seyed Mojtaba

    2016-02-15

    Highlights: • We synthesized ZnO nanorods by a simple hydrothermal process at 60 °C. • Effects of zinc salt concentration, solvent and alkaline mineralizer was studied. • Increasing concentration of zinc salt changed ZnO nucleation system. • NaOH yielded better results in the production of nanorods in both solvents. • Methanol performed better in the formation of nanorods using the two mineralizers. - Abstract: ZnO has been produced using various methods in the solid, gaseous, and liquid states, and the hydrothermal synthesis at low temperatures has been shown to be an environmentally-friendly one. The current work utilizes a low reaction temperature (60 °C) for the simple hydrothermal synthesis of ZnO nanorod morphologies. Furthermore, the effects of zinc salt concentration, solvent type and alkaline mineralizer type on ZnO nanorods synthesis at a low reaction temperature by hydrothermal processing was studied. Obtained samples were analyzed using X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Increasing the concentration of the starting zinc salt from 0.02 to 0.2 M changed ZnO nucleation system from the homogeneous to the heterogeneous state. The XRD results confirmed the production hexagonal ZnO nanostructures of with a crystallite size of 40.4 nm. Varying the experimental parameters (mineralizer and solvent) yielded ZnO nanorods with diameters ranging from 90–250 nm and lengths of 1–2 μm.

  1. Alkaline deoxygenated graphene oxide as adsorbent for cadmium ions removal from aqueous solutions.

    PubMed

    Liu, Jun; Du, Hongyan; Yuan, Shaowei; He, Wanxia; Yan, Pengju; Liu, Zhanhong

    2015-01-01

    Alkaline deoxygenated graphene oxide (aGO) was prepared through alkaline hydrothermal treatment and used as adsorbent to remove Cd(II) ions from aqueous solutions for the first time. The characterization results of transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and Fourier transform infrared (FT-IR) spectra indicate that aGO was successfully synthesized. The batch adsorption experiments showed that the adsorption kinetics could be described by the pseudo-second-order kinetic model, and the isotherms equilibrium data were well fitted with the Langmuir model. The maximum adsorption capacity of Cd(II) on aGO was 156 mg/g at pH 5 and T=293 K. The adsorption thermodynamic parameters indicated that the adsorption process was a spontaneous and endothermic reaction. The mainly adsorption mechanism speculated from FT-IR results may be attributed to the electrostatic attraction between Cd2+ and negatively charged groups (-CO-) of aGO and cation-π interaction between Cd2+ and the graphene planes. The findings of this study demonstrate the potential utility of the nanomaterial aGO as an effective adsorbent for Cd(II) removal from aqueous solutions.

  2. Electrochemical behavior of immobilized hemoglobin in alkaline solution

    NASA Astrophysics Data System (ADS)

    Jović-Jovičić, Nataša; Mojović, Zorica; Mojović, Miloš; Banković, Predrag; Ajduković, Marija; Milutinović-Nikolić, Aleksandra; Jovanović, Dušan

    2017-04-01

    Glassy carbon electrode was modified with different synthesized hybrid clay-based materials and tested in alkaline solution with and without H2O2. The hybrid materials were obtained by immobilizing hemoglobin (Hb) on acid activated (AA) clay, or on AA clay modified with different sodium dodecyl sulfate (SDS) loadings. The obtained materials were characterized using DR UV-vis and ESR spectroscopy, elemental analysis, and SEM. The characterization confirmed higher degree of hemoglobin incorporation in the presence of SDS. The presence of SDS on the surface of clay particles resulted in the partial oxidation/denaturation of hemoglobin and formation of hemichrome. Cyclic voltammetry was used for the investigation of the electrochemical behavior of immobilized hemoglobin in alkaline solution. Two cathodic peaks at -0.45 V and -0.70 V were recorded and ascribed to the reduction of heme Fe(III)/Fe(II), and formation of HbFe(I) - highly reduced form of hemoglobin - respectively. The latter peak reflects hemoglobin denaturation. The presence of H2O2 in the alkaline solution increased current intensities corresponding to both peaks (-0.45 V and -0.7 V). Linear response of peak current intensity vs. H2O2 concentration was monitored for all investigated samples within different H2O2 concentration ranges. The AA-SDS1.0-Hb electrode exhibited the highest current response with linear regression equation in the following form: I(μA) = 7.99 + 1.056 × [H2O2] (mM) (R = 0.996). The limit of detection of 28 μM was estimated using the 3 sigma method. Different modified electrodes exhibited different degrees of denaturation resistance. The obtained values of Michaelis-Menten constant indicated that prolonged cycling in the presence of SDS increases protein denaturation.

  3. Modification of FGD gypsum in hydrothermal mixed salt solution.

    PubMed

    Wu, Xiao-Qin; Wu, Zhong-Biao

    2006-01-01

    A novel utilization way of the sludge from wet calcium-based flue gas desulfurization (FGD) processes has been developed in this paper. This study focused on the conversion of the FGD gypsum into alpha-hemihydrate calcium sulfate by a hydrothermal salt solution method at atmospheric pressure. Experimental study has been carried out in a batch reactor. Qualitative and quantitative analyses were made by DSC/TG thermal analysis, SEM, XRD, metalloscope and chemical analysis. The experimental results showed that the modification of FGD gypsum was controlled by the dissolution and recrystallization mechanisms. With the introduction of FGD gypsum the salt solution was supersaturated, then crystal nucleus of alpha-hemihydrate calcium sulfate were produced in the solution. With the submicroscopic structure of FGD gypsum crystal changed, the crystal nucleus grew up into alpha-hemihydrate calcium sulfate crystals. Thus, the modification of FGD gypsum was fulfilled.

  4. Corrosion of silicon nitride in high temperature alkaline solutions

    NASA Astrophysics Data System (ADS)

    Qiu, Liyan; Guzonas, Dave A.; Qian, Jing

    2016-08-01

    The corrosion of silicon nitride (Si3N4) in alkaline solutions was studied at temperatures from 60 to 300 °C. Si3N4 experienced significant corrosion above 100 °C. The release rates of silicon and nitrogen follow zero order reaction kinetics and increase with increasing temperature. The molar ratio of dissolved silicon and nitrogen species in the high temperature solutions is the same as that in the solid phase (congruent dissolution). The activation energy for silicon and nitrogen release rates is 75 kJ/mol which agrees well with that of silica dissolution. At 300 °C, the release of aluminum is observed and follows first order reaction kinetics while other minor constituents including Ti and Y are highly enriched on the corrosion films due to the low solubility of their oxides.

  5. Mercury(II) Penicillamine Complex Formation in Alkaline Aqueous Solution

    SciTech Connect

    Leung, B.O.; Jalilehvand, F.; Mah, V.

    2009-06-01

    The complex formation between mercury(II) and penicillamine (H{sub 2}Pen = 3,3'-dimethyl cysteine) in alkaline aqueous solutions (pH {approx}2) has been investigated with extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy. By varying the penicillamine concentration (C{sub H{sub 2}Pen} = 0.2--1.25 M) in {approx}0.1 M Hg(II) solutions, two coexisting major species [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sub 4-} were characterized with mean Hg-S bond distances 2.34(2) and 2.44(2) {angstrom}, respectively. The [Hg(Pen){sub 2}]{sup 2-} complex with two deprotonated penicillamine ligands forms an almost linear S-Hg-S entity with two weak chelating Hg-N interactions at the mean Hg-N distance 2.52(2) {angstrom}. The same type of coordination is also found for the corresponding [Hg(Cys){sub 2}]{sup 2-} complex in alkaline aqueous solution with the mean bond distances Hg-S 2.34(2) {angstrom} and Hg-N 2.56(2) {angstrom}. The relative amounts of the [Hg(Pen){sub 2}]{sup 2-} and [Hg(Pen){sub 3}]{sup 4-} complexes were estimated by fitting linear combinations of the EXAFS oscillations to the experimental spectra. Also their {sup 199}Hg NMR chemical shifts were used to evaluate the complex formation, showing that the [Hg(Pen){sub 3}]{sup 4-} complex dominates already at moderate excess of the free ligand ([Pen{sup 2-}] > {approx} 0.1 M).

  6. Massive sulfide deposits and hydrothermal solutions: incremental reaction modeling of mineral precipitation and sulfur isotopic evolution

    SciTech Connect

    Janecky, D.R.

    1986-01-01

    Incremental reaction path modeling of chemical and sulfur isotopic reactions occurring in active hydrothermal vents on the seafloor, in combination with chemical and petrographic data from sulfide samples from the seafloor and massive sulfide ore deposits, allows a detailed examination of the processes involved. This paper presents theoretical models of reactions of two types: (1) adiabatic mixing between hydrothermal solution and seawater, and (2) reaction of hydrothermal solution with sulfide deposit materials. In addition, reaction of hydrothermal solution with sulfide deposit minerals and basalt in feeder zones is discussed.

  7. Properties of hydroxyapatite crystallized from high temperature alkaline solutions

    NASA Astrophysics Data System (ADS)

    Lazić, S.; Katanić-Popović, J.; Zec, S.; Miljević, N.

    1996-07-01

    Hydroxyapatite was prepared from alkaline solutions at 95°C by the method of slow titration in an atmosphere of nitrogen. The crystals were ripened under reflux for various periods of time, and then characterized by X-ray diffraction, infrared analysis, transmission electron microscopy, differential thermal analysis, thermogravimetric analysis, surface area measurements and chemical analysis. The obtained crystals are pure apatites with stoichiometric {Ca}/{P} ratio. The phase composition of the prepared powders remains unchanged after heating at 900°C during 2 h. The lattice constants of maturated powders were in excellent agreement with ASTM 9-432 diffraction file data for the hydrohxyapatite. Ripening under reflux improved lattice ordering but did not have a marked effect on the {Ca}/{P} ratio. Crystallite size and morphology significantly changed during the first day of refluxing following synthesis.

  8. Metal adsorbent for alkaline etching aqua solutions of Si wafer

    NASA Astrophysics Data System (ADS)

    Tamada, Masao; Ueki, Yuji; Seko, Noriaki; Takeda, Toshihide; Kawano, Shin-ichi

    2012-08-01

    High performance adsorbent is expected to be synthesized for the removal of Ni and Cu ions from strong alkaline solution used in the surface etching process of Si wafer. Fibrous adsorbent was synthesized by radiation-induce emulsion graft polymerization onto polyethylene nonwoven fabric and subsequent amination. The reaction condition was optimized using 30 L reaction vessel and nonwoven fabric, 0.3 m width and 18 m long. The resulting fibrous adsorbent was evaluated by 48 wt% NaOH and KOH contaminated with Ni and Cu ions, respectively. The concentration levels of Ni and Cu ions was reduced to less than 1 μg/kg (ppb) at the flow rate of 10 h-1 in space velocity. The life of adsorbent was 30 times higher than that of the commercialized resin. This novel adsorbent was commercialized as METOLATE® since the ability of adsorption is remarkably higher than that of commercial resin used practically in Si wafer processing.

  9. Experimental investigation of As, Sb and Cs behavior during olivine serpentinization in hydrothermal alkaline systems

    NASA Astrophysics Data System (ADS)

    Lafay, Romain; Montes-Hernandez, German; Janots, Emilie; Munoz, Manuel; Auzende, Anne Line; Gehin, Antoine; Chiriac, Rodica; Proux, Olivier

    2016-04-01

    While Fluid-Mobile Elements (FMEs) such as B, Sb, Li, As or Cs are particularly concentrated in serpentinites, data on FME fluid-serpentine partitioning, distribution, and sequestration mechanisms are missing. In the present experimental study, the behavior of Sb, As and Cs during San Carlos olivine serpentinization was investigated using accurate mineralogical, geochemical, and spectroscopic characterization. Static-batch experiments were conducted at 200 °C, under saturated vapor pressure (≈1.6 MPa), for initial olivine grain sizes of <30 μm (As), 30-56 μm (As, Cs, Sb) and 56-150 μm (Cs) and for periods comprised between 3 and 90 days. High-hydroxyl-alkaline fluid enriched with 200 mg L-1 of a single FME was used and a fluid/solid weight ratio of 15. For these particular conditions, olivine is favorably replaced by a mixture of chrysotile, polygonal serpentine and brucite. Arsenic, Cs or Sb reaction product content was determined as a function of reaction advancement for the different initial olivine grain sizes investigated. The results confirm that serpentinization products have a high FME uptake capacity with the partitioning coefficient increasing such as CsDp/fl = 1.5-1.6 < AsDp/fl = 3.5-4.5 < SbDp/fl = 28 after complete reaction of the 30-56 μm grain-sized olivine. The sequestration pathways of the three elements are however substantially different. While the As partition coefficient remains constant throughout the serpentinization reaction, the Cs partition coefficient decreases abruptly in the first stages of the reaction to reach a constant value after the reaction is 40-60% complete. Both As and Cs partitioning appear to decrease with increasing initial olivine grain size, but there is no significant difference in the partitioning coefficient between the 30-56 and 56-150 μm grain size after complete serpentinization. X-ray absorption spectroscopy (XAS) measurements combined with X-ray chemical measurements reveal that the As(V) is mainly

  10. Cu(II) complex formation with xylitol in alkaline solutions.

    PubMed

    Norkus, Eugenijus; Vaiciūniene, Jūrate; Vuorinen, Tapani; Gaidamauskas, Ernestas; Reklaitis, Jonas; Jääskeläinen, Anna-Stiina; Crans, Debbie C

    2004-02-25

    The formation of four Cu(II)-xylitol complexes was observed in aqueous alkaline solutions (11.0< or =pH< or =14.0, I=1.0, 20 degrees C) by means of direct current polarography and VIS spectrophotometry. Mononuclear hydroxy complexes, CuXyl(OH)- (log beta=17.7 +/- 0.5), CuXyl(OH)2(2-) (log beta=20.2 +/- 0.3) and CuXyl2(OH)2(4-) (log beta=22.4 +/- 0.3), are formed at high ligand-to-metal ratios (L:M> or =10), whereas dinuclear complex Cu2Xyl (log beta=29.2 +/- 0.3) is the predominant species at low ligand-to-metal ratio (L:M=0.5). Diffusion coefficients and molar absorptivities of the complex species were determined. pH variable 13C NMR suggested that pKa values of xylitol are rather similar and equal to 13.8 +/- 0.2, 13.9 +/- 0.1 and 13.9 +/- 0.2 for OH-groups adjacent to (C-1,C-5), (C-3) and (C-2,C-4) carbon atoms, respectively.

  11. Hydrothermal Carbonization: a feasible solution to convert biomass to soil?

    NASA Astrophysics Data System (ADS)

    Tesch, Walter; Tesch, Petra; Pfeifer, Christoph

    2013-04-01

    The erosion of fertile soil is a severe problem arising right after peak oil (Myers 1996). That this issue is not only a problem of arid countries is shown by the fact that even the European Commission defined certain milestones to address the problem of soil erosion in Europe (European Commission 2011). The application of bio-char produced by torrefaction or pyrolysis for the remediation, revegetation and restoration of depleted soils started to gain momentum recently (Rillig 2010, Lehmann 2011, Beesley 2011). Hydrothermal carbonization (HTC) is a promising thermo-chemical process that can be applied to convert organic feedstock into fertile soil and water, two resources which are of high value in regions being vulnerable to erosion. The great advantage of HTC is that organic feedstock (e.g. organic waste) can be used without any special pretreatment (e.g. drying) and so far no restrictions have been found regarding the composition of the organic matter. By applying HTC the organic material is processed along a defined pathway in the Van Krevelen plot (Behrendt 2006). By stopping the process at an early stage a nutritious rich material can be obtained, which is known to be similar to terra preta. Considering that HTC-coal is rich in functional groups and can be derived from the process under "wet" conditions, it can be expected that it shall allow soil bacteria to settle more easily compared to the bio-char derived by torrefaction or pyrolysis. In addition, up to 10 tons process water per ton organic waste can be gained (Vorlop 2009). Thus, as organic waste, loss of fertile soil and water scarcity becomes a serious issue within the European Union, hydrothermal carbonization can provide a feasible solution to address these issues of our near future. The presentation reviews the different types of feedstock investigated for the HTC-Process so far and gives an overview on the current stage of development of this technology. References Beesley L., Moreno-Jiménez E

  12. Abiotic Synthesis of Methane Under Alkaline Hydrothermal Conditions: the Effect of pH in Heterogeneous Catalysis

    NASA Astrophysics Data System (ADS)

    Foustoukos, D. I.; Qi, F.; Seyfried, W. E.

    2004-12-01

    Abiotic formation of methane in hydrothermal reaction zones at mid-ocean ridges likely occurs by Fischer-Tropsch catalytic processes involving reaction of CO2-bearing fluids with mineral surfaces. The elevated concentrations of dissolved methane and low molecular weight hydrocarbons observed in high temperature vent fluids issuing from ultramafic-hosted hydrothermal systems, in particular, suggest that Fe and Cr-bearing mineral phases attribute as catalysts, enhancing abiotic production of alkanes. The chemi-adsorption of dissolved CO2 on the catalytic mineral surface, however, might be influenced by a pH dependent surface electron charge developed within the mineral-fluid interface. Thus, a series of experiments was conducted to evaluate the role of pH on rates of carbon reduction in fluids coexisting with Fe-oxides at 390 degree C and 400 bars. At two distinct pH conditions, acidic (pH = 5) and alkaline (pH = 8.8), the abiotic production of isotopically labelled CH4(aq) was monitored during FeO reaction with aqueous NaCl-NaHCO3-H2-bearing fluid (0.56 mol/kg NaCl, 0.03 mol/kg NaH13CO3). Despite the lower H2(aq) concentrations (120 mmol/kg) in the high pH system, concentrations of abiogenic methane attained values of 195 umol/kg and 120 umol/kg respectively, suggesting enhanced catalytic properties of mineral under moderately high pH. X-ray photoelectron spectroscopy (XPS), performed on unreacted and final solid products, reveal the significantly greater abundances of alkyl (C-C-) groups on the surface of FeO oxidized at elevated pH, in comparison with mineral reacted at low pH conditions. Thus, enhanced adsorption of dissolved CO2 and the resulting Fischer-Tropsch formation of alkyl groups likely contributes to methane production observed at alkaline conditions. Introducing the effect of pH in the Fischer-Tropsch mechanism of alkane formation has important implications for the recently discovered Lost City ultramafic-hosted hydrothermal system, where elevated p

  13. Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw

    PubMed Central

    Chen, Xue; Li, Hanyin; Sun, Shaoni; Cao, Xuefei; Sun, Runcang

    2016-01-01

    Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120–200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4′, β-β′, β-5′ linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature. PMID:27982101

  14. Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw

    NASA Astrophysics Data System (ADS)

    Chen, Xue; Li, Hanyin; Sun, Shaoni; Cao, Xuefei; Sun, Runcang

    2016-12-01

    Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120–200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4‧, β-β‧, β-5‧ linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature.

  15. Decomposition Studies of Triphenylboron, Diphenylborinic Acid and Phenylboric Acid in Aqueous Alkaline Solutions Containing Copper

    SciTech Connect

    Crawford, C.L.; Peterson, R. A.

    1997-02-11

    This report documents the copper-catalyzed chemical kinetics of triphenylboron, diphenylborinic acid and phenylboric acid (3PB, 2PB and PBA) in aqueous alkaline solution contained in carbon-steel vessels between 40 and 70 degrees C.

  16. Development of alkaline solution separations for potential partitioning of used nuclear fuels

    SciTech Connect

    Jarvinen, Gordon D; Runde, Wolfgang H; Goff, George S

    2009-01-01

    The processing of used nuclear fuel in alkaline solution provides potentially useful new selectivity for separating the actinides from each other and f rom the fission products. Over the ast decade, several research teams around the world have considered dissolution of used fuel in alkaline solution and further partitioning in this medium as an alternative to acid dissolution. The chemistry of the actinides and fission products in alkaline soilltion requires extensive investigation to more carefully evaluate its potential for developing useful separation methods for used nuclear fueI.

  17. Titrimetric determination of hydrogen peroxide in alkaline solution.

    PubMed

    McCurdy, W H; Bell, H F

    1966-07-01

    Direct titration of hydrogen peroxide in alkaline bromide media has been accomplished with sodium hypochlorite. The relative standard deviation is 0.2%. A photometric end-point is recommended for the determination of 0.10-1.0 mequiv of peroxide. Larger samples are evaluated by use of Bordeaux Red as visual indicator. The hypochlorite procedure compares favourably with iodometry and permanganate in the analysis of commercial peroxides.

  18. Upwelling of hydrothermal solutions through ridge flank sediments shown by pore water profiles

    SciTech Connect

    Maris, C.R.P.; Bender, M.L.

    1982-05-07

    High calcium ion and low magnesium ion concentrations in sediment pore waters in cores from the Galapagos Mounds Hydrothermal Field on the flank of the Galapagos Spreading Center are believed to be due to a calcium-magnesium exchange reaction between circulating seawater and basement basalt. The nonlinearity of the calcium ions and magnesium ion gradients indicates that these discharging hydrothermal solutions on the ridge flank are upwelling at the rate of about 1 centimeter per year through the pelagic sediments of the Mounds Field and at about 20 centimeters per year through the hydrothermal mounds themselves.

  19. The alkaline solution to the emergence of life: energy, entropy and early evolution.

    PubMed

    Russell, Michael J

    2007-01-01

    The Earth agglomerates and heats. Convection cells within the planetary interior expedite the cooling process. Volcanoes evolve steam, carbon dioxide, sulfur dioxide and pyrophosphate. An acidulous Hadean ocean condenses from the carbon dioxide atmosphere. Dusts and stratospheric sulfurous smogs absorb a proportion of the Sun's rays. The cooled ocean leaks into the stressed crust and also convects. High temperature acid springs, coupled to magmatic plumes and spreading centers, emit iron, manganese, zinc, cobalt and nickel ions to the ocean. Away from the spreading centers cooler alkaline spring waters emanate from the ocean floor. These bear hydrogen, formate, ammonia, hydrosulfide and minor methane thiol. The thermal potential begins to be dissipated but the chemical potential is dammed. The exhaling alkaline solutions are frustrated in their further attempt to mix thoroughly with their oceanic source by the spontaneous precipitation of biomorphic barriers of colloidal iron compounds and other minerals. It is here we surmise that organic molecules are synthesized, filtered, concentrated and adsorbed, while acetate and methane--separate products of the precursor to the reductive acetyl-coenzyme-A pathway-are exhaled as waste. Reactions in mineral compartments produce acetate, amino acids, and the components of nucleosides. Short peptides, condensed from the simple amino acids, sequester 'ready-made' iron sulfide clusters to form protoferredoxins, and also bind phosphates. Nucleotides are assembled from amino acids, simple phosphates carbon dioxide and ribose phosphate upon nanocrystalline mineral surfaces. The side chains of particular amino acids register to fitting nucleotide triplet clefts. Keyed in, the amino acids are polymerized, through acid-base catalysis, to alpha chains. Peptides, the tenuous outer-most filaments of the nanocrysts, continually peel away from bound RNA. The polymers are concentrated at cooler regions of the mineral compartments through

  20. Hydrothermal Solute Flux from Ebeko Volcanic Center, Paramushir, Kuril Islands

    NASA Astrophysics Data System (ADS)

    Taran, Y.; Kalacheva, E.; Kotenko, T.; Chaplygin, I.

    2014-12-01

    Ebeko volcano on the northern part of Paramushir Island, Northern Kurils, is characterized by frequent phreatic eruptions, a strong low-temperature fumarolic activity at the summit and was the object of comprehensive volcanological and geochemical studies during the last half a century. The volcanic center is composed of several Pleistocene volcanic structures aadjacent to Ebeko and hosts a hydrothermal system with a high outflow rate of hot SO4-Cl acidic water (Upper Yurieva springs) with the current maximum temperature of ~85oC, pH 1.3 and TDS ~ 10 g/L. All discharging thermal waters are drained by the Yurieva River to the Sea of Okhotsk. The hot springs have been changing in time, generally decreasing their activity from near boiling in 1960s, with TDS ~ 20 g/L and the presence of a small steaming field at the upper part of the ~ 700 m long discharging area, to a much lower discharge rate of main vents, lower temperature and the absence of the steaming ground. The spring chemistry did not react to the Ebeko volcanic activity (14 strong phreato-magmatic events during the last 60 years).The total measured outputs of chloride and sulfur from the system last time (2006-2010) were estimated on average as 730 g/s and 980 g/s, respectively, which corresponds to the equivalent fluxes of 64 t/d of HCl and 169 t/d of SO2. These values are higher than the fumarolic volatile output from Ebeko. The estimated discharge rate of hot (85oC) water from the system with ~ 3500 ppm of chloride is about 0.3 m3/s which is much higher than the thermal water discharge from El Chichon or Copahue volcano-hydrothermal systems and among the highest hot water natural outputs ever measured for a volcano-hydrothermal system. We also report the chemical composition (major and ~ 60 trace elements including REE) of water from the main hot spring vents and the Yurieva river mouth.

  1. Vapor-liquid partitioning of alkaline earth and transition metals in NaCl-dominated hydrothermal fluids: An experimental study from 360 to 465 °C, near-critical to halite saturated conditions

    NASA Astrophysics Data System (ADS)

    Pester, Nicholas J.; Ding, Kang; Seyfried, William E.

    2015-11-01

    Multi-phase fluid flow is a common occurrence in magmatic hydrothermal systems; and extensive modeling efforts using currently established P-V-T-x properties of the NaCl-H2O system are impending. We have therefore performed hydrothermal flow experiments (360-465 °C) to observe vapor-liquid partitioning of alkaline earth and first row transition metals in NaCl-dominated source solutions. The data allow extraction of partition coefficients related to the intrinsic changes in both chlorinity and density along the two-phase solvus. The coefficients yield an overall decrease in vapor affinity in the order Cu(I) > Na > Fe(II) > Zn > Ni(II) ⩾ Mg ⩾ Mn(II) > Co(II) > Ca > Sr > Ba, distinguished with 95% confidence for vapor densities greater than ∼0.2 g/cm3. The alkaline earth metals are limited to purely electrostatic interactions with Cl ligands, resulting in an excellent linear correlation (R2 > 0.99) between their partition coefficients and respective ionic radii. Though broadly consistent with this relationship, relative behavior of the transition metals is not well resolved, being likely obscured by complex bonding processes and the potential participation of Na in the formation of tetra-chloro species. At lower densities (at/near halite saturation) partitioning behavior of all metals becomes highly non-linear, where M/Cl ratios in the vapor begin to increase despite continued decreases in chlorinity and density. We refer to this phenomenon as "volatility", which is broadly associated with substantial increases in the HCl/NaCl ratio (eventually to >1) due to hydrolysis of NaCl. Some transition metals (e.g., Fe, Zn) exhibit volatility prior to halite stability, suggesting a potential shift in vapor speciation relative to nearer critical regions of the vapor-liquid solvus. The chemistry of deep-sea hydrothermal fluids appears affected by this process during magmatic events, however, our results do not support suggestions of subseafloor halite precipitation

  2. Extraction of starch from wheat flour by alkaline solution

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Separation of starch from wheat flour with high purity is very important for the analysis of starch such as amylose and amylopectin determination by size exclusion HPLC (SE-HPLC). A procedure that extracts starch from flour by ethanol precipitation after dissolving flour in KOH and urea solution wa...

  3. A Special Issue (Part-II): Mafic-ultramafic rocks and alkaline-carbonatitic magmatism and associated hydrothermal mineralization - dedication to Lia Nikolaevna Kogarko

    NASA Astrophysics Data System (ADS)

    Kogarko, Lia N.; Gwalani, Lalchand G.; Downes, Peter J.; Randive, Kirtikumar R.

    2015-10-01

    This is the second part of a two-volumespecial issue of Open Geoscience (formerly Central European Journal of Geosciences) that aims to be instrumental in providing an update of Mafic-Ultramafic Rocks and Alkaline- Carbonatitic Magmatism and Associated Hydrothermal Mineralization. Together, these two volumes provide a detailed and comprehensive coverage of the subjects that are relevant to the research work of P.Comin-Chiaramonti (Italy) and LiaN. Kogarko (Russia) towhomPart-I and Part- II have been respectively dedicated. To a significant extent, the development of advanced sampling technologies related to alkaline and carbonatitic magmatism by Lia N. Kogarko, has allowed geoscientists to measure and sample the deep crust of the planet not only for the exploration for the mineral deposits, but also to answer basic scientific questions about the origin and evolution of alkaline rocks (kimberlites, lamproites and related rocks associated with carbonatites). The papers presented in this Part-II of the special issue cover the petrology and geochemistry of the rocks collected from the surface and penetrated by drilling. Lia Kogarko proposed a new theory for the evolution of alkaline magmatism in the geological history of the Earth - that the appearance of alkaline magmatism at the Archaean-Proterozoic boundary (~2.5 - 2.7 Ga), and its growing intensity, was related to changes in the geodynamic regime of the Earth and oxidation of the mantle due to mantle-crust interaction.

  4. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  5. Solid / solution interaction: The effect of carbonate alkalinity on adsorbed thorium

    NASA Astrophysics Data System (ADS)

    LaFlamme, Brian D.; Murray, James W.

    1987-02-01

    Elevated activities of dissolved Th have been found in Soap Lake, an alkaline lake in Eastern Washington. Dissolved 232Th ranges from less than 0.001 to 4.9 dpm/L compared to about 1.3 × 10 -5 dpm/ L in sea water. The enhanced activity in the lake coincides with an increase in carbonate alkalinity. Experiments were conducted to evaluate the effect of pH, ionic strength and carbonate alkalinity on Th adsorption on goethite. Thorium (10 -13 M total) in the presence of 5.22 mg/L α-FeOOH and 0.1 M NaNO 3 has an adsorption edge from pH 2-5. At pH 9.0 ± 0.6 the percent Th absorbed on the solid began to decrease from 100% at 100 meq/L carbonate alkalinity and exhibited no adsorption above 300 meq/L. The experimental data were modeled to obtain the intrinsic adsorption equilibrium constants for Th hydrolysis species. These adsorption constants were incorporated in the model to interpret the observed effect of carbonate alkalinity on Th adsorption. There are two main effects of the alkalinity. To a significant degree the decrease in Th adsorption is due to competition of HCO -3 and CO 2-3 ions for surface sites. Dissolved Th carbonate complexes also contribute to the increase of Th in solution.

  6. Electrochemical Recovery of Sodium Hydroxide from Alkaline Salt Solution

    SciTech Connect

    Hobbs, D.T.; Edwards, T.B.

    1996-10-01

    A statistically designed set of tests determined the effects of current density, temperature, and the concentrations of nitrate/nitrite, hydroxide and aluminate on the recovery of sodium as sodium hydroxide (caustic) from solutions simulating those produced from the Savannah River Site (SRS) In-Tank Precipitation process. These tests included low nitrate and nitrite concentrations which would be produced by electrolytic nitrate/nitrite destruction. The tests used a two compartment electrochemical cell with a Nafion Type 324 ion-exchange membrane. Caustic was successfully recovered from the waste solutions. Evaluation of the testing results indicated that the transport of sodium across the membrane was not significantly affected by any of the varied parameters. The observed variance in the sodium flux is attributed to experimental errors and variations in the performance characteristics of individual pieces of the organic-based Nafion membrane.Additional testing is recommended to determine the maximum current density, to evaluate the chemical durability of the organic membrane as a function of current density and to compare the durability and performance characteristics of the organic-based Nafion membrane with that of other commercially available organic membranes and the inorganic class of membranes under development by Ceramatec and PNNL.

  7. PMBP extraction and TPE separation in alkaline pyrophosphate solutions

    SciTech Connect

    Karalova, Z.K.; Bukina, T.I.; Lavrinovich, E.A.; Trofimov, T.I.; Kulyako, Yu.M.; Myasoedov, B.F.

    1988-11-01

    Measurements have been made on the solvent extraction of Am(III), Am(V), Cm(III), and Eu(III) in trace and macroscopic amounts from (NH/sub 4/)/sub 4/P/sub 2/O/sub 7/ (pH = 7.6) and Na/sub 4/P/sub 2/O/sub 7/ (pH = 10) solutions as coordination compounds with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP). A method has been devised for separating weighable amounts of americium and curium, which is based in trivalent curium being extracted quantitatively from 0.1 M sodium pyrophosphate (pH 10) by 0.1 M PMBP solution in chloroform, where high distribution coefficients apply, while americium is electrochemically oxidized in that medium to Am(VI) and on contact with the extraction agent is reduced to Am(V) and remains in the aqueous phase. The separation factor for the Cm(III)-Am(V) pair is about 10/sup 3/.

  8. USING CERAMIC MEMBRANES TO RECYCLE TWO NONIONIC ALKALINE METAL-CLEANING SOLUTIONS

    EPA Science Inventory

    One ZrO2 ultrafilter (0.05 um pore size) and two a-Al2O3 microfilters (0.2 and 0.8 um) were used to remove one synthetic ester oil and two polyalphaolefin-based and two petroleum hydrocarbon-based oils and greases from two nonionic alkaline cleaning solutions (e.g., Turco 4215-NC...

  9. Bioprecipitation of uranium from alkaline waste solutions using recombinant Deinococcus radiodurans.

    PubMed

    Kulkarni, Sayali; Ballal, Anand; Apte, Shree Kumar

    2013-11-15

    Bioremediation of uranium (U) from alkaline waste solutions remains inadequately explored. We engineered the phoK gene (encoding a novel alkaline phosphatase, PhoK) from Sphingomonas sp. for overexpression in the radioresistant bacterium Deinococcus radiodurans. The recombinant strain thus obtained (Deino-PhoK) exhibited remarkably high alkaline phosphatase activity as evidenced by zymographic and enzyme activity assays. Deino-PhoK cells could efficiently precipitate uranium over a wide range of input U concentrations. At low uranyl concentrations (1 mM), the strain precipitated >90% of uranium within 2h while a high loading capacity of around 10.7 g U/g of dry weight of cells was achieved at 10 mM U concentration. Uranium bioprecipitation by Deino-PhoK cells was not affected in the presence of Cs and Sr, commonly present in intermediate and low level liquid radioactive waste, or after exposure to very high doses of ionizing radiation. Transmission electron micrographs revealed the extracellular nature of bioprecipitated U, while X-ray diffraction and fluorescence analysis identified the precipitated uranyl phosphate species as chernikovite. When immobilized into calcium alginate beads, Deino-PhoK cells efficiently removed uranium, which remained trapped in beads, thus accomplishing physical separation of precipitated uranyl phosphate from solutions. The data demonstrate superior ability of Deino-PhoK, over earlier reported strains, in removal of uranium from alkaline solutions and its potential use in bioremediation of nuclear and other waste.

  10. Measurement and control of pH in hydrothermal solutions

    SciTech Connect

    Wesolowski, D.J.; Palmer, D.A.; Mesmer, R.E.

    1995-12-31

    Hydrogen-electrode concentration cells with liquid junction are routinely used to measure the pH of aqueous solutions from 0 to 300 C. Results include the dissociation constants of common acids and bases and the hydrolysis and complexation of metal ions in aqueous electrolytes over a wide range of salinities. Recently, we have utilized these cells to examine the sorption of H{sup +} on mineral surfaces, the solubility of minerals with continuous in situ pH measurement, and the thermal decompositon rates of organic acids.

  11. Inhibition of Brass Corrosion by 2-Mercapto-1-methylimidazole in Weakly Alkaline Solution

    NASA Astrophysics Data System (ADS)

    Radovanovic, Milan B.; Antonijevic, Milan M.

    2016-03-01

    The electrochemical behavior of brass and anticorrosion effect of 2-mercapto-1-methylimidazole (2-MMI) in weakly alkaline solution with and without presence of chloride ions was investigated using electrochemical techniques in addition to SEM-EDS analysis. Results show that inhibition efficiency depended on inhibitor concentration and immersion time of brass electrode in inhibitor solution. Inhibition mechanism of 2-mercapto-1-methylimidazole includes adsorption of inhibitor on active sites on electrode surface which was confirmed by SEM-EDS analysis of the brass. Adsorption of the 2-MMI in sodium tetraborate solution obeys Flory-Huggins adsorption isotherm, while in the presence of chloride, ions adsorption of inhibitor obeys Langmuir adsorption isotherm.

  12. Effect of different alkaline solutions on crystalline structure of cellulose at different temperatures.

    PubMed

    Keshk, Sherif M A S

    2015-01-22

    Effect of alkaline solutions such as 10% NaOH, NaOH/urea and NaOH/ethylene glycol solutions on crystalline structure of different cellulosic fibers (cotton linter and filter paper) was investigated at room temperature and -4°C. The highest dissolution of cotton linter and filter paper was observed in NaOH/ethylene glycol at both temperatures. X-ray patterns of treated cotton linter with different alkaline solutions at low temperature showed only two diffractions at 2θ=12.5° and 21.0°, which belonged to the crystalline structure of cellulose II. CP/MAS (13)C NMR spectra showed the doublet peaks at 89.2 ppm and 88.3 ppm representing C4 resonance for cellulose I at room temperature, Whereas, at low temperature the doublet peaks were observed at 89.2 ppm and 87.8 ppm representing C4 resonance for cellulose II. Degree of polymerization of cellulose plays an important role in cellulose dissolution in different alkaline solutions and temperatures, where, a low temperature gives high dissolutions percentage with change in crystalline structure from cellulose I to cellulose II forms.

  13. Temperature dependence of the absorbance of alkaline solutions of 4-nitrophenyl phosphate--a potential source of error in the measurement of alkaline phosphatase activity.

    PubMed

    Burtis, C A; Seibert, L E; Baird, M A; Sampson, E J

    1977-09-01

    The absorbance of an alkaline solution of 4-nitrophenyl phosphate is a function of temperature. Quantitative evaluation of this phenomenon indicates that it (a) depends on the concentration of the compound and is independent of source, buffer concentration, and pH above 9.0; (b) is reversible; (c) is not a result of alkaline hydrolysis or 4-nitrophenol contamination; and (d) correlates with a temperature-induced shift of its absorbance spectrum. The phenomenon may represent a potential analytical problem in methods for alkaline phosphatase in which this compound is the substrate. If thermal equilibrium is not reached and maintained during an alkaline phosphatase assay, the thermochromic response will be included in the measured rate. The magnitude of this error depends on the thermal response and control characteristics of each particular instrument and the reaction conditions under which such an analysis is performed.

  14. Simulation of hydrogen sulphide absorption in alkaline solution using a packed column.

    PubMed

    Azizi, Mohamed; Biard, Pierre-François; Couvert, Annabelle; Ben Amor, Mohamed

    2014-01-01

    In this work, a simulation tool was developed for hydrogen sulphide (H₂S) removal in an alkaline solution in packed columns working at countercurrent. Modelling takes into account the mass-transfer enhancement due to the reversible reactions between H₂S and the alkaline species (CO(²⁻)(3), HCO⁻(3), and HO⁻) in the liquid film. Many parameters can be controlled by the user such as the gas and liquid inlet H₂S concentrations, the gas and liquid flow rates, the scrubbing liquid pH, the desired H₂S removal efficiency, the temperature, the alkalinity, etc. Since the influence of the hydrodynamic and mass-transfer performances in a packed column is well known, the numerical resolutions performed were dedicated to the study of the influence of the chemical conditions (through the pH and the alkalinity), the temperature and the liquid-to-gas mass flow rate ratio (L/G). A packed column of 3 m equipped with a given random packing material working at countercurrent and steady state has been modelled. The results show that the H₂S removal efficiency increases with the L/G, the pH, the alkalinity and more surprisingly with the temperature. Alkalinity has a very significant effect on the removal efficiency through the mass-transfer enhancement and buffering effect, which limits pH decreasing due to H₂S absorption. This numerical resolution provides a tool for designers and researchers involved in H₂S treatment to understand deeper the process and optimize their processes.

  15. Characterization of Laboratory Prepared Concrete Pastes Exposed to High Alkaline and High Sodium Salt Solutions

    SciTech Connect

    Langton, C. A.

    2016-06-30

    The objective of this study was to identify potential chemical degradation mechanisms for the Saltstone Disposal Unit (SDU) concretes, which over the performance life of the structures may be exposed to highly alkaline sodium salt solutions containing sulfate, hydroxide, and other potentially corrosive chemicals in salt solution and saltstone flush water, drain water, leachate and / or pore solution. The samples analyzed in this study were cement pastes prepared in the SIMCO Technologies, Inc. concrete laboratory. They were based on the paste fractions of the concretes used to construct the Saltstone Disposal Units (SDUs). SDU 1 and 4 concrete pastes were represented by the PV1 test specimens. The paste in the SDU 2, 3, 5, and 6 concrete was represented by the PV2 test specimens. SIMCO Technologies, Inc. selected the chemicals and proportions in the aggressive solutions to approximate proportions in the saltstone pore solution [2, 3, 5, and 6]. These test specimens were cured for 56 days in curing chamber before being immersed in aggressive solutions. After exposure, the samples were frozen to prevent additional chemical transport and reaction. Selected archived (retrieved from the freezer) samples were sent to the Savannah River National Laboratory (SRNL) for additional characterization using x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX) spectroscopy. Characterization results are summarized in this report. In addition, a correlation between the oxide composition of the pastes and their chemical durability in the alkaline salt solutions is provided.

  16. MODELING AN ION EXCHANGE PROCESS FOR CESIUM REMOVAL FROM ALKALINE RADIOACTIVE WASTE SOLUTIONS

    SciTech Connect

    Smith, F; Luther Hamm, L; Sebastian Aleman, S; Johnston Michael, J

    2008-08-26

    The performance of spherical Resorcinol-Formaldehyde ion-exchange resin for the removal of cesium from alkaline radioactive waste solutions has been investigated through computer modeling. Cesium adsorption isotherms were obtained by fitting experimental data using a thermodynamic framework. Results show that ion-exchange is an efficient method for cesium removal from highly alkaline radioactive waste solutions. On average, two 1300 liter columns operating in series are able to treat 690,000 liters of waste with an initial cesium concentration of 0.09 mM in 11 days achieving a decontamination factor of over 50,000. The study also tested the sensitivity of ion-exchange column performance to variations in flow rate, temperature and column dimensions. Modeling results can be used to optimize design of the ion exchange system.

  17. Unique chemistry of the hydrothermal solution in the mid-Okinawa Trough Backarc Basin

    SciTech Connect

    Sakai, H.; Gamo, T.; Kim, E.S.; Shitashima, K.; Yanagisawa, F.; Tsutsumi, M.; Ishibashi, J.; Sano, Y.; Wakita, H. ); Tanaka, T.; Matsumoto, T.; Naganuma, T.; Mitsuzawa, K. )

    1990-11-01

    Submarine hydrothermal fluids from JADE and CLAM sites in the mid-Okinawa Trough Backarc Basin are highly enriched in CO{sub 2}, K, Li, NH{sub 4}, CH{sub 4} and titration alkalinity compared to MOR fluids so far studied, while their H{sub 2}S and {sup 3}He contents are similar. The He and C isotropic ratios as well as these chemical features indicate that the hydrothermal systems are controlled by reaction between seawater and CO{sub 2}-rich intermediate to acid volcanic rocks of island-arc type, with strong influence of organic matter and are consistent with its initial stage of rifting on a continental plate margin. While the endmember JADE fluid is nearly devoid of Mg and SO{sub 4}, the CLAM fluid has definite concentrations of Mg (upper limit 22 {plus minus} 5 mM) and, most interestingly of {sup 34}S-enriched SO{sub 4} (upper limit 10 {plus minus} 2 mM, {delta}{sup 34}S = 27 to 39{per thousand}).

  18. Adsorption of Pb(II) and Cd(II) from aqueous solutions using titanate nanotubes prepared via hydrothermal method.

    PubMed

    Xiong, Lin; Chen, Cheng; Chen, Qing; Ni, Jinren

    2011-05-30

    Titanate nanotubes (TNs) with specific surface areas of 272.31 m(2)g(-1) and pore volumes of 1.264 cm(3)g(-1) were synthesized by alkaline hydrothermal method. The TNs were investigated as adsorbents for the removal of Pb(II) and Cd(II) from aqueous solutions. The FT-IR analysis indicated that Pb(II) and Cd(II) adsorption were mainly ascribed to the hydroxyl groups in the TNs. Batch experiments were conducted by varying contact time, pH and adsorbent dosage. It was shown that the initial uptake of each metal ion was very fast in the first 5 min, and adsorption equilibrium was reached after 180 min. The adsorption of Pb(II) and Cd(II) were found to be maximum at pH in the range of 5.0-6.0. The adsorption kinetics of both metal ions followed the pseudo-second-order model. Equilibrium data were best fitted with the Langmuir isotherm model, and the maximum adsorption capacities of Pb(II) and Cd(II) were determined to be 520.83 and 238.61 mg g(-1), respectively. Moreover, more than 80% of Pb(II) and 85% of Cd(II) adsorbed onto TNs can be desorbed with 0.1M HCl after 3h. Thus, TNs were considered to be effective and promising materials for the removal of both Pb(II) and Cd(II) from wastewater.

  19. Inhibitive effects of palm kernel oil on carbon steel corrosion by alkaline solution

    NASA Astrophysics Data System (ADS)

    Zulkafli, M. Y.; Othman, N. K.; Lazim, A. M.; Jalar, A.

    2013-11-01

    The behavior of carbon steel SAE 1045 in 1 M NaOH solution containing different concentrations of palm kernel oil (PKO) has been studied by weight loss and polarization measurement. Results showed that the corrosion of carbon steel in NaOH solution was considerably reduced in presence of such inhibitors. The inhibition efficiency increases when concentration of inhibitor increase. Maximum inhibition efficiency (≈ 96.67%) is obtained at PKO concentration 8 v/v %. This result revealed that palm kernel oil can act as a corrosion inhibitor in an alkaline medium. Corrosion rates of carbon steel decrease as the concentration of inhibitor is increased.

  20. Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

    NASA Astrophysics Data System (ADS)

    Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

    1997-10-01

    Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

  1. Alkaline earth metal-based metal-organic framework: hydrothermal synthesis, X-ray structure and heterogeneously catalyzed Claisen-Schmidt reaction.

    PubMed

    Saha, Debraj; Maity, Tanmoy; Koner, Subratanath

    2014-09-14

    Two alkaline earth metal-based carboxylate systems, [Mg(HL)(H2O)2]n (1) and [Ca(H2L)2]n (2) (H3L = chelidamic acid) have been hydrothermally synthesized, and characterized by single-crystal X-ray diffraction, IR, elemental analysis, and thermo-gravimetric analysis. Compound 1 has a 2D structure incorporating two water molecules. The dehydrated species, 1a, generated from 1 by removal of the coordinated water, has been characterized by thermo-gravimetric analysis, IR, elemental analysis and variable temperature powder X-ray diffraction. Both 1 and its dehydrated species 1a catalyze the Claisen-Schmidt reaction under heterogeneous conditions, but 1a is a more effective catalyst under environmentally friendly conditions. The catalyst can readily be recovered and reused in successive cycles without detectable loss of activity. Compound 2 has a 3D structure and is thermally stable up to 540 °C, but is inactive catalytically.

  2. Organic compounds in olive mill wastewater and in solutions resulting from hydrothermal carbonization of the wastewater.

    PubMed

    Poerschmann, J; Weiner, B; Baskyr, I

    2013-09-01

    Organic components in olive mill wastewater (OMW) were analyzed by exhaustive solvent extraction of the lyophilisate followed by pre-chromatographic derivatization techniques and GC/MS-analysis of the extracts. Simple biophenols including tyrosol (Tyr), hydroxytyrosol (OH-Tyr) and homovanillic alcohol as well as complex biophenols including decarbomethoxy ligostride aglycon and decarbomethoxy oleuropein aglycon proved most abundant analytes. Hydroxylated benzoic and cinnamic acids are less abundant, which may indicate a humification process to have occurred. The pattern of organic components obtained from native OMW was compared with that obtained from hydrothermal carbonization (HTC) of the waste product. Former results provided strong evidence that HTC of OMW at 220°C for 14h results in an almost complete hydrolysis of complex aglycons. However, simple biophenols were not decomposed on hydrothermal treatment any further. Phenol and benzenediols as well as low molecular weight organic acids proved most abundant analytes which were generated due to HTC. Similarly to aglycons, lipids including most abundant acylglycerines and less abundant wax esters were subjected almost quantitatively to hydrolysis under hydrothermal conditions. Fatty acids (FAs) released from lipids were further decomposed. The pathways of volatile analytes in both native OMW and aqueous HTC solutions were studied by solventless headspace-Solid Phase Micro Extraction. Basically, a wide array low molecular alcohols and ketones occurring in native OMW survived the HTC process.

  3. Combined pretreatment using alkaline hydrothermal and ball milling to enhance enzymatic hydrolysis of oil palm mesocarp fiber.

    PubMed

    Zakaria, Mohd Rafein; Hirata, Satoshi; Hassan, Mohd Ali

    2014-10-01

    Hydrothermal pretreatment of oil palm mesocarp fiber was conducted in tube reactor at treatment severity ranges of log Ro = 3.66-4.83 and partial removal of hemicellulose with migration of lignin was obtained. Concerning maximal recovery of glucose and xylose, 1.5% NaOH was impregnated in the system and subsequent ball milling treatment was employed to improve the conversion yield. The effects of combined hydrothermal and ball milling pretreatments were evaluated by chemical composition changes by using FT-IR, WAXD and morphological alterations by SEM. The successful of pretreatments were assessed by the degree of enzymatic digestibility of treated samples. The highest xylose and glucose yields obtained were 63.2% and 97.3% respectively at cellulase loadings of 10 FPU/g-substrate which is the highest conversion from OPMF ever reported.

  4. A water-ethanol mixed-solution hydrothermal route to silicates nanowires

    SciTech Connect

    Wang Xun . E-mail: wangxun@mail.tsinghua.edu.cn; Zhuang Jing; Peng Qing; Li Yadong . E-mail: ydli@mail.tsinghua.edu.cn

    2005-07-15

    In this manuscript, series of silicates nanowires, such as calcium silicate, strontium silicate, barium silicate, zinc silicate and cadmium silicate, etc., have been successfully prepared from a water-ethanol mixed solution system through a hydrothermal synthetic way. The formation process of these silicates nanowires has been studied in detail. Due to their rich sources and possible novel properties from reduced dimensionalities, we believe that the synthesis of these silicates nanowires may bring some new opportunity in the solid state chemistry and nanoscience and technology fields, etc.

  5. Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.

    PubMed

    Zhan, Yi; Du, Guojun; Yang, Shiliu; Xu, Chaohe; Lu, Meihua; Liu, Zhaolin; Lee, Jim Yang

    2015-06-17

    Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc-air cell assembled with a Co(OH)2-air electrode also showed a performance comparable to that of the state-of-the-art zinc-air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts.

  6. THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

    PubMed

    Brdicka, R

    1936-07-20

    1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

  7. Influence of Acidic and Alkaline Waste Solution Properties on Uranium Migration in Subsurface Sediments

    SciTech Connect

    Szecsody, James E.; Truex, Michael J.; Qafoku, Nikolla; Wellman, Dawn M.; Resch, Charles T.; Zhong, Lirong

    2013-08-01

    This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments has significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH 2) resulted in a rapid (< 10 h) increase in aqueous carbonate (with Ca2+, Mg2+) and phosphate and a slow (100s of hours) increase in silica, Al3+, and K+, likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH 13) resulted in a rapid (< 10 h) increase in carbonate, followed by a slow (10s to 100s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity.

  8. Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments

    NASA Astrophysics Data System (ADS)

    Szecsody, Jim E.; Truex, Mike J.; Qafoku, Nikolla P.; Wellman, Dawn M.; Resch, Tom; Zhong, Lirong

    2013-08-01

    This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH 2) resulted in a rapid (< 10 h) increase in aqueous carbonate (with Ca2 +, Mg2 +) and phosphate and a slow (100 s of hours) increase in silica, Al3 +, and K+, likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH 13) resulted in a rapid (< 10 h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity.

  9. Thiols in Hydrothermal Solution: Standard Partial Molal Properties and Their Role in the Organic Geochemistry of Hydrothermal Environments

    NASA Technical Reports Server (NTRS)

    Schulte, Mitchell D.; Rogers, Karyn L.; DeVincenzi, D. (Technical Monitor)

    2001-01-01

    Modern seafloor hydrothermal systems are locations where great varieties of geochemistry occur due to the enormous disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Despite the incomplete understanding of the carbon budget in hydrothermal systems, the organic geochemistry of these sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols, thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments, as well as in a variety of biological processes and other abiotic reactions. The reduction of CO2 to thesis, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power. We have used recent advances in theoretical geochemistry to estimate the standard partial moral thermodynamic properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for aqueous straight-chain alkyl thesis. With these data and parameters we have evaluated the role that organic sulfur compounds may play as reaction intermediates during organic compound synthesis. We conclude that organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life in hydrothermal settings. These results may also explain the presence of sulfur in a number of biomolecules present in ancient thermophilic microorganisms.

  10. Reaction of montmorillonite in alkaline solution at 60 C, 90 C, 120 C and 180 C

    SciTech Connect

    Amaya, Takayuki; Shimojo, Mikio; Fujihara, Hiroshi; Yokoyama, Katsuhiko

    1999-07-01

    The reaction of montmorillonite was investigated. Three kinds of bentonites with different montmorillonite composition were mixed with 0.3M NaOH solution and 0.3M Ca(OH){sub 2} slurry. They were immersed at 60 C, 90 C, 120 C, and 180 C for one month, three months and six months. The concentrations of the soluble ions were measured and the bentonites were analyzed quantitatively after the immersion. 50% of the montmorillonite was reacted within two weeks at greater than 90 C. Montmorillonite reacts less when mixed with Si-minerals. It extensively reacted in 0.3M Ca(OH){sub 2} slurry. These results suggest that the reaction mechanism of the montmorillonite in alkaline solution was dominantly Si dissolution, and would decrease by controlling the concentration of Si ion. The cement/bentonite system under Si saturated conditions is discussed.

  11. On the complex structural diffusion of proton holes in nanoconfined alkaline solutions within slit pores

    PubMed Central

    Muñoz-Santiburcio, Daniel; Marx, Dominik

    2016-01-01

    The hydroxide anion OH−(aq) in homogeneous bulk water, that is, the solvated proton hole, is known to feature peculiar properties compared with excess protons solvated therein. In this work, it is disclosed that nanoconfinement of such alkaline aqueous solutions strongly affects the key structural and dynamical properties of OH−(aq) compared with the bulk limit. The combined effect of the preferred hypercoordinated solvation pattern of OH−(aq), its preferred perpendicular orientation relative to the confining surfaces, the pronounced layering of nanoconfined water and the topology of the hydrogen bond network required for proton hole transfer lead to major changes of the charge transport mechanism, in such a way that the proton hole migration mechanism depends exquisitely on the width of the confined space that hosts the water film. Moreover, the anionic Zundel complex, which is of transient nature in homogeneous bulk solutions, can be dynamically trapped as a shallow intermediate species by suitable nanoconfinement conditions. PMID:27550616

  12. Spatial distribution of microbial communities in the shallow submarine alkaline hydrothermal field of the Prony Bay, New Caledonia.

    PubMed

    Quéméneur, Marianne; Bes, Méline; Postec, Anne; Mei, Nan; Hamelin, Jérôme; Monnin, Christophe; Chavagnac, Valérie; Payri, Claude; Pelletier, Bernard; Guentas-Dombrowsky, Linda; Gérard, Martine; Pisapia, Céline; Gérard, Emmanuelle; Ménez, Bénédicte; Ollivier, Bernard; Erauso, Gaël

    2014-12-01

    The shallow submarine hydrothermal field of the Prony Bay (New Caledonia) discharges hydrogen- and methane-rich fluids with low salinity, temperature (< 40°C) and high pH (11) produced by the serpentinization reactions of the ultramafic basement into the lagoon seawater. They are responsible for the formation of carbonate chimneys at the lagoon seafloor. Capillary electrophoresis single-strand conformation polymorphism fingerprinting, quantitative polymerase chain reaction and sequence analysis of 16S rRNA genes revealed changes in microbial community structure, abundance and diversity depending on the location, water depth, and structure of the carbonate chimneys. The low archaeal diversity was dominated by few uncultured Methanosarcinales similar to those found in other serpentinization-driven submarine and subterrestrial ecosystems (e.g. Lost City, The Cedars). The most abundant and diverse bacterial communities were mainly composed of Chloroflexi, Deinococcus-Thermus, Firmicutes and Proteobacteria. Functional gene analysis revealed similar abundance and diversity of both Methanosarcinales methanoarchaea, and Desulfovibrionales and Desulfobacterales sulfate-reducers in the studied sites. Molecular studies suggest that redox reactions involving hydrogen, methane and sulfur compounds (e.g. sulfate) are the energy driving forces of the microbial communities inhabiting the Prony hydrothermal system.

  13. Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Fu, Li-cai; Qin, Wen; Yang, Jun; Liu, Wei-min; Zhou, Ling-ping

    2017-01-01

    The corrosion-wear behavior of a nanocrystalline Fe88Si12 alloy disc coupled with a Si3N4 ball was investigated in acid (pH 3) and alkaline (pH 9) aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe88Si12 alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe88Si12 alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe88Si12 alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si3N4 ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe88Si12 alloy in the pH 9 aqueous solution.

  14. Fabrication of strongly attached hydroxyapatite coating on titanium by hydrothermal treatment of Ti-Zn-PO4 coated titanium in CaCl 2 solution.

    PubMed

    Valanezhad, Alireza; Tsuru, Kanji; Ishikawa, Kunio

    2015-07-01

    Hydroxyapatite (HAp) coating was formed on zinc phosphate (Ti-Zn-PO4) coated Ti plates by hydrothermal treatment in CaCl2 solution at 200 °C for 12 h. Uniform surface coverage of the fabricated HAp coating was obtained by this method. SEM-EDX analysis of the adhesion test area showed that the presence of fractures only occurred in HAp crystals. On the other words cohesive fracture was seen in HAp coating layer formed on the Ti-Zn-PO4. The measured strength was around 42.3 ± 17 MPa. Rat bone marrow (RBM) mesenchymal stem cells were cultured and differentiation-induced on each sample (Ti plate, Ti-Zn-PO4 coated and HAp coated), and cell calcification properties were examined. Apparent differences in morphology and extension of the RBM cells were obtained, while the Ti-Zn-PO4 coated samples showed the highest cell number among all samples. After differentiation-induction, HAp coated samples showed the highest amount of alkaline phosphatase activity, and the highest level of cell calcification. Therefore, the hard tissue compatibility of Ti is improved by hydrothermally HAp coating of samples.

  15. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  16. Hexavalent uranium diffusion into soils from concentrated acidic and alkaline solutions

    SciTech Connect

    Tokunaga, Tetsu K.; Wan, Jiamin; Pena, Jasquelin; Sutton, Stephen R.; Newville, Matthew

    2004-03-29

    Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro x-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs, and U(VI) concentration profiles within soil columns yielded K{sub d} values consistent with those determined in batch tests at similar concentrations ({approx} 1 mM), and much lower than values for sorption at much lower concentrations (nM to {mu}M). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.

  17. The use of X-ray fluorescence (XRF) analysis in predicting the alkaline hydrothermal conversion of fly ash precipitates into zeolites.

    PubMed

    Somerset, V S; Petrik, L F; White, R A; Klink, M J; Key, D; Iwuoha, E

    2004-09-08

    The use and application of synthetic zeolites for ion exchange, adsorption and catalysis has shown enormous potential in industry. In this study, X-ray fluorescence (XRF) analysis was used to determine Si and Al in fly ash (FA) precipitates. The Si and Al contents of the fly ash precipitates were used as indices for the alkaline hydrothermal conversion of the fly ash compounds into zeolites. Precipitates were collected by using a co-disposal reaction wherein fly ash is reacted with acid mine drainage (AMD). These co-disposal precipitates were then analysed by XRF spectrometry for quantitative determination of SiO(2) and Al(2)O(3). The [SiO(2)]/[Al(2)O(3)] ratio obtained in the precipitates range from 1.4 to 2.5. The [SiO(2)]/[Al(2)O(3)] ratio was used to predict whether the fly ash precipitates could successfully be converted to faujasite zeolitic material by the synthetic method of [J. Haz. Mat. B 77 (2000) 123]. If the [SiO(2)]/[Al(2)O(3)] ratio is higher than 1.5 in the fly ash precipitates, it favours the formation of faujasite. The zeolite synthesis included an alkaline hydrothermal conversion of the co-disposal precipitates, followed by aging for 8h and crystallization at 100 degrees C. Different factors were investigated during the synthesis of zeolite to ascertain their influence on the end product. The factors included the amount of water in the starting material, composition of fly ash related starting material and the FA:NaOH ratio used for fusing the starting material. The mineralogical and physical analysis of the zeolitic material produced was performed by X-ray diffraction (XRD) and nitrogen Brunauer-Emmett-Teller (N(2) BET) surface analysis. Scanning electron microscopy (SEM) was used to determine the morphology of the zeolites, while inductively coupled mass spectrometry (ICP-MS), Fourier transformed infrared spectrometry (FT-IR) and Cation exchange capacity (CEC) [Report to Water Research Commission, RSA (2003) 15] techniques were used for

  18. A chelating ion exchanger for gallium recovery from alkaline solution using 5-palmitoyl-8-hydroxyquinoline immobilized on a nonpolar adsorbent

    SciTech Connect

    Filik, H.; Apak, R.

    1998-06-01

    The recently developed method of gallium recovery from alkaline solution by alkanoyl oxine/chloroform extraction has been improved by immobilizing palmitoyl oxine on hydrophobic macroporous styrene-divinylbenzene copolymer Amberlite XAD-2 and passing the GA-containing alkaline solution of pH 13.5 through the synthesized resin column. The developed column showed reasonable efficiency after successive passages, and the selectivity of Ga over Al was very high, suggesting the utilizibility of the method in Ga recovery from the basic aluminate liquor of the Bayer process. The Ga capacity of the oxine-based resin was 3.94 {micro}mol/g. Two mg Ga retained on 10 g resin could be eluted with 25 mL of 2 N HCl at a throughput rate of 2 mL/min. The developed process has prospective use in Ga separation from Al in a strongly alkaline solution.

  19. Removal of copper and cadmium from aqueous solution using switchgrass biochar produced via hydrothermal carbonization process.

    PubMed

    Regmi, Pusker; Garcia Moscoso, Jose Luis; Kumar, Sandeep; Cao, Xiaoyan; Mao, Jingdong; Schafran, Gary

    2012-10-30

    Biochar produced from switchgrass via hydrothermal carbonization (HTC) was used as a sorbent for the removal of copper and cadmium from aqueous solution. The cold activation process using KOH at room temperature was developed to enhance the porous structure and sorption properties of the HTC biochar. The sorption efficiency of HTC biochar and alkali activated HTC biochar (HTCB) for removing copper and cadmium from aqueous solution were compared with commercially available powdered activated carbon (PAC). The present batch adsorption study describes the effects of solution pH, biochar dose, and contact time on copper and cadmium removal efficiency from single metal ion aqueous solutions. The activated HTCB exhibited a higher adsorption potential for copper and cadmium than HTC biochar and PAC. Experiments conducted with an initial metal concentration of 40 mg/L at pH 5.0 and contact time of 24 h resulted in close to 100% copper and cadmium removal by activated HTCB at 2 g/L, far greater than what was observed for HTC biochar (16% and 5.6%) and PAC (4% and 7.7%). The adsorption capacities of activated HTCB for cadmium removal were 34 mg/g (0.313 mmol/g) and copper removal was 31 mg/g (0.503 mmol/g).

  20. Optical characterization of synthetic faceted gem materials grown from hydrothermal solutions

    NASA Astrophysics Data System (ADS)

    Lu, Taijin; Shigley, James E.

    1998-10-01

    Various non-destructive optical characterization techniques have been used to characterize and identify synthetic gem materials grown from hydrothermal solutions, to include ruby, sapphire, emerald, amethyst and ametrine (amethyst-citrine), from their natural counterparts. The ability to observe internal features, such as inclusions, dislocations, twins, color bands, and growth zoning in gem materials is strongly dependent on the observation techniques and conditions, since faceted gemstones have many polished surfaces which can reflect and scatter light in various directions which can make observation difficult. However, diagnostic gemological properties of these faceted synthetic gem materials can be obtained by choosing effective optical characterization methods, and by modifying optical instruments. Examples of some of the distinctive features of synthetic amethyst, ametrine, pink quartz, ruby and emerald are presented to illustrate means of optical characterization of gemstones. The ability to observe defects by light scattering techniques is discussed.

  1. Speciation and the structure of lead(II) in hyper-alkaline aqueous solution.

    PubMed

    Bajnóczi, Eva G; Pálinkó, István; Körtvélyesi, Tamás; Bálint, Szabolcs; Bakó, Imre; Sipos, Pál; Persson, Ingmar

    2014-12-14

    The identity of the predominating lead(ii) species in hyper-alkaline aqueous solution has been determined by Raman spectroscopy, and ab initio quantum chemical calculations and its structure has been determined by EXAFS. The observed and calculated Raman spectra for the [Pb(OH)3](-) complex are in agreement while they are different for two-coordinated complexes and complexes containing Pb[double bond, length as m-dash]O double bonds. Predicted bond lengths are also consistent with the presence of [Pb(OH)3](-) and exclude the formation of Pb[double bond, length as m-dash]O double bond(s). These observations together with experimentally established analogies between lead(ii) and tin(ii) in hyper-alkaline aqueous solutions suggest that the last stepwise hydroxido complex of lead(ii) is [Pb(OH)3](-). The Pb-O bond distance in the [Pb(OH)3](-) complex as determined is remarkably short, 2.216 Å, and has low symmetry as no multiple back-scattering is observed. The [Pb(OH)3](-) complex has most likely trigonal pyramidal geometry as all reported three-coordinated lead(ii) complexes in the solid state. From single crystal X-ray data, the bond lengths for O-coordinated lead(ii) complexes with low coordination numbers are spread over an unusually wide interval, 2.216-2.464 Å for N = 3. The Pb-O bond distance is at the short side and within the range of three coordinated complexes, as also observed for the trihydroxidostannate(ii) complex indicating that the hydroxide ion forms short bonds with d(10)s(2) metal ions with occupied anti-bonding orbitals.

  2. River solute fluxes reflecting active hydrothermal chemical weathering of the Yellowstone Plateau Volcanic Field, USA

    USGS Publications Warehouse

    Hurwitz, S.; Evans, William C.; Lowenstern, J. B.

    2010-01-01

    In the past few decades numerous studies have quantified the load of dissolved solids in large rivers to determine chemical weathering rates in orogenic belts and volcanic areas, mainly motivated by the notion that over timescales greater than ~100kyr, silicate hydrolysis may be the dominant sink for atmospheric CO2, thus creating a feedback between climate and weathering. Here, we report the results of a detailed study during water year 2007 (October 1, 2006 to September 30, 2007) in the major rivers of the Yellowstone Plateau Volcanic Field (YPVF) which hosts Earth's largest "restless" caldera and over 10,000 thermal features. The chemical compositions of rivers that drain thermal areas in the YPVF differ significantly from the compositions of rivers that drain non-thermal areas. There are large seasonal variations in river chemistry and solute flux, which increases with increasing water discharge. The river chemistry and discharge data collected periodically over an entire year allow us to constrain the annual solute fluxes and to distinguish between low-temperature weathering and hydrothermal flux components. The TDS flux from Yellowstone Caldera in water year 2007 was 93t/km2/year. Extensive magma degassing and hydrothermal interaction with rocks accounts for at least 82% of this TDS flux, 83% of the cation flux and 72% of the HCO3- flux. The low-temperature chemical weathering rate (17t/km2/year), calculated on the assumption that all the Cl- is of thermal origin, could include a component from low-temperature hydrolysis reactions induced by CO2 ascending from depth rather than by atmospheric CO2. Although this uncertainty remains, the calculated low-temperature weathering rate of the young rhyolitic rocks in the Yellowstone Caldera is comparable to the world average of large watersheds that drain also more soluble carbonates and evaporates but is slightly lower than calculated rates in other, less-silicic volcanic regions. Long-term average fluxes at

  3. Phenomenon and mechanism of capsule shrinking in alkaline solution containing calcium ions.

    PubMed

    She, Shupeng; Shan, Bowen; Li, Qinqin; Tong, Weijun; Gao, Changyou

    2012-11-15

    Shrinking phenomenon of poly(allylamine hydrochloride) (PAH)/poly(styrene sulfonate, sodium salt) (PSS) multilayer microcapsules was observed when they were incubated in alkaline solutions containing Ca(2+). The shrinking was universal to those polyelectrolyte multilayer capsules regardless of the wall thickness and wall compositions suppose the conditions were proper. The shrinking extent increased along with the increase of solution pH and Ca(2+) concentration, and reached to a maximum value of 70% (from 7.4 to 2.3 μm). The shrunk capsules with a hollow structure and thick wall could well maintain their spherical shape in a dry state. During the capsule shrinking partial loss of the polyelectrolytes especially PSS took place, and the loss amount increased along with the increase of solution pH although the alteration patterns were different at lower Ca(2+) concentration. The complexation of PSS with Ca(2+), which is believed one of the major reasons governing the capsule shrinking, was demonstrated by X-ray photoelectron spectroscopy and turbidity experiment. The mechanism is proposed, which relies on the synergistic effects of deprotonation of PAH and screening of PSS by Ca(2+) leading to the thermodynamically favored-capsule shrinking.

  4. Evaluation of alkaline electrolyzed water to replace traditional phosphate enhancement solutions: Effects on water holding capacity, tenderness, and sensory characteristics.

    PubMed

    Rigdon, Macc; Hung, Yen-Con; Stelzleni, Alexander M

    2017-01-01

    Sixty-four pork loins were randomly assigned to one of four treatments to evaluate the use of alkaline electrolyzed reduced water as a replacement for traditional enhancement solutions. Treatments included: alkaline electrolyzed reduced water (EOH; pH≈11.5), EOH plus 2.5% potassium-lactate (EOK), industry standard (IS; 0.35% sodium tri-polyphosphate, 0.14% sodium chloride, 2.5% potassium-lactate), and no enhancement (CON). After enhancement (targeting 110%) and rest period, chops were cut (2.54-cm) to test treatment effects on water holding capacity, Warner-Bratzler shear force (WBSF), and sensory attributes. Despite its alkaline nature EOH chops exuded more water (P<0.05) than EOK, IS, or CON chops. Control chops were similar (P>0.05) to EOK, however CON and EOK both lost more moisture (P<0.05) than IS. The use of alkaline electrolyzed reduced water did not improve WBSF or sensory characteristics compared to IS treated chops. As a stand-alone enhancement solution alkaline electrolyzed reduced water was not a suitable replacement for industry standard solutions.

  5. Americium/Lanthanide Separations in Alkaline Solutions for Advanced Nuclear Fuel Cycles

    SciTech Connect

    Goff, George S.; Long, Kristy Marie; Reilly, Sean D.; Jarvinen, Gordon D.; Runde, Wolfgang H.

    2012-06-11

    Project goals: Can used nuclear fuel be partitioned by dissolution in alkaline aqueous solution to give a solution of uranium, neptunium, plutonium, americium and curium and a filterable solid containing nearly all of the lanthanide fission products and certain other fission products? What is the chemistry of Am/Cm/Ln in oxidative carbonate solutions? Can higher oxidation states of Am be stabilized and exploited? Conclusions: Am(VI) is kinetically stable in 0.5-2.0 M carbonate solutions for hours. Aliquat 336 in toluene has been successfully shown to extract U(VI) and Pu(VI) from carbonate solutions. (Stepanov et al 2011). Higher carbonate concentration gives lower D, SF{sub U/Eu} for = 4 in 1 M K{sub 2}CO{sub 3}. Experiments with Am(VI) were unsuccessful due to reduction by the organics. Multiple sources of reducing organics...more optimization. Reduction experiments of Am(VI) in dodecane/octanol/Aliquat 336 show that after 5 minutes of contact, only 30-40% of the Am(VI) has been reduced. Long enough to perform an extraction. Shorter contact times, lower T, and lower Aliquat 336 concentration still did not result in any significant extraction of Am. Anion exchange experiments using a strong base anion exchanger show uptake of U(VI) with minimal uptake of Nd(III). Experiments with Am(VI) indicate Am sorption with a Kd of 9 (10 minute contact) but sorption mechanism is not yet understood. SF{sub U/Nd} for = 7 and SF{sub U/Eu} for = 19 after 24 hours in 1 M K{sub 2}CO{sub 3}.

  6. Chemistry of submarine hydrothermal solutions at 21 °N, East Pacific Rise

    NASA Astrophysics Data System (ADS)

    Von Damm, K. L.; Edmond, J. M.; Grant, B.; Measures, C. I.; Walden, B.; Weiss, R. F.

    1985-11-01

    The three hydrothermal fields at 21°N latitude, East Pacific Rise, were resampled and an additional one was discovered. Maximum fluid temperatures observed were within a few degrees of 350°C and these waters had concentrations of Mg and sulfate indistinguishable from zero. One field, NGS, which had active 350°C springs in 1979, was inactive when first located in 1981. However, when a chimney was broken open during sampling, water issued at 273°C and continued to flow for at least five days. The chemical composition strongly suggests that these waters cooled conductively from 350°C in the sealed conduit. The major ion data are consistent with the estimates based on extrapolation of the original measurements made on the hot springs from the Galapagos Spreading Center ( EDMONDet al., 1979a). The fluids have a pH of 3.5 and the sulfide-forming element concentrations show significant inter-field variations. Fe levels range from 0.8 to 2.4 mmoles/kg; the ratio Fe:Mn varies from 0.9 to 2.9 similar to metalliferous sediments on the ridge flanks, but much higher than observed at Galapagos (where sub-surface precipitation of iron sulfides occurs) indicating that the overwhelming proportion of the mass flux from hydrothermal systems occurs at high temperatures. Zn ranges from 40 to 106 μmoles/kg with Cu being substantially lower. Since the ratio of these elements in tholeiites is about unity, there is strong net preferential mobilization of Zn. Lead ranges from 183 to 359 nmoles/kg. Nickel and Be are highly immobile relative to the other trace elements. The abundance of H 2S is about three times that of the total sulfide-forming cations. These data demonstrate that acid solutions at elevated temperatures can transport substantial amounts of ore-forming elements in the presence of large excesses of sulfide.

  7. Modeling experimental results of diffusion of alkaline solutions through a compacted bentonite barrier

    SciTech Connect

    Fernandez, Raul; Cuevas, Jaime; Maeder, Urs K.

    2010-08-15

    The interaction between concrete/cement and swelling clay (bentonite) has been modeled in the context of engineered barrier systems for deep geological disposal of high-level radioactive waste. The geochemical transformations observed in laboratory diffusion experiments at 60 and 90 {sup o}C between bentonite and different high-pH solutions (K-Na-OH and Ca(OH){sub 2}-saturated) were reconciled with the reactive transport code CrunchFlow. For K-Na-OH solutions (pH = 13.5 at 25 {sup o}C) partial dissolution of montmorillonite and precipitation of Mg-silicates (talc-like), hydrotalcite and brucite at the interface are predicted at 60 {sup o}C, while at 90 {sup o}C the alteration is wider. Alkaline cations diffused beyond the mineralogical alteration zone by means of exchange with Mg{sup 2+} in the interlayer region of montmorillonite. Very slow reactivity and minor alteration of the clay are predicted in the Ca(OH){sub 2}-bentonite system. The model is a reasonable description of the experiments but also demonstrates the difficulties in modeling processes operating at a small scale under a diffusive regime.

  8. Effects of Alkali and Alkaline Earth Cocations on the Activity and Hydrothermal Stability of Cu/SSZ-13 NH3-SCR Catalysts

    SciTech Connect

    Gao, Feng; Wang, Yilin; Washton, Nancy M.; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-10-13

    Using a three-step aqueous solution ion-exchange method, cocation modified Cu/SSZ-13 SCR catalysts were synthesized. These catalysts, in both fresh and hydrothermally aged forms, were characterized with several methods including temperature-programmed reduction by H2 (H2-TPR), temperature-programmed desorption of NH3 (NH3-TPD), and 27Al solid-state nuclear magnetic resonance (NMR) and diffuse reflectance Infrared Fourier Transform (DRIFT) spectroscopies. Their catalytic performance was probed using steady-state standard NH3-SCR. Characterization results indicate that cocations weaken interactions between Cu-ions and the CHA framework making them more readily reducible. By removing a portion of Brønsted acid sites, cocations also help to mitigate hydrolysis of the zeolite catalysts during hydrothermal aging as evidenced from 27Al NMR. Reaction tests show that certain cocations, especially Li+ and Na+, promote low-temperature SCR rates while others show much less pronounced effects. In terms of applications, our results indicate that introducing cocations can be a viable strategy to improve both low- and high-temperature performance of Cu/SSZ-13 SCR catalysts.

  9. Hydrothermal synthesis and properties of controlled α-Fe2O3 nanostructures in HEPES solution.

    PubMed

    Li, Hui; Lu, Zhong; Li, Qin; So, Man-Ho; Che, Chi-Ming; Chen, Rong

    2011-09-05

    A facile, template-free, and environmentally friendly hydrothermal strategy was explored for the controllable synthesis of α-Fe(2)O(3) nanostructures in HEPES solution (HEPES=2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid). The effects of experimental parameters including HEPES/FeCl(3) molar ratio, pH value, reaction temperature, and reaction time on the formation of α-Fe(2)O(3) nanostructures have been investigated systematically. Based on the observations of the products, the function of HEPES in the reaction is discussed. The different α-Fe(2)O(3) nanostructures possess different optical, magnetic properties, and photocatalytic activities, depending on the shape and size of the sample. In addition, a novel and facile approach was developed for the synthesis of Au/α-Fe(2)O(3) and Ag/α-Fe(2)O(3) nanocomposites in HEPES buffer solution; this verified the dual function of HEPES both as reductant and stabilizer. This work provides a new strategy for the controllable synthesis of transition metal oxide nanostructures and metal-supported nanocomposites, and gives a strong evidence of the relationship between the property and morphology/size of nanomaterials.

  10. Influence of solution viscosity on hydrothermally grown ZnO thin films for DSSC applications

    NASA Astrophysics Data System (ADS)

    Marimuthu, T.; Anandhan, N.; Thangamuthu, R.; Surya, S.

    2016-10-01

    Zinc oxide (ZnO) nanowire arrays (NWAs) were grown onto zinc oxide-titanium dioxide (ZnO-TiO2) seeded fluorine doped tin oxide (FTO) conductive substrate by hydrothermal technique. X-ray diffraction (XRD) patterns depict that ZnO thin films are preferentially oriented along the (002) plane with hexagonal wurtzite structure. Viscosity measurements reveal that viscosity of the solutions linearly increases as the concentrations of the polyvinyl alcohol (PVA) increase in the growth solution. Field emission scanning electron microscope (FE-SEM) images show that the NWAs are vertically grown to seeded FTO substrate with hexagonal structure, and the growth of NWAs decreases as the concentration of the PVA increases. Stylus profilometer and atomic force microscopic (AFM) studies predict that the thickness and roughness of the films decrease with increasing the PVA concentrations. The NWAs prepared at 0.1% of PVA exhibits a lower transmittance and higher absorbance than that of the other films. The band gap of the optimized films prepared at 0.0 and 0.1% of PVA is found to be 3.270 and 3.268 eV, respectively. The photo to current conversion efficiency of the DSSC based on photoanodes prepared at 0.0 and 0.1% of PVA exhibits about 0.64 and 0.82%, respectively. Electrochemical impedance spectra reveal that the DSSC based on photoanode prepared at 0.1% of PVA has the highest charge transfer recombination resistance.

  11. Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

    SciTech Connect

    Mah, V.; Jalilehvand, F.

    2009-05-19

    The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes were evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg

  12. Uranium mobility during interaction of rhyolitic glass with alkaline solutions: dissolution of glass

    USGS Publications Warehouse

    Zielinski, Robert A.

    1977-01-01

    This report concerns investigations designed to identify the important physical and chemical parameters influencing the rate of release of uranium from glass shards of rhyolitic air-fall ash. Oxidizing, silica undersaturated, alkaline solutions are eluted through a column of rhyolitic glass shards at a carefully controlled temperature, pressure, and flow rate. The solutions are monitored for the concentration of uranium and selected additional elements (Si, K, Li, F), and the glass is recovered and examined for physical and/or chemical evidence of attack. The flushing mode is designed to mimic leaching of glass shards by intermittent, near-surface waters with which the glass is not in equilibrium. Reported rates are applicable only to the experimental conditions (120?C, 7,000 psi), but it is assumed that the reaction mechanisms and the relative importance of rate-influencing parameters remain unchanged, at reduced temperature and pressure. Results of the above experiment indicate that silica and uranium are released from glass shards at comparable rates, while lithium and potassium are released faster and fluorine slower than either Si or U. Rates of release of silica and uranium correlate positively with the surface area of the shards. Rhyolitic shards release uranium at faster rates than rhyodacitic shards of comparable surface area. Changes in the shards resulting from experimental treatment and observed in the original glass separates from an Oligocene ash (compared to a Pleistocene ash) include; surface pitting, increased surface area, devitrification rinds (<1l micron wide) and reduced lithium contents. Future investigations will study the effect of temperature, pressure, solution composition, and flow rate on the relative mobility of U, Si, Li, F, and K.

  13. Critical anomalies of alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water

    NASA Astrophysics Data System (ADS)

    Du, Zhongyu; Yin, Handi; Hao, Zhiguo; Zheng, Peizhu; Shen, Weiguo

    2013-12-01

    We have used three-wavelength UV-spectrophotometry to study the reaction of the alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water. It was found that when the temperature was far away from the critical point, the values of the natural logarithm of the rate constant k and the natural logarithm of the chemical equilibrium K determined in our experiments had good linear relationships with the reciprocal of temperature, which served as the backgrounds and were used for correcting k and K in the critical region. The critical slowing down of the reaction and the critical anomaly of the chemical equilibrium were detected near the critical point. The value of the critical exponent characterizing the slowing down effect of the reaction rate was obtained to be 0.156, which was close to the value 0.11 associated with the heat capacity divergence and agreed with the theoretical prediction. The experimental result also confirmed the theoretical prediction of 0.11 for the critical exponent characterizing the weak divergence of the singularity of the chemical equilibrium.

  14. Structural and thermal characterization of hemicelluloses isolated by organic solvents and alkaline solutions from Tamarix austromongolica.

    PubMed

    Sun, Yong-Chang; Wen, Jia-Long; Xu, Feng; Sun, Run-Cang

    2011-05-01

    Three organosolv and three alkaline hemicellulosic fractions were prepared from lignocellulosic biomass of the fast-growing shrub Tamarix austromongolica (Tamarix Linn.). Sugar analysis revealed that the organosolv-soluble fractions contained a higher content of glucose (33.7-6.5%) and arabinose (14.8-5.6%), and a lower content of xylose (62.2-54.8%) than the hemicellulosic fractions isolated with aqueous alkali solutions. A relatively high concentration of alkali resulted in a decreasing trend of the xylose/4-O-methyl-D-glucuronic acid ratio in the alkali-soluble fractions. The results of NMR analysis supported a major substituted structure based on a linear polymer of β-(1→4)-linked d-xylopyranosyl residues, having ramifications of α-L-arabinofuranose and 4-O-methyl-D-glucuronic acid residues monosubstituted at O-3 and O-2, respectively. Thermogravimetric analysis revealed that one step of major mass loss occurred between 200-400°C, as hemicelluloses devolatilized with total volatile yield of about 55%. It was found that organosolv-soluble fractions are more highly ramified, and showed a higher thermal stability than the alkali-soluble fractions.

  15. Spectroscopic study of the authentic emitter of AMPPD chemiluminescence in alkaline aqueous solution.

    PubMed

    Tu, Langping; Wang, Yu; Yang, Yifei; Bakker, Bert H; Kong, Xianggui; Brouwer, Albert M; Buma, Wybren J; Zhang, Hong

    2010-07-07

    To design more effective CIEEL (chemically initiated electron exchange luminescence) systems demands a complete picture of the dynamics of the chemiluminescence, which is often a challenge. In this work, photoluminescence of the methyl m-oxybenzoate anion - the authentic emitter of AMPPD (3-[2-spiroadamantane]-4-methoxy-4-[3-phosphoryloxy]-phenyl-1,2-dioxetane) in aqueous solvent has been studied. Combining the effect of solvent properties, e.g. pH value, and spectroscopic studies employing steady-state and ultrafast time-resolved emission and absorption and (1)H NMR techniques, a novel mechanism is proposed. We conclude that the deviation of emission peaks between chemiluminescence and photoluminescence of the authentic emitter of AMPPD i.e. the methyl m-oxybenzoate anion, in alkaline aqueous solvents is due to its hydrolysis, rather than the hydrogen-bonding effect as has been assumed so far. Besides, the hydrogen-bonding is suggested to play a key role in significantly decreasing the chemiluminescence yield of AMPPD in aqueous solution by shortening the lifetime of the excited authentic emitter to 10 ps order of magnitude - three orders of magnitude shorter than the previously reported value ( approximately 10 ns). These results shed light on the chemiluminescence dynamics of AMPPD and facilitate the design of more effective CIEEL systems.

  16. The electrochemical behaviour of copper in alkaline solutions containing fluoride, studied by in situ ellipsometry

    NASA Astrophysics Data System (ADS)

    Berlouis, L. E. A.; Mamman, D. A.; Azpuru, I. G.

    1998-06-01

    In situ ellipsometry has been used to reveal a number of interesting features in the growth of passivating films on Cu in 0.1 M KOH containing KF. Fluoride ions are shown to affect the growth of the oxide layer and enhanced dissolution of copper as the Cu II species occurs as a result of stress corrosion cracking. A restructuring of the oxide film within the passive region is attributed to loss of water and this effect becomes less distinct with increasing F - ion concentration in the electrolyte and disorder in the oxide layer. The enhanced reduction of the conductively inhibited bulk CuO/Cu(OH) 2 layer back to copper found in alkaline solutions containing fluoride would indicate that the formation of this layer is the dominant one for passivation of copper in this medium. The difference between the start and the end Δ- Ψ values of the metal surface of the cyclic voltammogram at -1.5 V versus SCE indicates either roughening arising from the oxide formation/reduction or the presence of a residual surface oxide.

  17. Reaction rate modeling in cryoconcentrated solutions: alkaline phosphatase catalyzed DNPP hydrolysis.

    PubMed

    Champion, D; Blond, G; Le Meste, M; Simatos, D

    2000-10-01

    The hydrolysis of disodium p-nitrophenyl phosphate catalyzed by alkaline phosphatase was chosen as a model to study the kinetics of changes in frozen food products. The initial reaction rate was determined in concentrated sucrose solutions down to -24 degrees C, and the enzymatic characteristics K(M) and V(max) were calculated. The experimental data were compared to the kinetics predicted by assuming that the reaction was viscosity dependent. Indeed, an analysis of the enzymatic reaction demonstrated that both the diffusion of the substrate and the flexibility of the enzyme segments were controlled by the high viscosity of the media. When the temperature was too low for the viscosity to be measured simply, the Williams-Landel-Ferry equation was used to predict the viscosity, taking, as reference temperature, the glass transition temperature (T(g)) corresponding to the concentration of the freeze-concentrated phase at the test temperature. Predicted values of the reaction rate were very close to the experimental ones in the studied temperature range.

  18. The inhibition of the spongy electrocrystallization of zinc from doped flowing alkaline zincate solutions

    NASA Astrophysics Data System (ADS)

    Wen, Yue-hua; Cheng, Jie; Zhang, Li; Yan, Xu; Yang, Yu-sheng

    The effects of the presence of additives like lead and tungstate ions in flowing alkaline zincate solutions on suppressing spongy zinc electrogrowth are examined. The results show that the two additives with optimal concentrations in flowing electrolytes can suppress spongy zinc initiation and propagation. And, the two additives can bring about more uniform and compact deposits and, thereby, reduce spongy zinc growth. The influence of lead and tungstate ions on the zinc deposition/dissolution is evaluated by cyclic voltammetry. It also shows that the addition of the two additives is largely a blocking action, and the co-deposition of lead and zinc ions may occur. The performance of the zinc-air flow battery with zinc regeneration electrolysis is determined. It shows that by the addition of 0.6 M Na 2WO 4 or 10 -4 M to 10 -3 M lead, compact or mixed compact-spongy zinc deposits are created and the favorable charge/discharge performance of the battery is achieved with an energy efficiency of approximately 60%.

  19. Speciation and structure of tin(II) in hyper-alkaline aqueous solution.

    PubMed

    Bajnóczi, Eva G; Czeglédi, Eszter; Kuzmann, Ernő; Homonnay, Zoltán; Bálint, Szabolcs; Dombi, György; Forgo, Péter; Berkesi, Ottó; Pálinkó, István; Peintler, Gábor; Sipos, Pál; Persson, Ingmar

    2014-12-28

    The identity of the predominating tin(ii)-hydroxide complex formed in hyper-alkaline aqueous solutions (0.2 ≤CNaOH≤ 12 mol dm(-3)) is determined by potentiometric titrations, Raman, Mössbauer and XANES spectroscopy, supplemented by quantum chemical calculations. Thermodynamic studies using a H2/Pt electrode up to free hydroxide concentrations of 1 mol dm(-3) showed the presence of a single monomeric complex with a tin(II) : hydroxide ratio of 1 : 3. This observation together with Raman and Mössbauer spectroscopic measurements supplemented by quantum mechanical calculations proved that the predominating complex is [Sn(OH)3](-), and that the presence of the other possible complex, [SnO(OH)](-), could not be proven with either experiments or simulations. The structure of the trihydroxidostannate(II) complex, [Sn(OH)3](-), was determined by EXAFS and was found to be independent of the applied hydroxide and tin(II) concentrations. The mean Sn-O bond distance is short, 2.078 Å, and in very good agreement with the only structure reported in the solid state. It is also shown that at pH values above 13 the speciation of the predominant trihydroxidostannate(II) complex is not affected by the presence of high concentrations of chloride ions.

  20. Characteristics of hydrolysis of the complex Na2SnF6 in hydrothermal solutions-An experimental study

    USGS Publications Warehouse

    Wang, Y.; I-Ming, C.

    1987-01-01

    Characteristics of hydrolysis of the complex Na2SnF6, which is used as the starting material, in hydrothermal solutions have been studied at 200-602??C and 1 kbar. Experimental results show that intense hydrolysis of Na2SnF6 occurs at high temperatures and that with the rise of temperature the hydrolysis will become more intense. Under the present experimental conditions the most possible existing form of Sn in the hydrothermal solutions is SnF3(OH) or Na2SnF3(OH). In addition, the hydrolysis constants for Na2SnF6 have also been calculated at 200-602??C, and the relationship between Na2SnF6 hydrolysis and temperature is discussed. ?? 1987 Science Press.

  1. Kinetics of quartz dissolution in electrolyte solutions using a hydrothermal mixed flow reactor

    NASA Astrophysics Data System (ADS)

    Dove, Patricia M.; Crerar, David A.

    1990-04-01

    A hydrothermal mixed flow reactor has been developed to study the reaction kinetics of a wide variety of mineral/solution systems. The reactor is constructed of commercially pure titanium to minimize corrosion and operates at temperatures of 25 to 300°C and pressures up to 124 bars. This system is used to measure the dissolution rates of quartz at near-neutral pH in 0.0 to 0.15 m solutions of NaCl, KCl, LiCl, MgCl 2 over a temperature range of 100 to 300°C. In all cases, small concentrations of electrolytes increase the rate, some by as much as 1.5 orders of magnitude above the values measured for deionized water. The effect is greatest for solutions of NaCl and KCl where reaction rates increase with increasing electrolyte concentrations up to 0.05 molal and become constant at higher molalities. Smaller rate increases are observed for LiCl and MgCl 2 solutions. The first-order rate equation for quartz dissolution in pure water at temperatures of 100 to 300°C is given by r H 4sio 4 = k +(a sio2)(a H 2o ) 2(1 - Q/K) for a standard system of 1 m 2 of surface area and 1 kg of solution. The addition of electrolytes to reacting solutions at near-neutral pH accelerates the rate according to a Langmuir adsorption model and has the form r H 4sio 4 = (k + + k adK me +/1 + k me +)(a sio2)(a H 2o ) 2(1 - Q/K). m me + Analysis of the data indicates that the observed rate increases are controlled by the identity and concentration of the cation where alkali cations coordinate with the surface to increase the reactivity of siloxane groups by disrupting the structure of the mineral-solution interface. The rate-limiting step for the dissolution mechanism is described by (Si - O - Si) + H 2O = (Si - O - Si · OH 2)† → 2(Si - O - H) where the intermediate species is probably the same in deionized water and electrolyte solutions, but the reaction frequency is higher in electrolyte solutions due to increases in the accessibility of water to the mineral surface structures

  2. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

    DOE PAGES

    Liu, Shizhong; White, Michael G.; Liu, Ping

    2016-06-30

    Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e– or 4e– transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e– transfers is identified, where the reduction stepsmore » via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH–(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e– transfer mechanism.« less

  3. Conformational instability of the N- and C-terminal lobes of porcine pepsin in neutral and alkaline solutions.

    PubMed Central

    Lin, X.; Loy, J. A.; Sussman, F.; Tang, J.

    1993-01-01

    Pepsin contains, in a single chain, two conformationally homologous lobes that are thought to have been evolutionarily derived by gene duplication and fusion. We have demonstrated that the individual recombinant lobes are capable of independent folding and reconstitution into a two-chain pepsin or a two-chain pepsinogen (Lin, X., et al., 1992, J. Biol. Chem. 267, 17257-17263). Pepsin spontaneously inactivates in neutral or alkaline solutions. We have shown in this study that the enzymic activity of the alkaline-inactivated pepsin was regenerated by the addition of the recombinant N-terminal lobe but not by the C-terminal lobe. These results indicate that alkaline inactivation of pepsin is due to a selective denaturation of its N-terminal lobe. A complex between recombinant N-terminal lobe of pepsinogen and alkaline-denatured pepsin has been isolated. This complex is structurally similar to a two-chain pepsinogen, but it contains an extension of a denatured pepsin N-terminal lobe. Acidification of the complex is accompanied by a cleavage in the pro region and proteolysis of the denatured N-terminal lobe. The structural components that are responsible for the alkaline instability of the N-terminal lobe are likely to be carboxyl groups with abnormally high pKa values. The electrostatic potentials of 23 net carboxyl groups in the N-terminal domain (as compared to 19 in the C-terminal domain) of pepsin were calculated based on the energetics of interacting charges in the tertiary structure of the domain. The groups most probably causing the alkaline denaturation are Asp11, Asp159, Glu4, Glu13, and Asp118.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8401224

  4. Zinc(II) oxide stability in alkaline sodium phosphate solutions at elevated temperatures

    SciTech Connect

    Ziemniak, S.E.; Opalka, E.P.

    1993-04-01

    Zinc oxide (ZnO) is shown to transform into either of two phosphate-containing compounds in relatively dilute alkaline sodium phosphate solutions at elevated temperatures via ZnO(s) + Na{sup +} + H{sub 2}PO{sub 4}{sup {minus}} {r_reversible} NaZnPO{sub 4}(s) + H{sub 2}O or 2 ZnO(s) + H{sub 3}PO{sub 4}(aq) {r_reversible} Zn{sub 2}(OH)PO{sub 4}(s) + H{sub 2}O. X-ray diffraction analyses indicate that NaZnPO{sub 4} possesses an orthorhombic unit cell having lattice parameters a = 8.710 {+-} 0.013, b = 15.175 {+-} 0.010, and c = 8.027 {+-} 0.004 {angstrom}. The thermodynamic equilibria for these reactions were defined in the system ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O for Na/P molar ratios between 2.1 and 3. Based on observed reaction threshold values for sodium phosphate concentration and temperature, the standard entropy (S{degrees}) and free energy of formation ({Delta}G{sub f}{degrees}) for NaZnPO{sub 4} were calculated to be 169.0 J/mol-K and {minus}1510.6 kJ/mol, respectively; similar values for Zn{sub 2}(OH)PO{sub 4} (tarbuttite) were 235.9 J/mol-K and {minus}1604.6 kJ/mol. Additions of sodium sulfite and sulfate did not alter the above reactions.

  5. Batch and dynamic biosorption of basic dyes from binary solutions by alkaline-treated cypress cone chips.

    PubMed

    Fernandez, M E; Nunell, G V; Bonelli, P R; Cukierman, A L

    2012-02-01

    A simple alkaline pre-treatment of Cupressus sempervirens cone chips was performed to improve their biosorption capacity towards methylene blue and rhodamine B from aqueous solutions, in batch and continuous modes. Biosorption kinetics were determined from single and binary dyes solutions, and properly described by the pseudo-second-order rate model. Experimental single-dye equilibrium isotherms fitted the Langmuir-Freundlich model, with maximum biosorption capacities of 0.68mmol/g for methylene blue and 0.50mmol/g for rhodamine B. Single-dye dynamic biosorption showed that breakthrough time for methylene blue biosorption was almost four times longer than for rhodamine B and that the alkaline modification of the chips greatly improved the biosorption performance. Competitive dynamic biosorption demonstrated the preference of the modified cone chips for biosorbing methylene blue, confirmed by the exit concentration overshoots obtained in the breakthrough curves of rhodamine B.

  6. Growth of tourmaline single crystals containing transition metal elements in hydrothermal solutions

    NASA Astrophysics Data System (ADS)

    Setkova, Tatiana; Shapovalov, Yury; Balitsky, Vladimir

    2011-03-01

    Interest in the growth of tourmaline single crystals is based on the promising piezoelectric and pyroelectric properties of this material compared to quartz crystals currently in use. Moreover, synthetic tourmaline can be used as a substitute for the natural stone in the jewelry industry similar to other synthetic analogues of gemstones. Single crystals of colored Co-, Ni-, Fe-, (Ni,Cr)-, (Ni,Fe)-, and (Co,Ni,Cr)-containing tourmalines with concentration of transition metal elements up to 16 wt% on a seed have been grown from complex boron-containing hydrothermal solutions at a range of temperatures 400-750 °C and pressures 100 MPa. Experiments were conducted under conditions of a thermal gradient in titanium and chromium-nickel autoclaves. Tourmaline growth on a seed crystal occurs only if separate tourmaline-forming components (monocrystalline corundum and quartz bars) are used as charge. All tourmalines specified above grow in analogous (+) direction of the optical axis with a speed of 0.05 mm/day by faces of the trigonal pyramid, except tourmalines containing chromium. They grow in analogous (+0001) direction with a speed 0.05 mm/day, and in antilogous (-0001) direction with a speed of 0.01 mm/day by faces of the trigonal pyramid and in prism direction with a speed of 0.001 mm/day. Along with the large single crystals, a great amount of finest (30-150 μm in size) tourmaline crystals was formed during the runs by spontaneous nucleation both on the surface of the seed crystals and in the charge.

  7. Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

    USGS Publications Warehouse

    Bassett, William A.; Anderson, Alan J.; Mayanovic, Robert A.; Chou, I.-Ming

    2000-01-01

    A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

  8. Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

    DOEpatents

    Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

    1994-01-01

    A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

  9. The effects of alkalinity and acidity of process water and hydrochar washing on the adsorption of atrazine on hydrothermally produced hydrochar.

    PubMed

    Flora, Justine F R; Lu, Xiaowei; Li, Liang; Flora, Joseph R V; Berge, Nicole D

    2013-11-01

    Hydrothermal carbonization of simulated food waste was performed at 250 °C for 20 h using deionized water (DI) and 0.01 N solutions of HCl, NaCl, and NaOH. The hydrochars produced were washed with acetone and the adsorptive capacity of the washed and unwashed hydrochars for atrazine were characterized. Using a generalized linear model, it was shown that the adsorptive capacity of the washed hydrochar was significantly higher than that of the unwashed hydrochars. The HCl processed unwashed hydrochar has a slightly higher adsorptive capacity compared to the DI processed hydrochar while both the NaOH processed washed and unwashed hydrochars were slightly lower than the corresponding DI processed hydrochars. (13)C solid-state NMR results showed no discernible differences in surface functional groups among the washed hydrochars and among the unwashed hydrochars. A clear decrease in alkyl groups and an increase in aromatic/olefinic-C groups were observed after acetone washing. (1)H liquid-phase NMR showed carbon alkyl chains were present in the acetone wash. Interaction energies calculated using dispersion corrected density functional theory show that atrazine is more strongly adsorbed to surfaces without weakly associated alkyl groups.

  10. Removal of dissolved actinides from alkaline solutions by the method of appearing reagents

    DOEpatents

    Krot, Nikolai N.; Charushnikova, Iraida A.

    1997-01-01

    A method of reducing the concentration of neptunium and plutonium from alkaline radwastes containing plutonium and neptunium values along with other transuranic values produced during the course of plutonium production. The OH.sup.- concentration of the alkaline radwaste is adjusted to between about 0.1M and about 4M. [UO.sub.2 (O.sub.2).sub.3 ].sup.4- ion is added to the radwastes in the presence of catalytic amounts of Cu.sup.+2, Co.sup.+2 or Fe.sup.+2 with heating to a temperature in excess of about 60.degree. C. or 85.degree. C., depending on the catalyst, to coprecipitate plutonium and neptunium from the radwaste. Thereafter, the coprecipitate is separated from the alkaline radwaste.

  11. Removal of dissolved actinides from alkaline solutions by the method of appearing reagents

    SciTech Connect

    Krot, N.N.; Charushnikova, I.A.

    1997-06-17

    A method is described for reducing the concentration of neptunium and plutonium from alkaline radwastes containing plutonium and neptunium values along with other transuranic values produced during the course of plutonium production. The OH{sup {minus}} concentration of the alkaline radwaste is adjusted to between about 0.1M and about 4M. [UO{sub 2}(O{sub 2}){sub 3}]{sup 4{minus}} ion is added to the radwastes in the presence of catalytic amounts of Cu{sup +2}, Co{sup +2} or Fe{sup +2} with heating to a temperature in excess of about 60 C or 85 C, depending on the catalyst, to coprecipitate plutonium and neptunium from the radwaste. Thereafter, the coprecipitate is separated from the alkaline radwaste. 2 figs.

  12. Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

    SciTech Connect

    Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L.

    1996-06-06

    Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed.

  13. Spatial and temporal geochemical trends in the hydrothermal system of Yellowstone National Park: Inferences from river solute fluxes

    USGS Publications Warehouse

    Hurwitz, S.; Lowenstern, J. B.; Heasler, H.

    2007-01-01

    We present and analyze a chemical dataset that includes the concentrations and fluxes of HCO3-, SO42-, Cl-, and F- in the major rivers draining Yellowstone National Park (YNP) for the 2002-2004 water years (1 October 2001 - 30 September 2004). The total (molar) flux in all rivers decreases in the following order, HCO3- > Cl- > SO42- > F-, but each river is characterized by a distinct chemical composition, implying large-scale spatial heterogeneity in the inputs of the various solutes. The data also display non-uniform temporal trends; whereas solute concentrations and fluxes are nearly constant during base-flow conditions, concentrations decrease, solute fluxes increase, and HCO3-/Cl-, and SO42-/Cl- increase during the late-spring high-flow period. HCO3-/SO42- decreases with increasing discharge in the Madison and Falls Rivers, but increases with discharge in the Yellowstone and Snake Rivers. The non-linear relations between solute concentrations and river discharge and the change in anion ratios associated with spring runoff are explained by mixing between two components: (1) a component that is discharged during base-flow conditions and (2) a component associated with snow-melt runoff characterized by higher HCO3-/Cl- and SO42-/Cl-. The fraction of the second component is greater in the Yellowstone and Snake Rivers, which host lakes in their drainage basins and where a large fraction of the solute flux follows thaw of ice cover in the spring months. Although the total river HCO3- flux is larger than the flux of other solutes (HCO3-/Cl- ??? 3), the CO2 equivalent flux is only ??? 1% of the estimated emission of magmatic CO2 soil emissions from Yellowstone. No anomalous solute flux in response to perturbations in the hydrothermal system was observed, possibly because gage locations are too distant from areas of disturbance, or because of the relatively low sampling frequency. In order to detect changes in river hydrothermal solute fluxes, sampling at higher

  14. Reactivity of Tannic Acid with Common Corrosion Products and Its Influence on the Hydrolysis of Iron in Alkaline Solutions

    NASA Astrophysics Data System (ADS)

    Jaén, J. A.; Araúz, E. Y.; Iglesias, J.; Delgado, Y.

    2003-06-01

    To ascertain the role of tannic acid in the anticorrosive protection of steels, the reaction between 5% tannic acid aqueous solutions with lepidocrocite, goethite, superparamagnetic goethite, akaganeite, poorly crystalline maghemite, magnetite and hematite was studied using color changes, infrared and Mössbauer spectroscopy. After three months of interaction with lepidocrocite, the formation of an iron tannate complex was detected by its dark blue color and confirmed by infrared and Mössbauer analysis. Evidence for the chemical transformation was obtained for goethite in nanoparticles and poorly crystalline maghemite after reaction for six months. The other iron compounds do not transform to another oxide or phase upon treatment with the tannic acid solution. These results showed that lepidocrocite is the most reactive phase and that the size and degree of crystallinity have strong influence on the formation of the tannate complexes. The precipitation of iron phases from alkaline solutions of iron (II) sulfate heptahydrate containing different amount of tannic acid and potassium nitrate as oxidative agent was also studied. Mössbauer and infrared results show that in the absence of tannic acid some common rust components are obtained (viz. goethite, superparamagnetic goethite, maghemite and non-stoichiometric magnetite). The presence of 0.1% tannic acid in a low alkalinity solution results in the precipitation of iron oxyhydroxides and some iron tannates. Concentrations of 1% tannic acid are required for the formation of the tannates complexes as main reaction product.

  15. Effects of applied potential on the stress corrosion cracking behavior of 7003 aluminum alloy in acid and alkaline chloride solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-yan; Song, Ren-guo; Sun, Bin; Lu, Hai; Wang, Chao

    2016-07-01

    Potentiodynamic polarization tests and slow strain rate test (SSRT) in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking (SCC) behavior of 7003 aluminum alloy (AA7003) in acid and alkaline chloride solutions under various applied potentials ( E a). The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution (AD) at open-circuit potential (OCP) and is highly susceptible to hydrogen embrittlement (HE) at high negative E a in the solutions with pH levels of 4 and 11. The susceptibility increases with negative shift in the potential when E a is less than -1000 mV vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when E a is equal to -1000 mV vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.

  16. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

    SciTech Connect

    Liu, Shizhong; White, Michael G.; Liu, Ping

    2016-06-30

    Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e or 4e transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e transfers is identified, where the reduction steps via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e transfer mechanism.

  17. First-Principles Calculation of Solution Energy of Alkaline-Earth Metal Elements to BaTiO3

    NASA Astrophysics Data System (ADS)

    Moriwake, Hiroki; Hirayama, Tsukasa; Ikuhara, Yuichi; Tanaka, Isao

    2007-10-01

    Quantitative analysis of the solution energy of alkaline-earth metal elements to perovskite-type BaTiO3 was carried out by a first-principles calculation combined with thermodynamics theory. The solution energies of neutral solute and a compensated solute with an oxygen vacancy were systematically calculated. They were obtained for two cation sites and four thermodynamical conditions with different chemical potentials of constituent atoms. Both Ca and Sr preferably occupy the Ba site of BaTiO3. On the other hand, Mg occupies the Ti site. This corresponds well to the widely accepted experimental findings regarding site preference. Moreover, under the condition of coexising BaO, CaO and BaTiO3, energy difference between the Ba-site solution and O-vacancy compensated Ti-site solution of Ca ions has been found to be smaller than that of Sr. Under this condition, the O-vacancy compensated Ti-site solution of Ca should be favorable compared with that of Sr. The same number of oxygen vacancies as Ca ions occupying Ti sites can be introduced. This also explains well experimental feature of the Ca-doped BaTiO3-based nonreducible multilayer ceramics capacitor (MLCC) materials regarding solution site of the Ca ion and abundance of O-vacancy.

  18. Effects of Aging on PuO2∙xH2O Particle Size in Alkaline Solution

    SciTech Connect

    Delegard, Calvin H.

    2013-05-01

    Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g., iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.

  19. A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

    NASA Astrophysics Data System (ADS)

    Majari Kasmaee, L.; Gobal, F.

    Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

  20. The role of the interaction between oxygen and catechol in the pitting corrosion of steel in alkaline sulfide solutions

    SciTech Connect

    Kannan, S.; Kelly, R.G.

    1995-12-01

    Black liquor corrosivity is shown to depend on the interaction of the chemical species present. Specifically, an interaction between oxygen and 1,2-dihydroxybenzene compounds (catechols) in alkaline sulfide solutions leads to a distinct increase in the severity of the attack. This increased corrosivity is explained in terms of the oxidation of catechol leading to increased open circuit potentials for steel. The importance of the ratio of sulfide concentration to hydroxyl concentration in the initiation of pitting is stressed. The possible role of catechol in stabilizing metastable pits is also discussed.

  1. Enhancement of the absorption of CO{sub 2} in alkaline buffer solutions: Joint action of two enhancers

    SciTech Connect

    Vazquez, G.; Chenlo, F.; Pereira, G.; Vazquez, P.

    1999-05-01

    The authors measured the absorption of CO{sub 2} in alkaline 0.5 M/0.5 M sodium carbonate/bicarbonate buffers containing either saccharose and sodium arsenite or saccharose and formaldehyde. Absorption enhancement increased upon increasing the concentration of either of the catalysts, but the joint action of the two was always less than the sum of their individual effects, the difference being a function of the acidities and concentrations of the catalysts and the pH of the carbonate/bicarbonate buffer solution

  2. A study on the mechanism of stress corrosion cracking of duplex stainless steels in hot alkaline-sulfide solution

    NASA Astrophysics Data System (ADS)

    Chasse, Kevin Robert

    Duplex stainless steels (DSS) generally have superior strength and corrosion resistance as compared to most standard austenitic and ferritic stainless grades owing to a balanced microstructure of austenite and ferrite. As a result of having favorable properties, DSS have been selected for the construction of equipment in pulp and paper, chemical processing, nuclear, oil and gas as well as other industries. The use of DSS has been restricted in some cases because of stress corrosion cracking (SCC), which can initiate and grow in either the ferrite or austenite phase depending on the environment. Thorough understanding of SCC mechanisms of DSS in chloride- and hydrogen sulfide-containing solutions has been useful for material selection in many environments. However, understanding of SCC mechanisms of DSS in sulfide-containing caustic solutions is limited, which has restricted the capacity to optimize process and equipment design in pulp and paper environments. Process environments may contain different concentrations of hydroxide, sulfide, and chloride, altering corrosion and SCC susceptibility of each phase. Crack initiation and growth behavior will also change depending on the relative phase distribution and properties of austenite and ferrite. The role of microstructure and environment on the SCC of standard grade UNS S32205 and lean grade UNS S32101 in hot alkaline-sulfide solution were evaluated in this work using electrochemical, film characterization, mechanical testing, X-ray diffraction, and microscopy techniques. Microstructural aspects, which included residual stress state, phase distribution, phase ratio, and microhardness, were related to the propensity for SCC crack initiation in different simulated alkaline pulping liquors at 170 °C. Other grades of DSS and reference austenitic and superferritic grades of stainless steel were studied using exposure coupons for comparison to understand compositional effects and individual phase susceptibility

  3. Controlled synthesis of La{sub 1−x}Sr{sub x}CrO{sub 3} nanoparticles by hydrothermal method with nonionic surfactant and their ORR activity in alkaline medium

    SciTech Connect

    Choi, Bo Hyun; Park, Shin-Ae; Park, Bong Kyu; Chun, Ho Hwan; Kim, Yong-Tae

    2013-10-15

    Graphical abstract: We demonstrate that Sr-doped LaCrO{sub 3} nanoparticles were successfully prepared by the hydrothermal synthesis method using the nonionic surfactant Triton X-100 and the applicability of La{sub 1−x}Sr{sub x}CrO{sub 3} to oxygen reduction reaction (ORR) electrocatalysis in an alkaline medium. Compared with the nanoparticles synthesized by the coprecipitation method, they showed enhanced ORR activity. - Highlights: • Sr-doped LaCrO{sub 3} nanoparticles were successfully prepared by the hydrothermal method using the nonionic surfactant. • Homogeneously shaped and sized Sr-doped LaCrO{sub 3} nanoparticles were readily obtained. • Compared with the nanoparticles synthesized by the coprecipitation method, they showed an enhanced ORR activity. • The main origin was revealed to be the decreased particle size due to the nonionic surfactant. - Abstract: Sr-doped LaCrO{sub 3} nanoparticles were prepared by the hydrothermal method with the nonionic surfactant Triton X-100 followed by heat treatment at 1000 °C for 10 h. The obtained perovskite nanoparticles had smaller particle size (about 100 nm) and more uniform size distribution than those synthesized by the conventional coprecipitation method. On the other hand, it was identified with the material simulation that the electronic structure change by Sr doping was negligible, because the initially unfilled e{sub g}-band was not affected by the p-type doping. Finally, the perovskite nanoparticles synthesized by hydrothermal method showed much higher ORR activity by over 200% at 0.8 V vs. RHE than those by coprecipitation method.

  4. Synthesis and crystallographic study of Pb-Sr hydroxyapatite solid solutions by high temperature mixing method under hydrothermal conditions

    SciTech Connect

    Zhu Kongjun; Yanagisawa, Kazumichi; Shimanouchi, Rie; Onda, Ayumu; Kajiyoshi, Koji; Qiu Jinhao

    2009-06-03

    The solid solutions in the system of Pb and Sr hydroxyapatite, Sr{sub 10-x}Pb{sub x}HAp (x = 0-10), were successfully synthesized by high-temperature mixing method (HTMM) at 160 deg. C for 12 h under hydrothermal conditions. The samples were characterized by X-ray diffraction, chemical analysis and electron microscopic observation, and the site of the metal ions in the solid solutions was analyzed with the Rietveld method. The lattice constants, both a and c, of the solid solutions varied linearly with Pb content. It was found that Pb ions in the solid solutions preferentially occupied the M(2) site in the apatite structure. HTMM gives Sr-Pb HAp solid solutions much better crystallization. However, due to the formation of intermediate compound of Pb{sub 3}O{sub 2}(OH){sub 2} in the Pb(NO{sub 3}){sub 2}.4H{sub 2}O solution before mixing with (NH{sub 4}){sub 2}HPO{sub 4} solution at 160 deg. C, HTMM causes the decrease of crystallization of the samples with high Pb content.

  5. Fabrication of macroporous carbonate apatite foam by hydrothermal conversion of alpha-tricalcium phosphate in carbonate solutions.

    PubMed

    Wakae, H; Takeuchi, A; Udoh, K; Matsuya, S; Munar, M L; LeGeros, R Z; Nakasima, A; Ishikawa, K

    2008-12-15

    Bone consists of a mineral phase (carbonate apatite) and an organic phase (principally collagen). Cancellous bone is characterized by interconnecting porosity necessary for tissue ingrowth and nourishment of bone cells. The purpose of the present study was to fabricate macroporous carbonate apatite (CAP) blocks with interconnecting porosity as potential bone substitute biomaterials by hydrothermal conversion of alpha-TCP foam in carbonate solution. The fabrication of the macroporous CAP was accomplished in two steps: (1) preparation of alpha-TCP foams using polyurethane foams as templates, and (2) hydrothermal conversion at 200 degrees C of alpha-TCP foam in the presence of ammonium carbonate solutions of different concentrations. The maximum carbonate content of the resultant CAP foam was approximately 7.4 wt %. The mean porosity of the CAP foam was as high as 93 vol %. The macroporous CAP blocks or granules prepared in this manner has properties similar to that of bone in mineral composition and in having interconnecting macroporosity necessary for osteoconductivity and tissue ingrowth. On the basis of composition and interconnecting macroporosity, the CAP foam materials could be ideal biomaterials for bone repair and as scaffolds for tissue engineering.

  6. Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2015-01-15

    Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for construction purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.

  7. Cysteine as a green corrosion inhibitor for Cu37Zn brass in neutral and weakly alkaline sulphate solutions.

    PubMed

    Radovanović, Milan B; Petrović, Marija B; Simonović, Ana T; Milić, Snežana M; Antonijević, Milan M

    2013-07-01

    The aim of this study was to investigate electrochemical properties of brass in neutral and weakly alkaline solutions in the presence of cysteine as a nontoxic and ecological corrosion inhibitor. Potentiodynamic measurements, open circuit potential measurements, as well as chronoamperometric measurements were the methods used during investigation of the inhibitory effect of cysteine on the corrosion behaviour of brass. Potentiodynamic measurements showed that cysteine behaves as a mixed-type inhibitor in the investigated media. Based on polarization curves for brass in a weakly alkaline solution of sodium sulphate at varying cysteine concentrations, an interaction occurs between Cu(+) ions and the inhibitor, resulting in the formation of a protective complex on the electrode surface. The results of chronoamperometric measurements confirm the results obtained by potentiodynamic measurements. Optical microphotography of the brass surface also confirms the formation of a protective film in the presence of a 1 × 10(-4) mol/dm(3) cysteine. Adsorption of cysteine on the brass surface proceeds according to the Langmuir adsorption isotherm.

  8. Influence of grain refinement on the electrochemical behavior of AISI 430 ferritic stainless steel in an alkaline solution

    NASA Astrophysics Data System (ADS)

    Fattah-alhosseini, A.; Vafaeian, S.

    2016-01-01

    In this paper, the effect of grain refinement on the electrochemical behavior of AISI 430 ferritic stainless steel in 0.1 M NaOH solution was investigated. Potentiodynamic polarization curves showed that fine-grained samples have less corrosion potential, higher corrosion current density, and less protective passive film in comparison to coarse-grained samples. Electrochemical impedance spectroscopy (EIS) analysis revealed that implementing the thermomechanical operation led to lower polarization resistance. Also, Mott-Schottky analysis revealed that the passive films on both fine-grained and coarse-grained samples behave as n-type and p-type semiconductors and the semiconductor character of the passive films did not change by grain refinement. Moreover, it was found that the calculated donor and acceptor densities increased with grain refinement. Thus, the presented results indicated that grain refinement weakens the corrosion and passivation behavior of AISI 430 stainless steel in this alkaline solution.

  9. Composition and structure of Pt chloride complexes in hydrothermal solutions, according to X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tagirov, B. R.; Trigub, A. L.; Selivanov, P. V.; Koroleva, L. A.

    2017-03-01

    The local atomic environment of Pt in chloride solutions is studied at 25 and 300-350°C via X-ray absorption spectroscopy. A comparison of the Pt L 3-edge XANES spectra for aqueous chloride solutions and reference compounds (K2PtCl4 and K2PtCl6) shows that platinum is in oxidation state +2 at all temperatures, and the complex composition remains unchanged in the experimental range of temperatures (25-350°C) and solution compositions ( m(Cltot) > 0.4 mol kg-1 of H2O). Based on EXAFS spectral analysis, the composition of the complex being dominant in chloride solutions is found to be PtCl4 2- with interatomic Pt-Cl distances of 2.31 ± 0.01 Å, regardless of the temperature. It is concluded that the local environments of Pt and Pd in hydrothermal solutions are similar, and the main form of transfer for these metals is a square-planar complex with four Cl ligands and identical interatomic distances.

  10. Equilibrium and kinetic studies of phosphate removal from solution onto a hydrothermally modified oyster shell material.

    PubMed

    Chen, Jie; Cai, Yun; Clark, Malcolm; Yu, Yan

    2013-01-01

    Phosphate removal to a hydrothermally modified fumed silica and pulverized oyster shell material for use in wastewater treatments were made. Sorption data modeling (pH's 3-11, P concentrations of 3, 5, 10, 15, 20, & 25 mg/L, and at an ambient temperature of 23°C) indicate that an optimal removal of P occurs at pH 11. Three kinetic models were also applied (a pseudo-first-order Lagergren kinetic model, a pseudo-second-order (PSO) kinetic and Elovich) and indicate that a PSO model best describes P-removal. In addition, an application of the Weber and Morris intra-particle diffusion model indicates that external mass transfer and intra-particle diffusion were both involved in the rate-determining step. Langmuir, Freundlich modeling of the sorption data also indicate that the heterogeneous Freundlich sorption site model best describes the data although Langmuir data also fit with data tailing suggesting data are not linear. The data collected indicates that the hydrothermally modified fumed silica and pulverized oyster shell material is suitable for use in wastewater treatment, with P-removal to the solids being preferential and spontaneous.

  11. Equilibrium and Kinetic Studies of Phosphate Removal from Solution onto a Hydrothermally Modified Oyster Shell Material

    PubMed Central

    Chen, Jie; Cai, Yun; Clark, Malcolm; Yu, Yan

    2013-01-01

    Phosphate removal to a hydrothermally modified fumed silica and pulverized oyster shell material for use in wastewater treatments were made. Sorption data modeling (pH’s 3–11, P concentrations of 3, 5, 10, 15, 20, & 25 mg/L, and at an ambient temperature of 23°C) indicate that an optimal removal of P occurs at pH 11. Three kinetic models were also applied (a pseudo-first-order Lagergren kinetic model, a pseudo-second-order (PSO) kinetic and Elovich) and indicate that a PSO model best describes P-removal. In addition, an application of the Weber and Morris intra-particle diffusion model indicates that external mass transfer and intra-particle diffusion were both involved in the rate-determining step. Langmuir, Freundlich modeling of the sorption data also indicate that the heterogeneous Freundlich sorption site model best describes the data although Langmuir data also fit with data tailing suggesting data are not linear. The data collected indicates that the hydrothermally modified fumed silica and pulverized oyster shell material is suitable for use in wastewater treatment, with P-removal to the solids being preferential and spontaneous. PMID:23565207

  12. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium from a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant to and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate, nonsaturated in uranium. The uranium is stripped from, the organic extractant into the stripping solution, and the resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  13. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium for a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate or hydroxide thereby stripping uranium from the organic extractant into the stripping solution. The resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  14. Geochemistry and solute fluxes of volcano-hydrothermal systems of Shiashkotan, Kuril Islands

    NASA Astrophysics Data System (ADS)

    Kalacheva, Elena; Taran, Yuri; Kotenko, Tatiana

    2015-04-01

    Shiashkotan Island belongs to the Northern Kuril island arc and consists of two joined volcanoes, Sinarka and Kuntomintar, with about 18 km of distance between the summits. Both volcanoes are active, with historic eruptions, and both emit fumarolic gases. Sinarka volcano is degassing through the extrusive dome with inaccessible strong and hot (> 400 °C) fumaroles. A large fumarolic field of the Kuntomintar volcano situated in a wide eroded caldera-like crater hosts many fumarolic vents with temperatures from boiling point to 480 °C. Both volcanoes are characterized by intense hydrothermal activity discharging acid SO4-Cl waters, which are drained to the Sea of Okhotsk by streams. At least 4 groups of near-neutral Na-Mg-Ca-Cl-SO4 springs with temperatures in the range of 50-80 °C are located at the sea level, within tide zones and discharge slightly altered diluted seawater. Volcanic gas of Kuntomintar as well as all types of hydrothermal manifestations of both volcanoes were collected and analyzed for major and trace elements and water isotopes. Volcanic gases are typical for arc volcanoes with 3He/4He corrected for air contamination up to 6.4 Ra (Ra = 1.4 × 10- 6, the air ratio) and δ13C (CO2) within - 10‰ to - 8 ‰ VPDB. Using a saturation indices approach it is shown that acid volcanic waters are formed at a shallow level, whereas waters of the coastal springs are partially equilibrated with rocks at ~ 180 °C. Trace element distribution and concentrations and the total REE depend on the water type, acidity and Al + Fe concentration. The REE pattern for acidic waters is unusual but similar to that found in some acidic crater lake waters. The total hydrothermal discharge of Cl and S from the island associated with volcanic activity is estimated at ca. 20 t/d and 40 t/d, respectively, based on the measurements of flow rates of the draining streams and their chemistry. The chemical erosion of the island by surface and thermal waters is estimated at 27 and

  15. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    DOE PAGES

    Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; ...

    2014-12-04

    We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over themore » equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

  16. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    SciTech Connect

    Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A.

    2014-12-04

    We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.

  17. Hydrothermolysis of biomass-ethanol fermentation of hydrothermal solutions with Saccharomyces carlsbergensis W 34

    SciTech Connect

    Bonn, G.; Bobleter, O.; Pfeifer, P.; Schwald, W.

    1983-12-01

    Research on alternative energy sources and raw materials is gaining in importance owing to the increasing shortage of energy carriers and petrochemicals. Hydrothermolysis of lignocellulosic biomass (e.g., wood, straw) degrades the high molecular substrate into low molecular compounds (sugars, furfurals, phenols etc.). In this process water dissolves hemicellulose at approximately 180/sup 0/ C, cellulose at approximately 270/sup 0/ C, and lignin at about 300/sup 0/ C, without the addition of any chemicals / 1-4/. Over 50% of the cellulose thus hydrolyzed can be fermented to ethanol by saccharomyces carlsbergensis W 34. To obtain these results it was necessary to carry out basic fermentation experiments on the inhibition of certain by-products such as lignin compounds, glyceraldehyde, methylglyoxal etc.. On the basis of these experiments, the optimum conditions for the fermentation to ethanol of hydrothermally treated pure cellulose (filter paper), cotton with and without impurities, waste cotton from textile manufacture, and straw, were examined.

  18. RECENT STUDIES OF URANIUM AND PLUTONIUM CHEMISTRY IN ALKALINE RADIOACTIVE WASTE SOLUTIONS

    SciTech Connect

    King, W; Bill Wilmarth, B; David Hobbs, D; Tommy Edwards, T

    2006-06-13

    Solubility studies of uranium and plutonium in a caustic, radioactive Savannah River Site tank waste solution revealed the existence of uranium supersaturation in the as-received sample. Comparison of the results to predictions generated from previously published models for solubility in these waste types revealed that the U model poorly predicts solubility while Pu model predictions are quite consistent with experimental observations. Separate studies using simulated Savannah River Site evaporator feed solution revealed that the known formation of sodium aluminosilicate solids in waste evaporators can promote rapid precipitation of uranium from supersaturated solutions.

  19. Aloe vera plant-extracted solution hydrothermal synthesis and magnetic properties of magnetite (Fe3O4) nanoparticles

    NASA Astrophysics Data System (ADS)

    Phumying, Santi; Labuayai, Sarawuth; Thomas, Chunpen; Amornkitbamrung, Vittaya; Swatsitang, Ekaphan; Maensiri, Santi

    2013-06-01

    Magnetite (Fe3O4) nanoparticles have been successfully synthesized by a novel hydrothermal method using ferric acetylacetonate (Fe(C5H8O2)3) and aloe vera plant-extracted solution. The influences of different reaction temperatures and times on the structure and magnetic properties of the synthesized Fe3O4 nanoparticles were investigated. The synthesized nanoparticles are crystalline and have particle sizes of ˜6-30 nm, as revealed by transmission electron microscopy (TEM). The results of X-ray diffraction (XRD), High resolution TEM (HRTEM) and selected area electron diffraction (SAED) indicate that the synthesized Fe3O4 nanoparticles have the inverse cubic spinel structure without the presence of any other phase impurities. The hysteresis loops of the Fe3O4 nanoparticles at room temperature show superparamagnetic behavior and the saturation magnetization of the Fe3O4 samples increases with increasing reaction temperature and time.

  20. Dependence of the solubility of atmospheric oxygen in weakly alkaline aqueous solutions on surfactant concentration

    NASA Astrophysics Data System (ADS)

    Chistyakova, G. V.; Koksharov, S. A.; Vladimirova, T. V.

    2012-11-01

    The solubility of atmospheric oxygen in solutions of surfactants of different natures at 293 K and pH 8 is determined by gas chromatography. It is found that additives of nonionic surfactants decrease the oxygen content in the solution in the premicellar region and increase its solubility in the micellar region. It is shown that, for anionic surfactants, a decrease in the solubility of O2 is observed over the entire concentration range.

  1. Decomposition of N-chloroglycine in alkaline aqueous solution: kinetics and mechanism.

    PubMed

    Szabó, Mária; Baranyai, Zsolt; Somsák, László; Fábián, István

    2015-06-15

    The decomposition kinetics and mechanism of N-chloroglycine (MCG) was studied under very alkaline conditions ([OH(-)] = 0.01-0.10 M). The absorbance change is consistent with two consecutive first-order processes in the 220-350 nm wavelength range. The first reaction is linearly dependent on [OH(-)] and interpreted by the formation of a carbanion from MCG in an equilibrium step (KOH) and a subsequent loss of chloride ion from this intermediate: kobs1 = KOH k1 = (6.4 ± 0.1) × 10(-2) M(-1) s(-1), I = 1.0 M (NaClO4), and T = 25.0 °C. The second process is assigned to the first-order decomposition of N-oxalylglycine, which is also formed as an intermediate in this system: kobs2 = (1.2 ± 0.1) × 10(-3) s(-1). Systematic (1)H and (13)C NMR measurements were performed in order to identify and follow the concentration changes of the reactant, intermediate, and product. It is confirmed that the decomposition proceeds via the formation of glyoxylate ion and produces N-formylglycine as a final product. This compound is stable for an extended period of time but eventually hydrolyses into formate and glycinate ions. A detailed mechanism is postulated which resolves the controversies found in earlier literature results.

  2. A parallel-plate electrochemical reactor model for the destruction of nitrate and nitrite in alkaline waste solutions

    SciTech Connect

    Coleman, D.H.; White, R.E.; Hobbs, D.T.

    1995-04-01

    The electrochemical treatment of nuclear waste is the subject of much current interest. After radioactive decontamination, the liquid waste from nuclear fuel processing still contains many hazardous substances, among them nitrate and nitrite. A parallel-plate electrochemical reactor model with multiple reactions at both electrodes and anolyte and catholyte recirculation tanks was modeled for the electrochemical destruction of nitrate and nitrite species in an alkaline solution. The model can be used to predict electrochemical reaction current efficiencies and outlet concentrations of species from the reactor, given inlet feed conditions and cell operating conditions. Also, predictions are made for off-gas composition and liquid-phase composition in the recirculation tanks. The results of case studies at different applied potentials are shown here. At lower applied potentials, the model predictions show that the destruction process is more energy efficient, but the time required to destroy a given amount of waste is increased.

  3. Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations.

    PubMed

    Reimer, Joachim; Vogel, Frédéric; Steele-MacInnis, Matthew

    2016-05-18

    Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular-scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na-SO4 exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K-SO4 show significantly less clustering under equivalent conditions. In mixed systems (Nax K2-x SO4 ), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure-breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K(+) and SO4 (2-) , compared with the analogous Na(+) -SO4 (2-) interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na-K-SO4 . Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium-sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting-in in ternary hydrothermal solutions of Na-K-SO4 reflects the opposing, but complementary, natures of Na-SO4 versus K-SO4 interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system.

  4. Concentration- and pH-dependence of highly alkaline sodium silicate solutions.

    PubMed

    Nordström, Jonas; Nilsson, Erik; Jarvol, Patrik; Nayeri, Moheb; Palmqvist, Anders; Bergenholtz, Johan; Matic, Aleksandar

    2011-04-01

    In this study two routes for the gelation of water glass have been investigated; the destabilization by a change in pH and by an increase in concentration through evaporation. Both methods produce optically transparent, highly viscous, homogeneous solutions. The structure and dynamics of the solutions along the two routes have been investigated with dynamic light scattering, (29)Si-Nuclear Magnetic Resonance spectroscopy, viscosity measurements and infrared spectroscopy. We find that the two routes are fundamentally different. Increasing the concentration of the sodium silicate system leaves the silica speciation apparently unchanged. Lowering the pH leads to condensation reactions, thus a change in the silica speciation.

  5. Assessment of the Effects Exerted by Acid and Alkaline Solutions on Bone: Is Chemistry the Answer?

    PubMed

    Amadasi, Alberto; Camici, Arianna; Porta, Davide; Cucca, Lucia; Merli, Daniele; Milanese, Chiara; Profumo, Antonella; Rassifi, Nabila; Cattaneo, Cristina

    2017-02-01

    The treatment of corpses with extremely acid or basic liquids is sometimes performed in criminal contexts. A thorough characterization by chemical analysis may provide further help to macroscopic and microscopic analysis; 63 porcine bone samples were treated with solutions at different pH (1-14) for immersion periods up to 70 days, as well as in extremely acidic sulfuric acid solutions (9 M/18 M) and extremely basic sodium hydroxide. Inductively coupled optical emission spectrometry (ICP-OES)/plasma mass spectrometry (ICP-MS), Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray analysis (EDX), X-ray powder diffraction (XRPD), and scanning electron microscopy (SEM) showed that only the sulfuric acid solution 18 M was able to completely dissolve the sample. In addition, chemical analysis allowed to recognize the contact between bone and substances. Hydrated calcium sulfate arose from extreme pH. The possibility of detecting the presence of human material within the residual solution was demonstrated, especially with FT-IR, ICP-OES, and EDX.

  6. Mechanical and electrochemical properties of an IPMC actuator with palladium electrodes in acid and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Aoyagi, Wataru; Omiya, Masaki

    2013-05-01

    An ionic polymer-metal composite (IPMC) actuator, which consists of a thin perfluorinated ionomer membrane and electrodes plated on both surfaces, undergoes a large bending motion when a low electric field is applied across its thickness. IPMC actuators are lightweight and soft and can operate in solutions. They are thus promising for a wide range of applications including MEMS sensors, artificial muscles, biomimetic systems, and medical devices. The deformation behavior of IPMC actuators depends on the pH of the working solution. However, their basic mechanism is not well understood. Therefore, this study investigates the deformation mechanism of an IPMC actuator with palladium electrodes in various pH solutions. The tip displacements of IPMC actuators were measured under a step voltage in various pH solutions. Cyclic voltammetry (CV) and alternating-current (AC) impedance measurements were then performed to investigate the effects of pH on the electrochemical properties of IPMC actuators. The responses to a step voltage indicate that the deformation behavior of an IPMC actuator depends on the pH: a lower pH gives a larger maximum tip displacement and more pronounced relaxation. In CV measurements, a lower pH results in more active reduction on the palladium electrode. In AC impedance measurements, a lower pH leads to a greater charge transfer resistance and a smaller double layer capacitance in an acid solution. Based on these mechanical and electrochemical measurements, we conclude that the maximum tip displacement and relaxation are governed by reduction on the palladium electrode and that the residual tip displacement is related to the charge transfer resistance and the double layer capacitance. These results are helpful for the use and control of IPMC actuators.

  7. Chemistry of hydrothermal solutions from the southern Juan de Fuca Ridge

    SciTech Connect

    Von Damm, K.L.; Bischoff, J.L.

    1987-10-10

    Fluids from three vent fields on the southern Juan de Fuca Ridge were sampled in September 1984 using the DSRV Alvin. The fluids are uniquely high in both chloride, which ranges up to twice the seawater value, and in metal content. Simple vapor-liquid phase separation could not have produced both the high chlorinity and gas concentrations observed in these fluids. The cause of the elevated chlorinity can not be uniquely identified but may be the result of either or a combination of two processes: (1) subsurface formation of a degassed brine and subsequent mixing of a small amount of this brine with a hydrothermal seawater which has not undergone a phase separation and (2) dissolution of a chloride-rich phase combined with a possible small loss of gas during sampling procedures. Although measured temperatures were all less than 300 /sup 0/C, quartz geothermometry suggests that the fluids have equilibrated at greater than 340 /sup 0/C. Quartz geobarometry is also in agreement with geophysical estimates of depth to the local magma chamber. copyright American Geophysical Union 1987

  8. Corrosion of nickel metal by hydrothermal sodium tungstate solution observed by in-situ infrared spectroscopy

    SciTech Connect

    Hoffmann, M.M.; Fulton, J.L.

    2000-05-01

    Corrosion of nickel metal in a high-temperature aqueous tungstate solution was described. The corrosion altered the solution's pH, which affected the equilibrium of the solution chemistry. These secondary effects of the corrosion process were observed with in-situ infrared (IR) spectroscopy, demonstrating that important information on corrosion phenomena at the solid-fluid interface may be obtained from in-situ spectroscopic studies of the fluid phase. Subsequent scanning electron microscopy (SEM) analysis of the corroded nickel metal and solid corrosion products support conclusions drawn from solution chemistry measurements. The presented findings are of interest to researchers and engineers that use pure nickel or nickel-bearing alloys as a material for high-temperature, high-pressure applications in aqueous solutions.

  9. The Role of Oxygen in the Copper-Catalyzed Decomposition of Phenylborates in Aqueous Alkaline Solutions

    SciTech Connect

    Hyder, M.L.

    1997-03-17

    The effect of oxygen on the copper-catalyzed hydrolysis of phenyl borates containing from one to four phenyl groups was studied in 1 M aqueous sodium hydroxide solution at 59 degrees C. The results are tentatively explained if the effective catalyst for each of the reactions is either cupric or cuprous ion, with the latter being present in significant concentration only in the absence of air.

  10. Aqueous thiocyanate-urea solution as a powerful non-alkaline swelling agent for cellulose fibres.

    PubMed

    Mahmud-Ali, Amalid; Bechtold, Thomas

    2015-02-13

    For many applications cellulose fibres are treated with concentrated solutions of swelling agents to increase reactivity and to achieve reorganisation of fibre structure. Representative examples are caustic soda, potassium hydroxide solution or liquid ammonia. These highly concentrated media bear considerable safety hazards during the technical handling thus alternative swelling agents are of interest. The thiocyanate-urea system investigated in this work offers high swelling potential for regenerated cellulose fibres. Experiments with different cations of M(+) in M(+) SCN(-) demonstrate the significant influence of the cation on the degree of fibre swelling. In concentrated NaSCN/urea solutions, at 80 °C, lyocell fibres expand the diameter from 12-14 to 100 μm. The treatment in the swelling agent also led to a significant increase in the water retention value which was accompanied by a strength loss of 20-40% of the initial value. FTIR analysis of treated fibres did not indicate substantial changes in structure of the cellulose polymer. Limited weight loss of up to 20% was observed despite the high expansion of the fibre.

  11. Influence of monovalent ions on density fluctuations in hydrothermal aqueous solutions by small angle X-ray scattering.

    PubMed

    Da Silva-Cadoux, Cécile; Hazemann, Jean-Louis; Testemale, Denis; Proux, Olivier; Rochas, Cyrille

    2012-01-28

    Synchrotron small angle X-ray scattering measurements on water and alkaline bromine aqueous solutions (XBr, with X = Li, Rb, or Cs) were carried out from ambient to supercritical conditions. The temperature was increased from 300 to 750 K along several isobars between 24 and 35 MPa. The correlation length and the structure factor were extracted from the data following the Ornstein-Zernike formalism. We obtained experimental evidence of the shift of the critical point and isochore and their dependence on the ions concentration (0.33 mol/kg and 1.0 mol/kg). We also observed that the size of the density fluctuations and the structure factor increase with the presence of the ions and that this effect is positively correlated with the atomic number of the cation. These behaviors were compared with ZnBr(2) and NaCl systems from the literature.

  12. Experimental transport of Si, Al and Mg in hydrothermal solutions: an application to vein mineralization during high-pressure, low-temperature metamorphism in the French Alps

    NASA Astrophysics Data System (ADS)

    Goffé, Bruno; Murphy, William M.; Lagache, Martine

    1987-12-01

    A study of hydrothermal vein mineralization in meta-argillites subjected to high-pressure, low-temperature metamorphism reveals that ferromagnesian (e.g., chlorite) and pure aluminosilicate (e.g., pyrophyllite) mineralization can be correlated with regimes of increasing and decreasing temperature, respectively. An experimental study of the transport of silica, aluminum and magnesium in hydrothermal solutions has been undertaken to simulate variations in the physical conditions during metamorphism and the accompanying mass transport in a closed system. Thermodynamic and kinetic analysis of the experimental results indicates that local equilibrium among aqueous and mineral phases controls the distribution and composition of hydrothermal vein mineralization and that vein mineralogy can be used to infer the sense of variation of pressure and temperature during metamorphism.

  13. 1-Dodecane-sulfonic-acid-sodium-salt(LAS) assisted hydrothermal synthesis of CdxZn1-xS solid solution as efficient photocatalysts under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Jia, B.; Guo, L. J.

    2010-03-01

    With anionic surfactant LAS assisted, series of zinc cadmium sulfide semiconductor photocatalysts were synthesized by hydrothermal method. These products were characterized by X-ray diffraction (XRD), UV-Vis absorption spectra (UV-Vis) and scanning electron microscopy (FESEM). The photocatalytic activities of as-prepared samples were evaluated by photocatalytic hydrogen production from water under visible-light irradiation. The best synthesis parameters are: Composition 0.9:0.1 (Cd:Zn molar ratio), Temperature 160 °C, Hydrothermal Time 48 Hour, LAS Concentration 1.7 mmol/L, the maximum visible-light-catalytic hydrogen production rate is 161.25 μmol/h (λ>430 nm) which is higher than those of by coprecipitation method. The experiment results indicate that surfactant assisted hydrothermal method is an effective way to get highly active CdZnS solid solution photocatalyst.

  14. Observations on the crystallization of spodumene from aqueous solutions in a hydrothermal diamond-anvil cell

    USGS Publications Warehouse

    Li, Jianking; Chou, I-Ming; Yuan, Shunda; Burruss, Robert A.

    2013-01-01

    Crystallization experiments were conducted in a new type of hydrothermal diamond-anvil cell (HDAC; type V) using LiAlSi2O6 (S) gel and H2O (W) as starting materials. A total of 21 experiments were performed at temperatures up to 950°C and pressures up to 788 MPa. In the samples with relatively low W/S ratios, many small crystals formed in the melt phase during cooling. In those with high W/S ratios, only a few crystals with smooth surfaces crystallized from the aqueous fluid in the presence of melt droplets, which were gradually consumed during crystal growth, indicating rapid transfer of material from the melt to the crystals through the aqueous fluid. The nucleation of crystals started at 710 (±70)°C and 520 (±80) MPa, and crystal growth ended at 570 (±40)°C and 320 (±90) MPa, with the cooling P-T path within the stability field of spodumene + quartz in the S-W system. The observed linear crystal growth rates in the aqueous phase, calculated by dividing the maximum length of a single crystal by the duration of the entire growth step, were 4.7 × 10−6 and 5.7 × 10−6 cm s−1 for the cooling rates of 0.5 and 1°C min−1, respectively. However, a rapid crystal growth rate of 3.6 × 10−5 cm s−1 in the aqueous fluid was observed when the components were supplied by nearby melt droplets. Our results show that when crystals nucleate in the aqueous fluid instead of the melt phase, there are fewer nuclei formed, and they grow much faster due to the low viscosity of the aqueous fluid, which accelerates diffusion of components for the growth of crystals. Therefore, the large crystals in granitic pegmatite can crystallize directly from aqueous fluids rather than hydrosilicate melt.

  15. Spectroscopic study of Mg(II) ion influence on the autoxidation of gallic acid in weakly alkaline aqueous solutions

    NASA Astrophysics Data System (ADS)

    Nikolić, G. M.; Veselinović, A. M.; Nikolić, R. S.; Mitić, S. S.

    2011-12-01

    Gallic acid autoxidation in weakly alkaline aqueous solutions was studied by UV-Vis spectrophotometry and ESR spectroscopy under various conditions. Lowering the pH value from 10 to 8.5 probably changes the mechanism of the autoxidation reaction as evidenced by the different time variations of UV-Vis spectra of solutions. The presence of Mg(II) ions greatly influences the autoxidation reaction at pH 8.5. Although the UV-Vis spectral changes with time follow the similar pattern during the gallic acid autoxidation at pH 10 and at pH 8.5 in the presence of Mg(II) ions, some small differences indicate that Mg(II) ions not only affect the electron density of absorbing species but also influence the overall mechanism of the autoxidation reaction. ESR spectra of free radials formed during the initial stage of gallic acid autoxidation at pH 8.5 in the presence of Mg(II) ions were recorded. Computer simulation of ESR spectra allows partial characterization of these free radicals.

  16. Thermodynamic Model for ThO2(am) Solubility in Alkaline Silica Solutions

    SciTech Connect

    Rai, D; Yui, Mikazu; Moore, Dean A.; Lumetta, Gregg J.; Rosso, Kevin M.; Xia, Yuanxian; Felmy, Andrew R.; Skomurski, Frances N.

    2008-10-11

    literature, agreed closely with the extensive experimental data and showed that under alkaline conditions aqueous Si makes very strong complexes with Th.

  17. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

    PubMed Central

    2013-01-01

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

  18. Comprehensive study of the chemical reactions resulting from the decomposition of chloroform in alkaline aqueous solution

    NASA Astrophysics Data System (ADS)

    Estevez Mews, Jorge

    Chloroform (CHCl3) is a volatile liquid, which has a rather slow rate of decomposition in ground water. It is a known carcinogen and one of the most common contaminants found at toxic waste sites. The dominant degradation process for chloroform in both the atmosphere and the groundwater is the reaction with the hydroxyl radical or hydroxide ion. This process triggers a sequence of reactions which ultimately yield carbon monoxide, hydrogen chloride, and formic acid. The rate of chloroform degradation is considerably larger in solution than that in the gas phase and it increases dramatically with increasing pH. However, only one of the viable reactions had been studied previously at a high level of theory in solution. It is of great interest to gain a deeper understanding of the decomposition reaction mechanism. Quantum mechanical methods are well suited for studying the mechanism of organic reactions. However, a full quantum mechanical treatment of the entire fluid system is not computationally feasible. In this work, combined quantum mechanical and molecular mechanical (QM/MM) methods are used for studying chemical reactions in condensed phases. In these calculations, the solute molecules are treated quantum mechanically (QM), whereas the solvent molecules are approximated by empirical (MM) potential energy functions. The use of quantum mechanics and statistical sampling simulation is necessary to determine the reaction free energy profile. In the present study, the ab initio Hartree-Fock theory along with the 3-21G basis set was used in the quantum mechanical calculations to elucidate the reaction pathways of chloroform decomposition, with a focus on basic reaction conditions. Statistical mechanical Monte Carlo approach was then applied in molecular mechanical simulations, employing the empirical TIP3P model for water. We employed state-of-the-art electronic structure methods to determine the gas-phase inter-nuclear potential energy profile for all the relevant

  19. Electrochemical Behavior of Nano-grained Pure Copper in Dilute Alkaline Solution with Chloride Ion Trace

    NASA Astrophysics Data System (ADS)

    Fattah-Alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza

    2016-10-01

    Effect of nano-grained structure on the interface behavior of pure copper in 0.01M KOH solution with chloride ion trace is investigated by various electrochemical techniques. Nano-grained structure was achieved by accumulative roll bonding (ARB) technique. Before any electrochemical measurements, microstructure was evaluated by means of optical microscopy and transmission electron microscopy (TEM). TEM observations showed that nano-grains (with an average size of below 100 nm) appeared after eight passes of ARB. Polarization curves revealed that increasing chloride ion concentration leads to a decrease in the corrosion and pitting potentials of both annealed and nano-grained pure copper samples. Electrochemical impedance spectroscopy revealed that chloride ion trace lowers passive film resistance and charge-transfer resistance in both annealed and nano-grained samples. Mott-Schottky analysis showed that the surface films formed on annealed and nano-grained samples in KOH solution with and without NaCl addition are of p-type semiconducting behavior. Moreover, this analysis showed that the acceptor density increases by increasing chloride ion concentration.

  20. Hydrogen evolution at catalytically-modified nickel foam in alkaline solution

    NASA Astrophysics Data System (ADS)

    Pierozynski, Boguslaw; Mikolajczyk, Tomasz; Kowalski, Ireneusz M.

    2014-12-01

    This work reports on hydrogen evolution reaction (HER) studied at catalytically modified nickel foam material. The HER was examined in 0.1 M NaOH solution on as received, as well as for Pd and Ru-activated nickel foam catalyst materials, produced via spontaneous deposition of trace amounts of these elements. Catalytic modification of nickel foam results in significant facilitation of the HER kinetics, as manifested through considerably reduced, a.c. impedance-derived values of charge-transfer resistance parameter and substantially altered Tafel polarization slopes. The presence of catalytic additives is clearly revealed through hydrogen underpotential deposition (H UPD) phenomenon, as well as spectroscopically from SEM (Scanning Electron Microscopy) analysis.

  1. Electrochemiluminescence of luminol in alkaline solution at a paraffin-impregnated graphite electrode.

    PubMed

    Cui, Hua; Zou, Gui Zheng; Lin, Xiang-Qin

    2003-01-15

    The behavior of luminol electrochemiluminescence (ECL) at a paraffin-impregnated graphite electrode (PIGE) at different applied potentials was studied. Five ECL peaks were observed at 0.31, 0.59, 1.09, 1.54, and -0.58 V versus SCE, respectively, being related to potential scan direction and ranges, N2, O2, pH of the solution, and KCl concentration. The emission spectra of various ECL peaks at different potentials showed that all ECL peaks were initiated by luminol reactions. X-ray diffraction demonstrated that a simple mixture was formed between graphite and paraffin. The fluorescence spectra on the surface of the PIGE suggested that certain groups on the graphite were oxidized when the positive potential was applied to the electrode. In the presence of O2, three main ECL peaks were obtained in 0.1 mol/L KCl at pH 12.2. The ECL peak at 0.59 V with a shoulder is likely due to the reaction of luminol radicals with O2 and further electrooxidation of luminol radicals. The ECL peak at 1.54 V was suggested to be due to the electrooxidation of OH- to HO2- at higher potential and then to O2-, which reacted with luminol to produce light emission. Moreover, the oxygen-containing functional groups formed by the oxidation of the surface of the graphite electrode might enhance the ECL. At -0.58 V, the dissolved oxygen in solution was reduced to HO2-, resulting in light emission. At a potential higher than 1.64 V, ClO- was formed, leading to a broad emission wave and enhancement of the ECL peak at -0.58 V upon the reversal scan. Under nitrogen atmosphere, an ECL peak appeared at 1.09 V. At this potential, OH- was oxidized to O2, followed by the reaction with luminol to generate light emission. At pH 13.2 or 0.5 mol/L KCl, the shoulder of the ECL peak at 0.59 V became an ECL peak at 0.31 V. The conversion of luminol radicals into excited 3-aminophthalate may undergo two routes. Under these conditions, two routes might proceed at a different rate to form another ECL peak. It is

  2. Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

    NASA Astrophysics Data System (ADS)

    Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

    2014-11-01

    This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

  3. Kinetics of reduction of plutonium(VI) and neptunium(VI) by sulfide in neutral and alkaline solutions

    USGS Publications Warehouse

    Nash, K.L.; Cleveland, J.M.; Sullivan, J.C.; Woods, M.

    1986-01-01

    The rate of reduction of plutonium(VI) and neptunium(VI) by bisulfide ion in neutral and mildly alkaline solutions has been investigated by the stopped-flow technique. The reduction of both of these ions to the pentavalent oxidation state appears to occur in an intramolecular reaction involving an unusual actinide(VI)-hydroxide-bisulfide complex. For plutonium the rate of reduction is 27.4 (??4.1) s-1 at 25??C with ??H* = +33.2 (??1.0) kJ/mol and ??S* = -106 (??4) J/(mol K). The apparent stability constant for the transient complex is 4.66 (??0.94) ?? 103 M-1 at 25??C with associated thermodynamic parameters of ??Hc = +27.7 (??0.4) kJ/mol and ??Sc = +163 (??2) J/(mol K). The corresponding rate and stability constants are determined for the neptunium system at 25??C (k3 = 139 (??30) s-1, Kc. = 1.31 (??0.32) ?? 103 M-1), but equivalent parameters cannot be determined at reduced temperatures. The reaction rate is decreased by bicarbonate ion. At pH > 10.5, a second reaction mechanism, also involving a sulfide complex, is indicated. ?? 1986 American Chemical Society.

  4. Nuclear Magnetic Resonance Studies of Aluminosilicate Gels Prepared in High-Alkaline and Salt-Concentrated Solutions

    SciTech Connect

    Wang, Li Q.; Mattigod, Shas V.; Parker, Kent E.; Hobbs, David T.; McCready, David E.

    2005-11-01

    Solid-state 29Si, 27Al, and 23Na MAS (magic angle spinning) NMR techniques in combination with x-ray powder diffraction (XRD) are used to characterize aluminosilicate gels as a function of composition, pH, and reaction times. These gels were prepared at 80 C using initial solutions with low Si/Al ratios, high alkaline and salt concentrations that are characteristic of nuclear tank wastes. XRD data show that cancrinite and sodalite are the main crystalline phases in the aluminosilicate gels produced. It is found that the pH and the salt content have significant effects on the nature of the aluminosilicate gels. Higher pH appears to increase the rate of crystallization, the degree of overall crystallinity and the percentage of cancrinite phases in aluminosilicate gels, whereas the high salt concentration promotes the formation of cancrinite and sodalite and prohibits the formation of other zeolites. Complementary to XRD, NMR is extremely useful for providing the information on the structure of amorphous intermediate gels with no long-range order.

  5. Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions

    SciTech Connect

    Lima,F.; Zhang, J.; Shao, M.; Sasaki, K.; Vukmirovic, M.; Ticianelli, E.; Adzic, R.

    2007-01-01

    We determined, by the rotating disk electrode technique, the kinetics of the oxygen-reduction reaction (ORR) on the surfaces of single crystals of Au(111), Ag(111), Pd(111), Rh(111), Ir(111), and Ru(0001), on Pt monolayers deposited on their surfaces, and also on nanoparticles of these metals dispersed on high-surface-area carbon. Plotting the correlation between the experimentally determined activities of these three types of electrocatalysts with the calculated metal d-band center energies,{var_epsilon}{sub d}, revealed a volcano-type dependence. In all cases, the electronic properties of the metal electrocatalysts, represented by the {var_epsilon}{sub d} value, were used for elucidating the metal-dependent catalytic activities, and establishing their electronic properties-the ORR kinetics relationship. Pt(111), Pt/C, and Pt/Pd(111) were found to top their corresponding volcano plots. Pd in alkaline solutions showed particularly high activity, suggesting it may offer potential replacement for Pt in fuel cells.

  6. Hydrogen generation from catalytic hydrolysis of alkaline sodium borohydride solution using attapulgite clay-supported Co-B catalyst

    NASA Astrophysics Data System (ADS)

    Tian, Hongjing; Guo, Qingjie; Xu, Dongyan

    An attapulgite clay-supported cobalt-boride (Co-B) catalyst used in portable fuel cell fields is prepared in this paper by impregnation-chemical reduction method. The cost of attapulgite clay is much lower compared with some other inert carriers, such as activated carbon and carbon nanotube. Its microstructure and catalytic activity are analyzed in this paper. The effects of NaOH concentration, NaBH 4 concentration, reacting temperature, catalyst loadings and recycle times on the performance of the catalysts in hydrogen production from alkaline NaBH 4 solutions are investigated. Furthermore, characteristics of these catalysts are carried out in SEM, XRD and TEM analysis. The high catalytic activity of the catalyst indicates that it is a promising and practical catalyst. Activation energy of hydrogen generation using such catalysts is estimated to be 56.32 kJ mol -1. In the cycle test, from the 1st cycle to the 9th cycle, the average hydrogen generation rate decreases gradually from 1.27 l min -1 g -1 Co-B to 0.87 l min -1 g -1 Co-B.

  7. Microwave assisted synthesis and characterization of Ni/NiO nanoparticles as electrocatalyst for methanol oxidation in alkaline solution

    NASA Astrophysics Data System (ADS)

    Arunachalam, Prabhakarn; Ghanem, Mohamed A.; Al-Mayouf, Abdullah M.; Al-shalwi, Matar; Hamed Abd-Elkader, Omar

    2017-02-01

    Nickel/Nickel oxide (Ni/NiO) nanoparticles catalyst is prepared by microwave-assisted liquid-phase deposition using ethylene glycol (EG) and water mixture under atmospheric conditions. The physicochemical characterizations of the catalyst carried out by surface area analyzer, x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), electron microscopes measurements suggest the formation of crystalline nanoparticles structure of NiO. The surface area of Ni/NiO prepared using EG/water mixture reaches 70 m2 g‑1 which is 2-fold enhsancement in surface area in comparison with NiO prepared in pure EG and an order of magnitude higher than that of bulk nickel prepared in pure water. The methanol electro-oxidation activity of the Ni/NiO nanoparticles obtained in EG/water mixture displayed more than 4-fold increase in oxidation current at 1.7 V versus RHE in comparison with NiO nanoparticles obtained in EG and 20-fold increase compared to bulk nickel catalyst concord with the enhancement of electro-active surface area. The results show the Ni/NiO nanoparticles produced by microwave assisted synthesis has superior activity for methanol oxidation in alkaline solution over the other nickel based catalysts and has potential for mass production.

  8. Ni nanoparticles supported on graphene layers: An excellent 3D electrode for hydrogen evolution reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Wang, Lixin; Li, Yao; Xia, Meirong; Li, Zhiping; Chen, Zhouhao; Ma, Zhipeng; Qin, Xiujuan; Shao, Guangjie

    2017-04-01

    Metal Ni is a plentiful resource that can actively split water toward hydrogen evolution reaction (HER) in alkaline solution, but exploiting high-efficiency Ni-based composite catalysts is still a significant assignment. Therefore, we design a catalytic material with one-step approach to co-electrodeposit Ni nanoparticles and reduced graphene oxide (rGO) sheets on a three-dimensional Ni foam. When the carbon content existed in Ni-rGO composite catalyst is 3.335 at%, the catalyst exhibits excellent activity on HER with a low Tafel slope (b = 77 mV dec-1), a high exchange current density (j0 = 3.408 mA cm-2), small overpotentials of only 36, 129, and 183 mV to drive 10, 60, and 100 mA cm-2 respectively, and high stability under the different current densities. Such remarkable hydrogen evolution performance is attributed to good electrical conductivity, large specific surface area and harmonious synergistic effect between Ni particles and rGO sheets. In addition, density functional theory (DFT) calculations explain that Ni-rGO composite material presents superior interfacial activity in adsorption/desorption of H* compared with pure Ni and rGO sheet.

  9. The effect of solution chemistry on the preparation of MgAl{sub 2}O{sub 4} by hydrothermal-assisted sol-gel processing

    SciTech Connect

    Amini, M.M. . E-mail: m-pouramini@cc.sbu.ac.ir; Mirzaee, M.; Sepanj, N.

    2007-03-22

    Preparation of magnesium aluminate spinel powder by hydrothermal-assisted sol-gel processing from MgAl{sub 2}(OCH{sub 2}CH{sub 2}OR){sub 8}, R=CH{sub 3} (1), CH{sub 2}CH{sub 2}OCH{sub 3} (2), MgAl{sub 2}[OCH(CH{sub 3}){sub 2}]{sub 8} (3) and MgAl{sub 2}(O- {sup s}Bu){sub 8} (4) in toluene and parent alcohol has been investigated. Coordination status of aluminum atom in precursors was determined by {sup 27}Al NMR and correlation between coordination number of aluminum and development of spinel phase in hydrothermal-assisted sol-gel processing has been studied. The gels obtained from hydrothermal-assisted hydrolysis of magnesium-aluminum alkoxides that contain six-coordinated aluminum atoms in solution (1 and 2) after calcination at 700 deg. C resulted in the formation of pure spinel phase, whereas in similar hydrolysis and calcination processes of precursors that contain four-coordinated aluminum (3 and 4) spinel phase forms along with some Al{sub 2}O{sub 3} and MgO. Selected powders obtained from hydrothermal-assisted sol-gel processing were characterized by thermal analysis (TGA/DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Results indicate that the coordination status of aluminum in the precursor is very crucial for the formation of pure phase spinel. The morphology of prepared spinels was studied by SEM and the results showed that the solvent in hydrothermal-assisted sol-gel processing has a marked effect on the morphology of the resulting MgAl{sub 2}O{sub 4}. In hydrothermal-assisted sol-gel processing of aluminum-magnesium alkoxides in hydrophobic solvent, spherical particles are formed, while in the parent alcohol, non-spherical powders are formed.

  10. The relationship between coefficient of restitution and state of charge of zinc alkaline primary LR6 batteries [Bouncing alkaline batteries: A basic solution

    DOE PAGES

    Bhadra, S.; Hertzberg, B. J.; Croft, M.; ...

    2015-03-13

    The coefficient of restitution of alkaline batteries had been shown to increase as a function of depth of discharge. In this work, using non-destructive mechanical testing, the change in coefficient of restitution is compared to in situ energy-dispersive x-ray diffraction data to determine the cause of the macroscopic change in coefficient of restitution. The increase in coefficient of restitution correlates to the formation of a percolation pathway of ZnO within the anode of the cell, and that the coefficient of restitution saturates at a value of 0.63 ± .05 at 50% state if charge when the anode has densified intomore » porous ZnO solid. Of note is the sensitivity of coefficient of restitution to the amount of ZnO formation that rivals the sensitivity on in situ energy-dispersive x-ray diffraction spectroscopy.« less

  11. The relationship between coefficient of restitution and state of charge of zinc alkaline primary LR6 batteries [Bouncing alkaline batteries: A basic solution

    SciTech Connect

    Bhadra, S.; Hertzberg, B. J.; Croft, M.; Gallaway, J. W.; Van Tassell, B. J.; Chamoun, M.; Erdonmez, C.; Zhong, Z.; Steingart, D. A.

    2015-03-13

    The coefficient of restitution of alkaline batteries had been shown to increase as a function of depth of discharge. In this work, using non-destructive mechanical testing, the change in coefficient of restitution is compared to in situ energy-dispersive x-ray diffraction data to determine the cause of the macroscopic change in coefficient of restitution. The increase in coefficient of restitution correlates to the formation of a percolation pathway of ZnO within the anode of the cell, and that the coefficient of restitution saturates at a value of 0.63 ± .05 at 50% state if charge when the anode has densified into porous ZnO solid. Of note is the sensitivity of coefficient of restitution to the amount of ZnO formation that rivals the sensitivity on in situ energy-dispersive x-ray diffraction spectroscopy.

  12. Synchrotron x-ray spectroscopy of EuHN O3 aqueous solutions at high temperatures and pressures and Nb-bearing silicate melt phases coexisting with hydrothermal fluids using a modified hydrothermal diamond anvil cell and rail assembly

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    A modified hydrothermal diamond anvil cell (HDAC) rail assembly has been constructed for making synchrotron x-ray absorption spectroscopy, x-ray fluorescence, and x-ray mapping measurements on fluids or solid phases in contact with hydrothermal fluids up to ???900??C and 700 MPa. The diamond anvils of the HDAC are modified by laser milling grooves or holes, for the reduction of attenuation of incident and fluorescent x rays and sample cavities. The modified HDAC rail assembly has flexibility in design for measurement of light elements at low concentrations or heavy elements at trace levels in the sample and the capability to probe minute individual phases of a multiphase fluid-based system using focused x-ray microbeam. The supporting rail allows for uniform translation of the HDAC, rotation and tilt stages, and a focusing mirror, which is used to illuminate the sample for visual observation using a microscope, relative to the direction of the incident x-ray beam. A structure study of Eu(III) aqua ion behavior in high-temperature aqueous solutions and a study of Nb partitioning and coordination in a silicate melt in contact with a hydrothermal fluid are described as applications utilizing the modified HDAC rail assembly. ?? 2007 American Institute of Physics.

  13. A fuel-cell reactor for the direct synthesis of hydrogen peroxide alkaline solutions from H(2) and O(2).

    PubMed

    Yamanaka, Ichiro; Onisawa, Takeshi; Hashimoto, Toshikazu; Murayama, Toru

    2011-04-18

    The effects of the type of fuel-cell reactors (undivided or divided by cation- and anion-exchange membranes), alkaline electrolytes (LiOH, NaOH, KOH), vapor-grown carbon fiber (VGCF) cathode components (additives: none, activated carbon, Valcan XC72, Black Pearls 2000, Seast-6, and Ketjen Black), and the flow rates of anolyte (0, 1.5, 12 mL h(-1)) and catholyte (0, 12 mL h(-1)) on the formation of hydrogen peroxide were studied. A divided fuel-cell system, O(2) (g)|VGCF-XC72 cathode|2 M NaOH catholyte|cation-exchange membrane (Nafion-117)|Pt/XC72-VGCF anode|2 M NaOH anolyte at 12 mL h(-1) flow|H(2) (g), was effective for the selective formation of hydrogen peroxide, with 130 mA cm(-2) , a 2 M aqueous solution of H(2)O(2)/NaOH, and a current efficiency of 95 % at atmospheric pressure and 298 K. The current and formation rate gradually decreased over a long period of time. The cause of the slow decrease in electrocatalytic performance was revealed and the decrease was stopped by a flow of catholyte. Cyclic voltammetry studies at the VGCF-XC72 electrode indicated that fast diffusion of O(2) from the gas phase to the electrode, and quick desorption of hydrogen peroxide from the electrode to the electrolyte were essential for the efficient formation of solutions of H(2)O(2)/NaOH.

  14. Fabrication and characterization of silver/titanium dioxide composite nanoparticles in ethylene glycol with alkaline solution through sonochemical process.

    PubMed

    Jhuang, Ya-Yi; Cheng, Wen-Tung

    2016-01-01

    This paper aims to study fabrication and characterization of silver/titanium oxide composite nanoparticle through sonochemical process in the presence of ethylene glycol with alkaline solution. By using ultrasonic irradiation of a mixture of silver nitrate, the dispersed TiO2 nanoparticle in ethylene glycol associated with aqueous solution of sodium oxide yields Ag/TiO2 composite nanoparticle with shell/core-type geometry. The powder X-ray diffraction (XRD) of the Ag/TiO2 composites showed additional diffraction peaks corresponding to the face-centered cubic (fcc) structure of silver crystallization phase, apart from the signals from the cores of TiO2. Transmission electron microscopy (TEM) images of Ag/TiO2 composites, which average particle size is roughly 80 nm, reveal that the titanium oxide coated by Ag nanoparticle with a grain size of about 2-5 nm. Additionally, the formation of silver nanoparticles on TiO2 was monitored by ultraviolet visible light spectrophotometer (UV-Vis). As measured the optical absorption spectra of as-synthesized Ag nanoparticle varying with time, the mechanism of surface formatting silver shell on the cores of TiO2 could be explored by autocatalytic reaction; the conversion of Ag particle from silver ion is 98% for the reaction time of 1000 s; and the activity energy of synthesizing Ag nanoparticles on TiO2 is 40 kJ/mol at temperature ranging from 5 to 25°C. Hopefully, this preliminary investigation could be used for mass production of composite nanoparticles assisted by ultrasonic chemistry in the future.

  15. Removal of Mn from aqueous solution using fly ash and its hydrothermal synthetic zeolite.

    PubMed

    Belviso, Claudia; Cavalcante, Francesco; Di Gennaro, Spartaco; Lettino, Antonio; Palma, Achille; Ragone, Pietro; Fiore, Saverio

    2014-05-01

    A number of water purification processes have been developed in recent years based on the utilisation of low-cost materials with high pollutant removal efficiency. Among these materials, fly ash and zeolite synthesised from fly ash are two examples of high-efficiency adsorbents. Column absorption tests were performed in order to compare the manganese sorption behaviour of an Italian coal fly ash and zeolite synthesised from it. Different masses of both materials (10-60 g) were exposed to solutions containing a total metal concentration of 10 mg/L. Batch adsorption studies were also conducted to determine the effect of time on the removal on Mn sequestration. The results indicate that both materials are effective for the removal of Mn from aqueous solution by precipitation due to the high pH of the solid/liquid mixtures. However, the leaching tests reveal that the amount of Mn removed from the fly ash was greater than that leached from the zeolite, thereby indicating that the metal is partially sequestrated by zeolite.

  16. Hydrothermal synthesis and crystal structure of two new hydrated alkaline earth metal borates Sr3B6O11(OH)2 and Ba3B6O11(OH)2.

    PubMed

    Heyward, Carla; McMillen, Colin; Kolis, Joseph

    2012-04-02

    Two new hydrated borates Sr(3)B(6)O(11)(OH)(2) (1) and Ba(3)B(6)O(11)(OH)(2) (2) were hydrothermally synthesized. Their structures were determined by single-crystal X-ray diffraction and further characterized by IR, powder XRD, and DSC/TGA. Compound 1 crystallizes in the triclinic space group P-1 with unit cell parameters of a = 6.6275(13) Å, b = 6.6706(13) Å, c = 11.393(2) Å, α = 91.06(3)°, β = 94.50(3)°, and γ = 93.12(3)°, while compound 2 crystallizes in the noncentrosymmetric monoclinic space group Pc with a = 6.958(14) Å, b = 7.024(14) Å, c = 11.346(2) Å, and β = 90.10(3)°. In spite of the differences in symmetry and packing of the borate chains, both structures consist of the same fundamental building block (FBB) of a [B(6)O(11)(OH)(2)](-6) unit and three unique alkaline earth metal atoms.

  17. Spectrophotometric determination of copper in alkaline solutions and evaluation of some hydroxy-substituted 1,10-phenanthrolines as chromogenic reagents.

    PubMed

    Dunbar, W E; Schilt, A A

    1972-09-01

    Seven new hydroxy-substituted 1,10-phenanthroline derivatives have been evaluated as chromogenic reagents for the determination of copper in strongly alkaline solution. The most sensitive of these, 2,9-dimethyl-4,7-dihydroxy-1,10-phenanthroline, has proven to be highly effective in a simple, rapid procedure for determining trace amounts of copper in sodium hydroxide, potassium carbonate, sodium phosphate or ammonium hydroxide.

  18. Enzymatically mediated bioprecipitation of heavy metals from industrial wastes and single ion solutions by mammalian alkaline phosphatase.

    PubMed

    Chaudhuri, Gouri; Shah, Gaurav A; Dey, Pritam; S, Ganesh; Venu-Babu, P; Thilagaraj, W Richard

    2013-01-01

    The study was aimed at investigating the potential use of calf intestinal alkaline phosphatase (CIAP) enzyme in the removal of heavy metals (Cd(2+), Ni(2+), Co(2+) and Cr(3+/6+)) from single ion solutions as well as tannery and electroplating effluents. CIAP mediated bioremediation (white biotechnology) is a novel technique that is eco-friendly and cost effective unlike the conventional chemical technologies. Typical reactions containing the enzyme (CIAP) and p-nitrophenyl phosphate (pNPP) as substrate in Tris-HCl buffer (pH 8 and 11) and either single ion metal solutions (250 ppm and 1000 ppm) or effluents from tannery or electroplating industry were incubated at 37°C for 30 min, 60 min and 120 min. The inorganic phosphate (P(i)) generated due to catalytic breakdown of pNPP complexes free metal ions as metal-phosphate and the amount of metal precipitated was derived by estimating the reduction in the free metal ion present in the supernatant of reactions employing atomic absorption spectrophotometer (AAS). Better precipitation of metal was obtained at pH 11 than at pH 8 and between the two concentrations of different metals tested, an initial metal concentration of 250 ppm in the reaction gave more precipitation than with 1000 ppm. Experimental data showed that at pH 11, the percentage of removal of metal ions (for an initial concentration of 250 ppm) was in the following order: Cd(2+) (80.99%) > Ni(2+) (64.78%) > Cr(3+) > (46.15%) > Co(2+) (36.47%) > Cr(6+) (32.33%). The overall removal of Cr(3+) and Cr(6+) from tannery effluent was 32.77% and 37.39% respectively in 120 min at pH 11. Likewise, the overall removal of Cd(2+), Co(2+) and Ni(2+) from electroplating effluent was 50.42%, 13.93% and 38.64% respectively in 120 min at pH 11. The study demonstrates that bioprecipitation by CIAP may be a viable and environmental friendly method for clean-up of heavy metals from tannery and electroplating effluents.

  19. Influence of acid and alkaline sources on optical, structural and photovoltaic properties of CdSe nanoparticles precipitated from aqueous solution

    NASA Astrophysics Data System (ADS)

    Coria-Monroy, C. Selene; Sotelo-Lerma, Mérida; Hu, Hailin

    2016-06-01

    CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.

  20. Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

    NASA Astrophysics Data System (ADS)

    Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

    A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1

  1. Chemical speciation in concentrated alkaline aluminate solutions in sodium, potassium and caesium media. Interpretation of the unusual variations of the observed hydroxide activity.

    PubMed

    Sipos, Pál; Schibeci, Mark; Peintler, Gábor; May, Peter M; Hefter, Glenn

    2006-04-21

    A detailed electrochemical investigation using H2/Pt electrode potentiometry as well as Raman and NMR spectroscopy was carried out to develop a comprehensive chemical explanation for the unusual patterns of hydroxide concentrations observed in strongly alkaline, highly concentrated aluminate solutions (Bayer-liquors). For this, aluminate solutions with various alkaline metal background cations were investigated. The effect of the temperature on the observed patterns was also studied, and for comparison with solutions of similar concentrations, the chemical speciation of borate solutions was also studied. The formation of the NaOH 0 ion-pair has been proven with the formation constant (defined in terms of activities) beta 0 = 0.78 +/- 0.08. The formation of analogous KOH 0 or CsOH 0 ion-pairs under the experimental conditions applied is negligible. Assuming the formation of the NaAl(OH)4 (0) ion-pair is not necessary for modeling the experimental findings, as its formation causes only secondary effects on the potentiometric patterns. It has also been shown that all experimental data can be interpreted quantitatively if the formation of the doubly charged dimeric aluminate species is included in the calculation of the changes in the mean activity coefficients. The formation constant of the aluminate dimer could not be estimated purely from the H2/Pt potentiometric data but a lower limit for its formation constant (defined in terms of activities) has been derived. These conclusions are in full congruency with those derived from the Raman spectra of solutions with similar concentrations, so the two independent experimental methods lead to the same set of chemical species in highly concentrated alkaline aluminate solutions.

  2. Zeta potential of anoxygenic phototrophic bacteria and Ca adsorption at the cell surface: possible implications for cell protection from CaCO3 precipitation in alkaline solutions.

    PubMed

    Bundeleva, Irina A; Shirokova, Liudmila S; Bénézeth, Pascale; Pokrovsky, Oleg S; Kompantseva, Elena I; Balor, Stephanie

    2011-08-01

    Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation.

  3. Hydrothermal Processing

    SciTech Connect

    Elliott, Douglas C.

    2011-03-11

    This chapter is a contribution to a book on Thermochemical Conversion of Biomass being edited by Prof. Robert Brown of Iowa State University. It describes both hydrothermal liquefaction and hydrothermal gasification of biomass to fuels.

  4. Development of chemiluminescence method for determination of 10-hydroxycamptothecin based on luminol-[Ag(HIO₆)₂]⁵⁻ reaction in alkaline solution.

    PubMed

    Sun, Hanwen; Chen, Peiyun; Shi, Shasha; Li, Liqing

    2011-01-01

    A novel chemiluminescence (CL) method was developed for the determination of 10-hydroxycamptothecin(HCPT) based on the CL reaction between [Ag(HIO₆)₂]⁵⁻ and luminol in alkaline solution. CL emission of Ag(III) complex-luminol in alkaline medium was very different from that in acidic medium. A possible mechanism of enhanced CL emission was suggested. The enhanced effect of HCPT on CL emission of the [Ag(HIO₆)₂]⁵⁻-luminol system was found. The enhanced degree of CL emission was proportional to HCPT concentration. The effect of the reaction conditions on CL emission was examined. Under optimal conditions, the limit of detection was 6.5 × 10⁻⁹ g mL⁻¹. The proposed method was applied for the determination of HCPT in real samples with the recoveries of 93.2-109% with the RSD of 1.7-3.3%.

  5. Two chain gallium fluorodiphosphates: synthesis, structure solution, and their transient presence during the hydrothermal crystallisation of a microporous gallium fluorophosphate.

    PubMed

    Millange, Franck; Walton, Richard I; Guillou, Nathalie; Loiseau, Thierry; O'Hare, Dermot; Férey, Gérard

    2002-04-21

    Two novel gallium fluorodiphosphates have been isolated and their structures solved ab initio from powder X-ray diffraction data; the materials readily interconvert under hydrothermal conditions, and are metastable with respect to an open-framework zeolitic gallium fluorophosphate, during the synthesis of which they are present as transient intermediates.

  6. Structural studies of TiO2/wood coatings prepared by hydrothermal deposition of rutile particles from TiCl4 aqueous solutions on spruce (Picea Abies) wood

    NASA Astrophysics Data System (ADS)

    Pori, Pavel; Vilčnik, Aljaž; Petrič, Marko; Sever Škapin, Andrijana; Mihelčič, Mohor; Šurca Vuk, Angela; Novak, Urban; Orel, Boris

    2016-05-01

    A low temperature approach was developed for the deposition of rutile TiO2 particles on a wood surface by hydrolysis of TiCl4 in aqueous solutions acidified with HCl, and crystallization at 75 and 90 °C (1 h). Prior to hydrothermal treatment, Picea Abies wood was first soaked in a 0.5 mmol/l aqueous solution containing anionic surfactant sodium dodecyl sulphate (SDS, Sigma Aldrich) for 2 h at 80 °C. The crystal structure of the hydrothermally made rutile particles was determined with XRD, while the morphology of the deposited TiO2 particles and their distribution in the wood were examined with SEM and EDX measurements. The penetration and amount of deposited rutile particles could be modified by changing the deposition conditions. Thicker layers were obtained from more concentrated aqueous TiCl4 solutions with and without added HCl, and with longer deposition times and higher temperatures of the hydrothermal treatment. The interaction of TiO2 particles with hemicellulose and lignin in wood was established from infrared attenuated total reflection (FT-IR ATR) and Raman spectra measurements, from which the spectra of wood were subtracted. Analysis of the subtraction spectra showed the presence of titania particles on the wood surface, revealing also the establishment of TiO2-wood coordinative bonds of titanium ions with hemicellulose and lignin. The red frequency shift of the OH stretching modes suggested interaction of the TiO2 particles with water molecules of wood. TiO2 deposited on wood treated with SDS became hydrophobic (water contact angles (WCA) of 150°), contrasting the properties of untreated wood with a deposited TiO2 particle coating, which remained hydrophilic.

  7. On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd

  8. Advanced alkaline water electrolysis

    NASA Astrophysics Data System (ADS)

    Wakabayashi, N.; Torikai, E.; Kawami, Y.; Takenaka, H.

    Results are presented of experimental studies of possible separators and electrodes for use in advanced, high-temperature, high-pressure alkaline water electrolyzers. Material evaluations in alkaline water electrolyzers at temperatures from 100 to 120 C have shown a new type polytetrafluoroethylene membrane impregnated with potassium titanate to be the most promising when the separator is prepared by the hydrothermal treatment of a porous PFTE membrane impregnated with hydrated titanium oxide. Measurements of cell voltages in 30% KOH at current densities from 5 to 100 A/sq dm at temperatures up to 120 C with nickel electrodes of various structures have shown the foamed nickel electrode, with an average pore size of 1-1.5 mm, to have the best performance. When the foamed nickel is coated by fine powdered nickel, carbonyl nickel or Raney nickel to increase electrode surface areas, even lower cell voltages were found, indicating better performance.

  9. Distributions of 14 elements on 60 selected absorbers from two simulant solutions (acid-dissolved sludge and alkaline supernate) for Hanford HLW Tank 102-SY

    SciTech Connect

    Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

    1993-10-01

    Sixty commercially available or experimental absorber materials were evaluated for partitioning high-level radioactive waste. These absorbers included cation and anion exchange resins, inorganic exchangers, composite absorbers, and a series of liquid extractants sorbed on porous support-beads. The distributions of 14 elements onto each absorber were measured from simulated solutions that represent acid-dissolved sludge and alkaline supernate solutions from Hanford high-level waste (HLW) Tank 102-SY. The selected elements, which represent fission products (Ce, Cs, Sr, Tc, and Y); actinides (U, Pu, and Am); and matrix elements (Cr, Co, Fe, Mn, Zn, and Zr), were traced by radionuclides and assayed by gamma spectrometry. Distribution coefficients for each of the 1680 element/absorber/solution combinations were measured for dynamic contact periods of 30 min, 2 h, and 6 h to provide sorption kinetics information for the specified elements from these complex media. More than 5000 measured distribution coefficients are tabulated.

  10. Hydrothermal synthesis of hollow silica spheres under acidic conditions.

    PubMed

    Yu, Qiyu; Wang, Pengpeng; Hu, Shi; Hui, Junfeng; Zhuang, Jing; Wang, Xun

    2011-06-07

    It is well-known that silica can be etched in alkaline media or in a unique hydrofluoric acid (HF) solution, which is widely used to prepare various kinds of hollow nanostructures (including silica hollow structures) via silica-templating methods. In our experiments, we found that stöber silica spheres could be etched in generic acidic media in a well-controlled way under hydrothermal conditions, forming well-defined hollow/rattle-type silica spheres. Furthermore, some salts such as NaCl and Na(2)SO(4) were found to be favorable for the formation of hollow/rattle-type silica spheres.

  11. Decontamination of alkaline solution from technetium and other fission products and from some actinides by reductive coprecipitation and sorption on metals

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Tananaev, I.G.; Kareta, A.V.; Trushina, V.E.

    1997-09-01

    Effective decontamination of alkaline solutions and Hanford Site tank waste simulants from technetium has been accomplished by reductive coprecipitation with iron(III) hydroxide. Addition of 1 M (NH{sub 4}){sub 2}Fe(SO{sub 4}){sub 2} to 0.5 to 4.0 M NaOH to a final concentration of 0.1 to 0.15 M coprecipitates more than 99% of the technetium. from 0.5 to 1.0 M NaOH and 98 to 96% from 2.0 to 4.0 M NaOH. Similar results were obtained by reduction of Tc(VII) with 0.1 to 0.15 M hydrazine and subsequent addition of FeCl{sub 3} to a final concentration of 0.15 M. Inclusion of four complex-forming agents [0.01 M phosphate, 0.1 M EDTA (ethylenediaminetetraacetate), 0.03 M citrate, and 0.1 M glycolate (HOCH{sub 2}CO{sub 2}{sup -})] to the alkaline solution decreases technetium coprecipitation with iron hydroxide to 85% under otherwise similar conditions. Inclusion of 0.04 M Na{sub 2}CrO{sub 4} drastically decreases reductive coprecipitation of Tc(VII) in 0.5 to 4.0 M NaOH. Iron(II) salt, added to a 0.07 M excess over that of chromate, completely reduces chromate and provides greater than 99% coprecipitation of technetium with product iron(III) and chromium(III) hydroxides. Technetium(VII) reduction by hydrazine is slow in the presence of chromate in alkaline solution, and technetium coprecipitation is incomplete in these conditions. Decontamination of an alkaline Hanford Site tank waste simulant, containing 0.04M chromate and eleven salts and complex-forming agents, by adding 1 M iron(II) salt solution was studied. Coprecipitation of 15 to 28% of the technetium and more than 99% of the plutonium occurred in the Fe/Cr(III) hydroxide precipitate produced by adding 0.05 to 0.10 M iron(II). Chromate reduction was incomplete. About 75% of the technetium was coprecipitated, and the chromate was completely reduced, after adding 0.2 M iron(II) salt.

  12. High-pressure densified solid solutions of alkaline earth hexaborides (Ca/Sr, Ca/Ba, Sr/Ba) and their high-temperature thermoelectric properties

    SciTech Connect

    Gürsoy, M.; Takeda, M.; Albert, B.

    2015-01-15

    Solid solutions of alkaline earth hexaborides were synthesized and densified by spark plasma sintering at 100 MPa. The high-temperature thermoelectric properties (Seebeck coefficients, electrical and thermal diffusivities, heat capacities) were measured between room temperature and 1073 K. CaB{sub 6}, SrB{sub 6}, BaB{sub 6} and the ternary hexaborides Ca{sub x}Sr{sub 1−x}B{sub 6}, Ca{sub x}Ba{sub 1−x}B{sub 6}, Sr{sub x}Ba{sub 1−x}B{sub 6} (x = 0.25, 0.5, 0.75) are n-type conducting compounds over the whole compositional and thermal ranges. The values of the figure of merit ZT for CaB{sub 6} (ca. 0.3 at 1073 K) were found to be significantly increased compared to earlier investigations which is attributed to the densification process. - Highlights: • Solid solutions of alkaline earth hexaborides were synthesized. • High-temperature thermoelectric properties of mixed calcium borides are excellent. • Spark plasma source densification results in high ZT values. • Borides are rare-earth free and refractory materials.

  13. Purification of alkaline solutions and wastes from actinides and technetium by coprecipitation with some carriers using the method of appearing reagents: Final Report

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Kareta, A.V.; Gelis, A.V.; Shilov, V.P.; German, K.E.; Firsova, E.V.; Maslennikov, A.G.; Trushina, V.E.

    1998-09-01

    The coprecipitation of transuranium elements (TRU) and technetium from alkaline solutions and from simulants of Hanford Site tank wastes has been studied in reducing and oxidizing conditions on uranium(IV,VI) hydroxocompounds, tetraalkylammonium perrhenate and perchlorate, and on hydroxides of Fe(III), Co(III), Mn(II), and Cr(III) using the method of appearing reagents (MAR). Coprecipitations in alkaline solution have been shown to give high decontamination factors (DF) at low content of carrier and in the presence of high salt concentrations. Uranium(IV) hydroxide in concentrations higher than 3 {times} 10{sup {minus}3} M coprecipitates Pu and Cm in any oxidation state from 0.2 to 4 M NaOH with DFs of 110 to 1000 and Np and Tc with DFs of 51 to 176. Technetium (VII) coprecipitates with (5 to 8) {times} 10{sup {minus}4} M tetrabutylammonium (TBA) perrhenate in 0.01 to 0.02 M TBA hydroxide from 0.5 to 1.5 M NaOH to give DFs of 150 to 200. Coprecipitations of Np and Pu with Co(OH){sub 3}, Fe(OH){sub 3}, Cr(OH){sub 3}, and Mn(OH){sub 2} obtained by the MAR from precursors in the range from pH 10.5 to 0.4 M NaOH give DFs from 80 to 400.

  14. Effects of temperature and alkali concentration on the dynamic interfacial tension between heavy oil and alkaline solutions

    SciTech Connect

    Chiwetelu, C.I.; Neale, G.H.; Hornof, V. ); George, A.E. )

    1992-01-01

    This paper deals with the screening of a number of alkaline reagents for potential application in the waterflooding of heavy oil reservoirs at moderate temperatures. Sodium hydroxide, sodium metasilicate and sodium orthosilicate were all screened in accordance with a novel methodology that is based on physical and interfacial property measurements for selecting the most appropriate alkali for a target crude. The experimental oil was a Saskatchewan crude with an acid number of 1.88 mg KOH/g oil and a viscosity of 475 mPa.s at 25{degrees} C. The interfacial tension between this oil and distilled water was measured at various temperatures ranging from 25{degrees} C to 75{degrees} C. These tension values were relatively unaffected by changes in temperature as well as by the contact time between the two phases. However, the viscosity of the oil decreased by 87% when the temperature was raised from 35{degrees} C to 75{degrees} C. The addition of small quantities of the alkaline reagents (up to a maximum concentration of 500 mM in salt-free water) resulted in significant reductions in the interfacial tension.

  15. Plants increase arsenic in solution but decrease the non-specifically bound fraction in the rhizosphere of an alkaline, naturally rich soil.

    PubMed

    Obeidy, Carole; Bravin, Matthieu N; Bouchardon, Jean-Luc; Conord, Cyrille; Moutte, Jacques; Guy, Bernard; Faure, Olivier

    2016-04-01

    We aimed at determining the major physical-chemical processes that drive arsenic (As) dynamic in the rhizosphere of four species (Holcus lanatus, Dittrichia viscosa, Lotus corniculatus, Plantago lanceolata) tested for phytostabilization. Experiments were performed with an alkaline soil naturally rich in As. Composition of the soil solution of planted and unplanted pots was monitored every 15 days for 90 days, with a focus on the evolution of As concentrations in solution and in the non-specifically bound (i.e. easily exchangeable) fraction. The four species similarly increased As concentration in solution, but decreased As concentration in the non-specifically bound fraction. The major part (60%) of As desorbed from the non-specifically bound fraction in planted pots was likely redistributed on the less available fractions of As on the solid phase. A second part (35%) of desorbed As was taken up by plants. The minor part (5%) of desorbed As supplied As increase in solution. To conclude, plants induced a substantial redistribution of As on the less available fractions in the rhizosphere, as expected in phytostabilization strategies. Plants however concomitantly increased As concentration in the rhizosphere solution which may contribute to As transfer through plant uptake and leaching.

  16. Visualization of the missing role of hydrothermal interactions in a Japanese megalopolis for a win-win solution.

    PubMed

    Nakayama, T

    2012-01-01

    The urban heat island effect has become a serious environmental problem with the expansion of cities and industrial areas. Prohibition of the use of groundwater has caused a further serious problem such as floating of subways, stations and buildings through an imbalance of the hydrologic cycle in a Japanese megalopolis. Most of the previous research has evaluated separately hydrologic and thermal cycles in atmospheric, land and water areas because of the complexity in this feedback mechanism. In this study, the author used the process-based National Integrated Catchment-based Eco-hydrology (NICE) model, which includes surface-unsaturated-saturated water processes coupled with the urban canopy and regional atmospheric models, to simulate the effect of urban geometry and anthropogenic exhaustion on the hydrothermal changes in the atmospheric/land areas of the Japanese megalopolis. The simulation was conducted with multi-scale in horizontal regional-urban-point levels and in vertical atmosphere-surface-unsaturated-saturated layers, and projected the effect of water resources use to ameliorate the heat island and its impact on the hydrologic change in the catchment. Finally, the author presented the procedure to visualize the missing role of hydrothermal interactions in atmospheric, land and water areas, which would be effective to recover a sound hydrologic cycle and to create thermally pleasing environments in an eco-conscious megalopolis.

  17. Amino-functionalized alkaline clay with cationic star-shaped polymer as adsorbents for removal of Cr(VI) in aqueous solution

    NASA Astrophysics Data System (ADS)

    Pan, Yuanfeng; Cai, Pingxiong; Farmahini-Farahani, Madjid; Li, Yiduo; Hou, Xiaobang; Xiao, Huining

    2016-11-01

    Pentaerythritol (PER) was esterified with 2-bromoisobutyryl bromide to synthesize a four-arm initiator 4Br-PER for atom transfer radical polymerization (ATRP). Star-shaped copolymers (P(AM-co-DMAEMA)4, CSP) were prepared via ATRP using dimethyl aminoethyl methacrylate (DMAEMA) and acrylamide (AM) as comonomers, while Br-PER and CuBr/2,2‧-bipyridine (BPY) as the initiator and the catalyst, respectively. The resulting four-arm initiator and star-shaped polymer (CSP) were characterized with FT-IR, 1H NMR and Ubbelohde viscometry. Alkaline clay (AC) was immobilized with CSPs to yield amino groups, and the cationic star polymer-immobilized alkaline clay (CSP-AC) was applied to remove Cr(VI) from the aqueous solution in batch experiments. Various influencing factors, including pH, contact time and immobilization amount of CSP on adsorption capacity of CSP-AC for Cr(VI) were also investigated. The results demonstrated that Cr(VI) adsorption was highly pH dependent. The optimized pH value was 4.0. The adsorption isotherms of the adsorbent fit the Langmuir model well, with the maximum adsorption capacity of 137.9 mg/g at 30 °C. The material should be a promising adsorbent for Cr(VI) removal, with the advantages of high adsorption capacity.

  18. Design, fabrication, and test of a hydrothermal reactor for origin-of-life experiments.

    PubMed

    Mielke, Randall E; Russell, Michael J; Wilson, Philip R; McGlynn, Shawn E; Coleman, Max; Kidd, Richard; Kanik, Isik

    2010-10-01

    We describe a continuous high-pressure flow reactor designed to simulate the unforced convective interaction of hydrothermal solutions and ocean waters with submarine crust on early Earth-conditions appropriate to those that may have led to the onset of life. The experimental operating conditions are appropriate for investigating kinetic hydrothermal processes in the early history of any sizable wet, rocky planet. Beyond the description of the fabrication, we report an initial experiment that tested the design and investigated the feasibility of sulfide and silica dissolution in alkaline solution from iron sulfide and basaltic rock, and their possible subsequent transport as HS(-) and H(2)SiO(2-)(4) in hot alkaline solutions. Delivery of hydrogen sulfide and dihydrogen silicate ions would have led to the precipitation of ferrous hydroxide, hydroxysilicates, and iron sulfides as integral mineral components of an off-ridge compartmentalized hydrothermal mound in the Hadean. Such a mound could, we contend, have acted as a natural chemical and electrochemical reactor and, ultimately, as the source of all biochemistry on our planet. In the event, we show that an average of ∼1 mM/kg of both sulfide and silica were released throughout, though over 10 mM/kg of HS(-) was recorded for ∼100 minutes in the early stages of the experiment. This alkaline effluent from the reactor was injected into a reservoir of a simulacrum of ferrous iron-bearing "Hadean Ocean" water in an experiment that demonstrated the capacity of such fluids to generate hydrothermal chimneys and a variety of contiguous inorganic microgeode precipitates bearing disseminations of discrete metal sulfides. Comparable natural composite structures may have acted as hatcheries for emergent life in the Hadean.

  19. Facile synthesis of nitrogen-doped carbon nanotubes encapsulating nickel cobalt alloys 3D networks for oxygen evolution reaction in an alkaline solution

    NASA Astrophysics Data System (ADS)

    Yu, Jie; Zhong, Yijun; Zhou, Wei; Shao, Zongping

    2017-01-01

    Efficient oxygen evolution reaction (OER) catalysts are required to facilitate the large-scale exploitation of renewable energy resources and applications in electrochemical energy conversion technologies. Here, we show that metal alloy-based hybrids can provide higher electrocatalytic activity than their individual metal-based hybrids. In particular, NiCo alloys encapsulated within nitrogen-doped carbon nanotubes (NiCo@NCNTs) showed higher OER activities in an alkaline solution than the individual metal hybrids (Ni@NCNTs and Co@NCNTs), highlighting a synergy between the Ni and Co components. NiCo@NCNTs pyrolyzed at 800 °C displayed an overpotential of ∼41 mV at a current density of 10 mA cm-2 and were more stable than IrO2 during 1000-cycle accelerated durability testing at a scan rate of 100 mV s-1.

  20. Evaluation of packed-bed and fluidized-bed cell technology for the destruction and removal of contaminants in alkaline waste solutions. Final report

    SciTech Connect

    Hobbs, D.T.; Bockris, J.O.M.; Kim, Jinseong

    1995-12-31

    Disposing of the large quantity of nuclear waste that has been produced within the DOE complex is an area of active research and development. Electrochemical processes have been reported for the treatment of alkaline wastes including the destruction of nitrate and nitrite and the removal of metals such as Tc and Ru. Electrolytic recovery of metals from dilute solution has been reported using conventional porous electrodes such as felt electrode and reticulated electrode, but use of such electrodes is limited. The pores of such electrodes become blocked as a consequence of metal deposition. If an attempt is made to regenerate these electrodes by dissolution of the deposited metals, oxygen evolution on the matrix competes with dissolution of metals deposited within the pores. On the other hand, the use of three dimensional packed-bed and fluidized-bed electrodes having large surface area per unit volume would offer an improvement on felt or reticulated system because of the greater ease of regeneration.

  1. NiP₂ nanosheet arrays supported on carbon cloth: an efficient 3D hydrogen evolution cathode in both acidic and alkaline solutions.

    PubMed

    Jiang, Ping; Liu, Qian; Sun, Xuping

    2014-11-21

    Designing efficient and stable hydrogen evolution catalysts made from earth-abundant elements is essential to the development of solar-driven water-splitting devices. In this communication, we develop a two-step strategy for constructing NiP2 nanosheet arrays on carbon cloth (NiP2 NS/CC). As a novel 3D hydrogen evolution cathode, the NiP2 NS/CC electrode is highly active in acidic solutions and needs an overpotential of 75 and 204 mV to achieve current densities of 10 and 100 mA cm(-2), respectively, and it preserves its catalytic activity for at least 57 h. Moreover, it also operates efficiently under alkaline conditions.

  2. Electrodeposition, characterization and long term stability of NiW and NiWZn coatings on copper substrate in alkaline solution

    NASA Astrophysics Data System (ADS)

    Sürme, Yavuz; Gürten, A. Ali; Kayakırılmaz, Kadriye

    2013-07-01

    This paper describes the electrodeposition of Ni, NiW and NiWZn coatings onto copper surfaces from electrolyte solutions containing Na3C6H5O7, Na2WO4, NiSO4 and ZnSO4. The electrocatalytic effects of electrodeposited coatings were investigated for hydrogen evolution reactions in 1 M NaOH solution. Surface characterization studies were carried out by energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy and cross-section analysis. The effect of operating conditions on the chemical composition, microstructure and electrocatalytic properties of Ni-W coatings was studied. The Zn ions were used to improve the active surface area and catalytic activity of the electrodeposited surface. The electrocatalytic activity of NiW and NiWZn coated electrodes for the hydrogen evolution reaction in alkaline solution was compared with that of an electrodeposited Ni electrode and copper substrate by using cathodic polarization curves and electrochemical impedance spectroscopy techniques over 96 h of electrolysis. The results proved that the NiWZn coated electrode showed better electrocatalytic activity and durability than bare Cu, Ni and NiW coatings.

  3. Selective colorimetric determination of TNT partitioned between an alkaline solution and a strongly basic Dowex 1-X8 anion exchanger.

    PubMed

    Uzer, Ayşem; Erçağ, Erol; Apak, Reşat

    2008-01-30

    The Meisenheimer anions formed from TNT in KOH solutions in alcohol or acetone were used in screening tests for TNT among possible nitro-explosives. The same reaction was used for the spectrophotometric assay of TNT in soil by CRREL (Cold Regions Research & Engineering Laboratory of the U.S. Army) method, also known as Jenkins' method, but the color stability was too dependent on the solution composition and the water tolerance was low, necessitating complete drying of soil samples (which may cause partial analyte decomposition) prior to analysis. This study reports the development of a colorimetric method based on the solid phase extraction (SPE) of the Meisenheimer anion formed from TNT and aqueous NaOH into a strongly basic anion exchange resin Dowex 1-X8 (OH(-) form). The orange-red color that developed both in the solid resin and solution phases was persistent for at least 1h. The resin was let to swell in alcohol, washed first with 1M aqueous NaOH, and then with H(2)O before use. To 5 mL of 4-400 ppm TNT solutions in 1:1 (v/v) acetone-water, 0.5 mL of 5% NaOH was added, diluted to 50 mL with 1:1 acetone-water, and the resulting solutions (containing the orange-red Meisenheimer anion of TNT) were agitated at room temperature with 0.9 g resin for < or =50 min. TNT exhibited a reasonably constant distribution coefficient between the resin and aqueous phases. The absorbance of the filtered solutions was measured against a reagent blank at 500nm. The TNT-loaded resins were regenerated with 1M HCl containing sodium sulfite. The calibration line of filtrate absorbance versus analytical concentration was linear over two orders of magnitude between 0.4 and 40 ppm TNT in final solution. Unlike Jenkins' method, the method was tolerant to 100-fold (by mass) of common soil anions like sulfate, nitrate, and chloride. The basic advantages of the developed colorimetric method over the similar CRREL/Jenkins' method may be summarized as color stability, water and common ion

  4. Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-12-15

    Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.

  5. An ion-imprinted amino-functionalized silica gel sorbent prepared by hydrothermal assisted surface imprinting technique for selective removal of cadmium (II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Fan, Hong-Tao; Li, Jing; Li, Zhan-Chao; Sun, Ting

    2012-02-01

    A new ion-imprinted amino-functionalized silica gel sorbent was synthesized by the hydrothermal-assisted surface imprinting technique using Cd2+ as the template, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (AAAPTS) as the functional monomer, and epichlorohydrin as the cross-linking agent (IIP-AAAPTS/SiO2) for the selective removal of Cd2+ from aqueous solution, and was characterized by FTIR, SEM, nitrogen adsorption and the static adsorption-desorption experiment method. The specific surface area of the IIP-AAAPTS/SiO2 sorbents was found to be 149 m2 g-1. The results showed that the maximum static adsorption capacities of IIP-AAAPTS/SiO2 sorbents by hydrothermal heating method and by the conventional heating method were 57.4 and 31.6 mg g-1, respectively. The IIP-AAAPTS/SiO2 sorbents offered a fast kinetics for the adsorption and desorption of Cd(II). The relative selectivity coefficients of IIP-AAAPTS/SiO2 sorbents for Cd2+/Co2+, Cd2+/Ni2+, Cd2+/Zn2+, Cd2+/Pb2+ and Cd2+/Cu2+ were 30.68, 14.02, 3.00, 3.12 and 6.17, respectively. IIP-AAAPTS/SiO2 sorbents had a substantial binding capacity in the range of pH 4-8 and could be used repeatedly. Equilibrium data fitted perfectly with Langmuir isotherm model compared to Freundlich isotherm model. Kinetic studies indicated that adsorption followed a pseudo-second-order model. Negative values of ΔG° indicated spontaneous adsorption and the degree of spontaneity of the reaction increased with increasing temperature. ΔH° of 26.13 kJ mol-1 due to the adsorption of Cd2+ on the IIP-AAAPTS/SiO2 sorbents indicated that the adsorption was endothermic in the experimental temperature range.

  6. Catalytic hydrothermal liquefaction of water hyacinth.

    PubMed

    Singh, Rawel; Balagurumurthy, Bhavya; Prakash, Aditya; Bhaskar, Thallada

    2015-02-01

    Thermal and catalytic hydrothermal liquefaction of water hyacinth was performed at temperatures from 250 to 300 °C under various water hyacinth:H2O ratio of 1:3, 1:6 and 1:12. Reactions were also carried out under various residence times (15-60 min) as well as catalytic conditions (KOH and K2CO3). The use of alkaline catalysts significantly increased the bio-oil yield. Maximum bio-oil yield (23 wt%) comprising of bio-oil1 and bio-oil2 as well as conversion (89%) were observed with 1N KOH solution. (1)H NMR and (13)C NMR data showed that both bio-oil1 and bio-oil2 have high aliphatic carbon content. FTIR of bio-residue indicated that the usage of alkaline catalyst resulted in bio-residue samples with lesser oxygen functionality indicating that catalyst has a marked effect on nature of the bio-residue and helps to decompose biomass to a greater extent compared to thermal case.

  7. Catalytic hydrothermal upgradation of wheat husk.

    PubMed

    Singh, Rawel; Bhaskar, Thallada; Dora, Sambha; Balagurumurthy, Bhavya

    2013-12-01

    Catalytic hydrothermal upgradation of wheat husk was performed at 280°C for 15 min in the presence of alkaline catalysts (KOH and K2CO3). The effect of alkaline catalysts on the yield of bio-oil products and composition of bio-oils obtained were discussed. Total bio-oil yield (31%) comprising of bio-oil1 (ether fraction) and bio-oil2 (acetone fraction) was maximum with K2CO3 solution. Powder XRD (X-ray diffraction) analysis of wheat husk as well as bio-residue samples show that the peaks due to cellulose, hemicellulose and lignin become weak in bio-residue samples which suggest that these components have undergone hydrolytic cleavage/decomposition. The FTIR spectra of bio-oils indicate that the lignin in the wheat husk samples was decomposed to low molecular weight phenolic compounds. (1)H Nuclear Magnetic Resonance (NMR) spectrum of bio-oil1 shows more than 50% of the protons resonate in the up field region from 0.5 ppm to 3.0 ppm.

  8. Ion Association in Hydrothermal Sodium Sulfate Solutions Studied by Modulated FT-IR-Raman Spectroscopy and Molecular Dynamics.

    PubMed

    Reimer, Joachim; Steele-MacInnis, Matthew; Wambach, Jörg M; Vogel, Frédéric

    2015-07-30

    Saline aqueous solutions at elevated pressures and temperatures play an important role in processes such as supercritical water oxidation (SCWO) and supercritical water gasification (SCWG), as well as in natural geochemical processes in Earth and planetary interiors. Some solutions exhibit a negative temperature coefficient of solubility at high temperatures, thereby leading to salt precipitation with increasing temperature. Using modulated FT-IR Raman spectroscopy and classical molecular dynamics simulations (MD), we studied the solute speciation in solutions of 10 wt % Na2SO4, at conditions close to the saturation limit. Our experiments reveal that ion pairing and cluster formation are favored as solid saturation is approached, and ionic clusters form prior to the precipitation of solid sulfate. The proportion of such clusters increases as the phase boundary is approached either by decreasing pressure or by increasing temperature in the vicinity of the three-phase (vapor-liquid-solid) curve.

  9. 1-Dodecane-sulfonic-acid-sodium-salt(LAS) assisted hydrothermal synthesis of Cd{sub x}Zn{sub 1-x}S solid solution as efficient photocatalysts under visible light irradiation

    SciTech Connect

    Jia, B.; Guo, L. J.

    2010-03-01

    With anionic surfactant LAS assisted, series of zinc cadmium sulfide semiconductor photocatalysts were synthesized by hydrothermal method. These products were characterized by X-ray diffraction (XRD), UV-Vis absorption spectra (UV-Vis) and scanning electron microscopy (FESEM). The photocatalytic activities of as-prepared samples were evaluated by photocatalytic hydrogen production from water under visible-light irradiation. The best synthesis parameters are: Composition 0.9:0.1 (Cd:Zn molar ratio), Temperature 160 deg. C, Hydrothermal Time 48 Hour, LAS Concentration 1.7 mmol/L, the maximum visible-light-catalytic hydrogen production rate is 161.25 {mu}mol/h (lambda>430 nm) which is higher than those of by coprecipitation method. The experiment results indicate that surfactant assisted hydrothermal method is an effective way to get highly active CdZnS solid solution photocatalyst.

  10. Hydrothermal synthesis of a doped Mn-Cd-S solid solution as a visible-light-driven photocatalyst for H2 evolution.

    PubMed

    Ikeue, Keita; Shiiba, Satoshi; Machida, Masato

    2011-02-18

    The effect of metal doping (i.e., with Cr, Fe, Ni, Cu, Zn, Ag and Sn) on the crystal structure of hydrothermally synthesized Mn(1-x)Cd(x) S (where x≈0.1) is studied with the aim of enhancing photocatalytic activity. In contrast to the low-crystalline, undoped solid solution Mn(1-x)Cd(x)S, Ni doping yields a well-crystallized wurtzite-type Mn-Cd-S solid solution, which precipitates as planar hexagonal facets of several hundred nanometers in size, together with much larger grains of α-MnS (>10 μm). By removing inactive α-MnS through sedimentation, a single phase with composition of Ni(0.01)Mn(0.56)Cd(0.43)S is obtained successfully. The Ni doping achieved a threefold higher photocatalytic activity for H(2) evolution from a 0.1 M Na(2)S/0.5 M Na(2)SO(3) solution under visible-light irradiation (λ≥420 nm). The apparent quantum yield of 1 wt % Pt-loaded Ni(0.01)Mn(0.56)Cd(0.43)S measured at λ=420 nm reached 25 %. The enhanced photocatalytic activity is most likely the result of a decreased concentration of defects, responsible for electron-hole recombination, in the active solid-solution phase and a slightly higher bandgap energy (2.4 eV).

  11. Recycling of waste printed circuit boards with simultaneous enrichment of special metals by using alkaline melts: A green and strategically advantageous solution.

    PubMed

    Stuhlpfarrer, Philipp; Luidold, Stefan; Antrekowitsch, Helmut

    2016-04-15

    The increasing consumption of electric and electronic equipment has led to a rise in toxic waste. To recover the metal fraction, a separation of the organic components is necessary because harmful substances such as chlorine, fluorine and bromine cause ecological damage, for example in the form of dioxins and furans at temperature above 400°C. Hence, an alternative, environmentally friendly approach was investigated exploiting that a mixture of caustic soda and potassium hydroxide in eutectic composition melts below 200°C, enabling a fast cracking of the long hydrocarbon chains. The trials demonstrate the removal of organic compounds without a loss of copper and precious metals, as well as a suppressed formation of hazardous off-gases. In order to avoid an input of alkaline elements into the furnace and ensuing problems with refractory materials, a washing step generates a sodium and potassium hydroxide solution, in which special metals like indium, gallium and germanium are enriched. Their concentrations facilitate the recovery of these elements, because otherwise they become lost in the typical recycling processes. The aim of this work was to find an environmental solution for the separation of plastics and metals as well as a strategically important answer for the recycling of printed circuit boards and mobile phones.

  12. Uranium mobility during interaction of rhyolitic obsidian, perlite and felsite with alkaline carbonate solution: T = 120° C, P = 210 kg/cm2

    USGS Publications Warehouse

    Zielinski, Robert A.

    1979-01-01

    Well-characterized samples of rhyolitic obsidian, perlite and felsite from a single lava flow are leached of U by alkaline oxidizing solutions under open-system conditions. Pressure, temperature, flow rate and solution composition are held constant in order to evaluate the relative importance of differences in surface area and crystallinity. Under the experimental conditions U removal from crushed glassy samples proceeds by a mechanism of glass dissolution in which U and silica are dissolved in approximately equal weight fractions. The rate of U removal from crushed glassy samples increases with decreasing average grain size (surface area). Initial rapid loss of a small component (≈ 2.5%) of the total U from crushed felsite. followed by much slower U loss, reflects variable rates of attack of numerous uranium sites. The fractions of U removed during the experiment ranged from 3.2% (felsite) to 27% (perlite). An empirical method for evaluating the relative rate of U loss from contemporaneous volcanic rocks is presented which incorporates leaching results and rock permeability data.

  13. Chemical Corrosion of Liquid-Phase Sintered SiC in Acidic/Alkaline Solutions Part 1. Corrosion in HNO3 Solution

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhang, Ming; He, Xinnong; Tang, Wenming

    2016-03-01

    The corrosion behavior of the liquid-phase sintered SiC (LPS-SiC) was studied by dipping in 3.53 mol/L HNO3 aqueous solution at room temperature and 70 °C, respectively. The weight loss, strength reduction and morphology evolution of the SiC specimens during corroding were revealed and also the chemical corrosion process and mechanism of the SiC specimens in the acidic solution were clarified. The results show that the corrosion of the LPS-SiC specimens in the HNO3 solution is selective. The SiC particles are almost free from corrosion, but the secondary phases of BaAl2Si2O8 (BAS) and Y2Si2O7 are corroded via an acid-alkali neutralization reaction. BAS has a higher corrosion rate than Y2Si2O7, resulting in the formation of the bamboo-leaf-like corrosion pits. As the SiC specimens etched in the HNO3 solution at room temperature for 75 days, about 80 μm thickness corrosion layer forms. The weight loss and bending strength reduction of the etched SiC specimens are 2.6 mg/cm2 and 52%, respectively. The corrosion of the SiC specimens is accelerated in the 70 °C HNO3 solution with a rate about five times bigger than that in the same corrosion medium at room temperature.

  14. Volcano-hydrothermal system of Ebeko volcano, Paramushir, Kuril Islands: Geochemistry and solute fluxes of magmatic chlorine and sulfur

    NASA Astrophysics Data System (ADS)

    Kalacheva, Elena; Taran, Yuri; Kotenko, Tatiana; Hattori, Keiko; Kotenko, Leonid; Solis-Pichardo, Gabriela

    2016-01-01

    Ebeko volcano at the northern part of Paramushir Island in the Kuril island arc produces frequent phreatic eruptions and relatively strong fumarolic activity at the summit area ~ 1000 m above sea level (asl). The fumaroles are characterized by low-temperature, HCl- and S-rich gas and numerous hyper-acid pools (pH < 1) without drains. At ~ 550 m asl, in the Yurieva stream canyon, many hot (up to 87 °C) springs discharge ultra-acidic (pH 1-2) SO4-Cl water into the stream and finally into the Sea of Okhotsk. During quiescent stages of degassing, these fumaroles emit 1000-2000 t/d of water vapor, < 20 t/d of SO2 and < 5 t/d of HCl. The measurement of acidic hot Yurieva springs shows that the flux of Cl and S, 60-80 t/d each, is independent on the volcanic activity in the last two decades. Such high flux of Cl is among the highest ever measured in a volcano-hydrothermal system. Oxygen and hydrogen isotopic composition of water and Cl concentration for Yurieva springs show an excellent positive correlation, indicating a mixing between meteoric water and magmatic vapor. In contrast, volcanic gas condensates of Ebeko fumaroles do not show a simple mixing trend but rather a complicated data suggesting evaporation of the acidic brine. Temperatures calculated from gas compositions and isotope data are similar, ranging from 150 to 250 °C, which is consistent with the presence of a liquid aquifer below the Ebeko fumarolic fields. Saturation indices of non-silicate minerals suggest temperatures ranging from 150 to 200 °C for Yurieva springs. Trace elements (including REE) and Sr isotope composition suggest congruent dissolution of the Ebeko volcanic rocks by acidic waters. Waters of Yurieva springs and waters of the summit thermal fields (including volcanic gas condensates) are different in Cl/SO4 ratios and isotopic compositions, suggesting complicated boiling-condensation-mixing processes.

  15. Bottom-up synthesis of high-performance nitrogen-enriched transition metal/graphene oxygen reduction electrocatalysts both in alkaline and acidic solution

    NASA Astrophysics Data System (ADS)

    Lai, Qingxue; Gao, Qingwen; Su, Qi; Liang, Yanyu; Wang, Yuxi; Yang, Zhi

    2015-08-01

    Oxygen reduction electrocatalysts with low cost and excellent performance are urgently required for large-scale application in fuel cells and metal-air batteries. Though nitrogen-enriched transition metal/graphene hybrids (N-TM/G, TM = Fe, Co, and Ni and related compounds) have been developed as novel substitutes for precious metal catalysts (PMCs) towards oxygen reduction reaction (ORR), a significant challenge still remains for simple and efficient synthesis of N-TM/G catalysts with satisfactory electrocatalytic behavior. Herein, we demonstrate a universal bottom-up strategy for efficient fabrication of strongly-coupled N-TM/G catalysts. This strategy is implemented via direct polymerization of transition metal phthalocyanine (TMPc) in the two-dimensional confined space of in situ generated g-C3N4 and a subsequent pyrolysis. Such a space-confined bottom-up synthesis route successfully constructs a strongly-coupled triple junction of transition metal-graphitic carbon-nitrogen-doped graphene (TM-GC-NG) with extensive controllability over the specific surface area, nitrogen content/types as well as the states of metal. As a result, the optimized N-Fe/G materials have promising potential as high-performance NPMCs towards ORR both in alkaline and acidic solution.Oxygen reduction electrocatalysts with low cost and excellent performance are urgently required for large-scale application in fuel cells and metal-air batteries. Though nitrogen-enriched transition metal/graphene hybrids (N-TM/G, TM = Fe, Co, and Ni and related compounds) have been developed as novel substitutes for precious metal catalysts (PMCs) towards oxygen reduction reaction (ORR), a significant challenge still remains for simple and efficient synthesis of N-TM/G catalysts with satisfactory electrocatalytic behavior. Herein, we demonstrate a universal bottom-up strategy for efficient fabrication of strongly-coupled N-TM/G catalysts. This strategy is implemented via direct polymerization of transition

  16. Hydrothermal Reactivity of Amines

    NASA Astrophysics Data System (ADS)

    Robinson, K.; Shock, E.; Hartnett, H. E.; Williams, L. B.; Gould, I.

    2013-12-01

    The reactivity of aqueous amines depends on temperature, pH, and redox state [1], all of which are highly variable in hydrothermal systems. Temperature and pH affect the ratio of protonated to unprotonated amines (R-NH2 + H+ = R-NH3+), which act as nucleophiles and electrophiles, respectively. We hypothesize that this dual nature can explain the pH dependence of reaction rates, and predict that rates will approach a maximum at pH = pKa where the ratio of protonated and unprotonated amines approaches one and the two compounds are poised to react with one another. Higher temperatures in hydrothermal systems allow for more rapid reaction rates, readily reversible reactions, and unique carbon-nitrogen chemistry in which water acts as a reagent in addition to being the solvent. In this study, aqueous benzylamine was used as a model compound to explore the reaction mechanisms, kinetics, and equilibria of amines under hydrothermal conditions. Experiments were carried out in anoxic silica glass tubes at 250°C (Psat) using phosphate-buffered solutions to observe changes in reaction rates and product distributions as a function of pH. The rate of decomposition of benzylamine was much faster at pH 4 than at pH 9, consistent with the prediction that benzylamine acts as both nucleophile and an electrophile, and our estimate that the pKa of benzylamine is ~5 at 250°C and Psat. Accordingly, dibenzylamine is the primary product of the reaction of two benzylamine molecules, and this reaction is readily reversible under hydrothermal conditions. Extremely acidic or basic pH can be used to suppress dibenzylamine production, which also suppresses the formation of all other major products, including toluene, benzyl alcohol, dibenzylimine, and tribenzylamine. This suggests that dibenzylamine is the lone primary product that then itself reacts as a precursor to produce the above compounds. Analog experiments performed with ring-substituted benzylamine derivatives and chiral

  17. EXAFS analysis of cations distribution in structure of Co1-xNixFe2O4 nanoparticles obtained by hydrothermal method in aloe vera extract solution

    NASA Astrophysics Data System (ADS)

    Wongpratat, Unchista; Maensiri, Santi; Swatsitang, Ekaphan

    2016-09-01

    Effect of cations distribution upon EXAFS analysis on magnetic properties of Co1-xNixFe2O4 (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles prepared by the hydrothermal method in aloe vera extract solution were studied. XRD analysis confirmed a pure phase of cubic spinel ferrite of all samples. Changes in lattice parameter and particle size depended on the Ni content with partial substitution and site distributions of Co2+, Ni2+ ions of different ionic radii at both tetrahedral and octahedral sites in the crystal structure. Particle sizes of samples estimated by TEM images were found to be in the range of 10.87-62.50 nm. The VSM results at room temperature indicated the ferrimagnetic behavior of all samples. Superparamagnetic behavior was observed in NiFe2O4 sample. The coercivity (Hc) and remanance (Mr) values were related to the particle sizes of samples. The saturation magnetization (Ms) was increased by a factor of 1.4 to a value of 57.57 emu/g, whereas the coercivity (Hc) was decreased by a factor of 20 to a value of 63.15 Oe for a sample with x = 0.75. In addition to the cations distribution, the increase of aspect ratio (surface to volume ratio) due to the decrease of particle size could significantly affect the magnetic properties of the materials.

  18. Preparation of Cr2O3 precursors by hydrothermal reduction in the abundant Na2CO3 and Na2CrO4 solution

    NASA Astrophysics Data System (ADS)

    Wei, Guang-ye; Qu, Jing-kui; Zheng, Yu-dong; Qi, Tao; Guo, Qiang

    2012-11-01

    Precursors of chromium oxide (p-Cr2O3) were prepared by reducing hexavalent chromium in the presence of sodium carbonate solution under hydrothermal conditions. Methanal was used as the reductant, and carbon dioxide was the acidulating agent. The influences of reaction temperature, initial pressure of carbon dioxide, isothermal time and methanal coefficient on Cr(VI) reduction were investigated. Experimental results showed that Cr(VI) was reduced to Cr(III) with a yield of 99%. Chemical titration, thermogravimetry (TG), X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM) were used to characterize the p-Cr2O3 and Cr2O3. The series of p-Cr2O3 were found to be multiphase even if they presented different colors, from gray green to lavender. After these p-Cr2O3 samples were calcined, the product of rhombohedral Cr2O3 with a purity of 99.5wt% was obtained.

  19. Hydrothermal Processes

    NASA Astrophysics Data System (ADS)

    German, C. R.; von Damm, K. L.

    2003-12-01

    What is Hydrothermal Circulation?Hydrothermal circulation occurs when seawater percolates downward through fractured ocean crust along the volcanic mid-ocean ridge (MOR) system. The seawater is first heated and then undergoes chemical modification through reaction with the host rock as it continues downward, reaching maximum temperatures that can exceed 400 °C. At these temperatures the fluids become extremely buoyant and rise rapidly back to the seafloor where they are expelled into the overlying water column. Seafloor hydrothermal circulation plays a significant role in the cycling of energy and mass between the solid earth and the oceans; the first identification of submarine hydrothermal venting and their accompanying chemosynthetically based communities in the late 1970s remains one of the most exciting discoveries in modern science. The existence of some form of hydrothermal circulation had been predicted almost as soon as the significance of ridges themselves was first recognized, with the emergence of plate tectonic theory. Magma wells up from the Earth's interior along "spreading centers" or "MORs" to produce fresh ocean crust at a rate of ˜20 km3 yr-1, forming new seafloor at a rate of ˜3.3 km2 yr-1 (Parsons, 1981; White et al., 1992). The young oceanic lithosphere formed in this way cools as it moves away from the ridge crest. Although much of this cooling occurs by upward conduction of heat through the lithosphere, early heat-flow studies quickly established that a significant proportion of the total heat flux must also occur via some additional convective process (Figure 1), i.e., through circulation of cold seawater within the upper ocean crust (Anderson and Silbeck, 1981). (2K)Figure 1. Oceanic heat flow versus age of ocean crust. Data from the Pacific, Atlantic, and Indian oceans, averaged over 2 Ma intervals (circles) depart from the theoretical cooling curve (solid line) indicating convective cooling of young ocean crust by circulating seawater

  20. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    PubMed Central

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-01-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm−2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm−2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms. PMID:25765731

  1. A novel chemiluminescence quenching method for determination of sulfonamides in pharmaceutical and biological fluid based on luminol-Ag(III) complex reaction in alkaline solution.

    PubMed

    Sun, Hanwen; Chen, Peiyun; Li, Liqing; Cheng, Peng

    2011-05-01

    A novel chemiluminescence (CL) quenching method for the determination of sulfonamides is proposed. The CL reaction between Ag(III) complex [Ag(HIO₆)₂]⁵⁻ and luminol in alkaline solution was investigated. The quenching effect of sulfonamides on CL emission of [Ag(HIO₆)₂]⁵⁻-luminol system was found. Quenching degree of CL emission was proportional to sulfonamide concentration. The effects of the reaction conditions on CL emission and quenching were examined. Under optimal conditions, the detection limits (s/n = 3) were 7.2, 17 and 8.3 ng/mL for sulfadiazine, sulfameter, and sulfadimethoxine, respectively. The recoveries of the three drugs were in the range of 91.3-110% with RSDs of 1.9-2.7% for urine samples, and 106-112% with RSDs of 1.6-2.8% for serum samples. The proposed method was used for the determination of sulfadiazine at clinically relevant concentrations in real urine and serum samples with satisfactory results.

  2. Quantification of the dissolved inorganic carbon species and of the pH of alkaline solutions exposed to CO2 under pressure: a novel approach by Raman scattering.

    PubMed

    Beuvier, Thomas; Calvignac, Brice; Bardeau, Jean-François; Bulou, Alain; Boury, Frank; Gibaud, Alain

    2014-10-07

    Dissolved inorganic carbon (DIC) content of aqueous systems is a key function of the pH, of the total alkanility (TA), and of the partial pressure of CO2. However, common analytical techniques used to determine the DIC content in water are unable to operate under high CO2 pressure. Here, we propose to use Raman spectroscopy as a novel alternative to discriminate and quantitatively monitor the three dissolved inorganic carbon species CO2(aq), HCO3(-), and CO3(2-) of alkaline solutions under high CO2 pressure (from P = 0 to 250 bar at T = 40 °C). In addition, we demonstrate that the pH values can be extracted from the molalities of CO2(aq) and HCO3(-). The results are in very good agreement with those obtained from direct spectrophotometric measurements using colored indicators. This novel method presents the great advantage over high pressure conventional techniques of not using breakable electrodes or reference additives and appears of great interest especially in marine biogeochemistry, in carbon capture and storage and in material engineering under high CO2 pressure.

  3. A stopped-flow study of the dual chemiluminescence for the luminol-KIO4-Mn(2+) system in strong alkaline solutions.

    PubMed

    Huang, Tsung-Yuan; Lin, Wann-Yin

    2011-01-01

    A novel phenomenon of dual chemiluminescence (CL) was observed for the KIO4-luminol-Mn(2+) system in strong alkaline solutions using the stopped-flow technique. Scavenging study of the reactive oxygen species (ROS) suggested that the two CL peaks originated from different CL pathways precipated by distinct ROS (O2(-) and •OH for the first peak, mainly 1O2 for the second peak). Generation of these ROS at different time intervals from the reactions involving IO4(-), O2, and Mn(2+) and their subsequent reactions with luminol induced the intense CL emission. The relative intensity of the two CL peaks can be tuned over a wide range by varying the concentrations of Mn(2-), luminol and KIO4. Because of the involvement of different ROS in each pathway, the two CL peaks could respond quite differently to various substances. Moreover, variation of the intensity ratio of the two CL peaks altered the relative proportions of the corresponding ROS, thereby changing their responses to a given substance. The dual CL emission acts like a pair of tunable probes and it is believed that this CL system has great potential in analytical applications.

  4. Application of nano-sized nanoporous zinc 2-methylimidazole metal-organic framework for electrocatalytic oxidation of methanol in alkaline solution

    NASA Astrophysics Data System (ADS)

    Samadi-Maybodi, Abdolraouf; Ghasemi, Shahram; Ghaffari-Rad, Hamid

    2016-01-01

    In this work, a novel non-platinum group metals (non-PGM) catalyst based on modified zinc 2-methylimidazole metal-organic framework (ZIF-8) is proposed and used for electrooxidation of methanol. Nano-sized particles of nonporous ZIF-8 are synthesized at room temperature using a simple template-free method. The synthesized ZIF-8 nanoparticles are characterized by X-ray diffraction, scanning electronic microscopy and nitrogen adsorption-desorption techniques. In order to decrease the overvoltage of methanol oxidation on carbon paste electrode (CPE), nickel species doped ZIF-8 modified carbon paste electrode (Ni/ZIF-8CPE) is fabricated as a modified electrode. Electrochemical techniques such as cyclic voltammetry and chronoamperometry are used to investigate the electrocatalytic activity of Ni/ZIF-8CPE toward methanol oxidation in alkaline solution. Cyclic voltammetry results show that oxidation current is considerably increased using Ni/ZIF-8CPE in comparison with unmodified CPE. Catalytic rate constant of methanol oxidation on Ni/ZIF-8CPE is obtained using chronoamperometric studies. Besides the good catalytic activity of the modified electrode toward methanol oxidation, it has other advantages such as simple preparation, ease of operation, good stability and low cost, which can be promising in the field of preparation of non-PGM electrocatalysts for application in fuel cells.

  5. Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: the effects of pH, alkali and salt

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

    A chemical equilibrium model for interfacial activity of crude in aqueous alkaline solution is proposed. The model predicts the observed effects of pH and concentrations of alkali and salt on the interfacial tension (IFT). The model proposed was shown to describe the observed effects of acid content, pH, and sodium ions on the interfacial activity of crude oil in water. Once the pH of the interface reaches the pKa of the acids, sometimes with the help of addition of some salt, the IFT experiences a sudden steep drop to the range of 10/sup -2/ dynes/cm. After that, further addition of sodium either in the form of NaOH or NaCl is going to increase the IFT due to a shift of equilibriumn to the formation of undissociated soap. This was confirmed by the difference in the observed effect of sodium on the IFT of the extracted soap molecules which are dissociated easily and those which are associated highly and precipitated easily. These soap molecules have dissociation constant values ranging from below 10/sup -2/ to above one. 13 references.

  6. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

  7. Mechanochemical synthesis, structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1-xMbxF2 (M: Ca, Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2016-10-01

    The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides Ma1-xMbxF2 (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca1-xSrxF2 and Ba1-xSrxF2 samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and 19F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of 19F chemical shifts with the superposition model along with probability calculations for the intensity of the individual 19F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F- ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.

  8. Graphene oxide electrocatalyst on MnO₂ air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution.

    PubMed

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-13

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm(-2), in contrast to MnO2, which produced a maximum power density of 9.2 mW cm(-2). The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

  9. Structure and reactivity of thiazolium azo dyes: UV-visible, resonance Raman, NMR, and computational studies of the reaction mechanism in alkaline solution.

    PubMed

    Abbott, Laurence C; Batchelor, Stephen N; Moore, John N

    2013-03-07

    UV-visible absorption, resonance Raman, and (1)H NMR spectroscopy, allied with density functional theory (DFT) calculations, have been used to study the structure, bonding, and alkaline hydrolysis mechanism of the cationic thiazloium azo dye, 2-[2-[4-(diethylamino)phenyl]diazenyl]-3-methyl-thiazolium (1a), along with a series of six related dyes with different 4-dialkylamino groups and/or other phenyl ring substituents (2a-c, 3a-c) and the related isothiazolium azo dye, 5-[2-[4-(dimethylamino)phenyl]diazenyl]-2-methyl-isothiazolium (4). These diazahemicyanine dyes are calculated to have a similar low-energy structure that is cis, trans at the (iso)thiazolium-azo group, and for which the calculated Raman spectra provide a good match with the experimental data; the calculations on these structures are used to assign and discuss the transitions giving rise to the experimental spectra, and to consider the bonding and its variation between the dyes. UV-visible, Raman, and NMR spectra recorded from minutes to several weeks after raising the pH of an aqueous solution of 1a to ca. 11.5 show that the dominant initial step in the reaction is loss of diethylamine to produce a quinonimine (ca. hours), with subsequent reactions occurring on longer time scales (ca. days to weeks); kinetic analyses give a rate constant of 2.6 × 10(-2) dm(3) mol(-1) s(-1) for reaction of 1a with OH(-). UV-visible spectra recorded on raising the pH of the other dyes in solution show similar changes that are attributed to the same general reaction mechanism, but with different rate constants for which the dependence on structure is discussed.

  10. Conventional hydrothermal synthesis of Na-A zeolite from cupola slag and aluminum sludge.

    PubMed

    Anuwattana, Rewadee; Khummongkol, Pojanie

    2009-07-15

    Na-A type zeolites were prepared from two industrial wastes: the solid by-product of cupola slag and aluminum sludge from an aluminum plating plant. Two preparation methods using the same starting material compositions were carried out. In the first method, alkaline fusion was introduced, followed by the hydrothermal treatment to obtain sodium aluminosilicate which was then crystallized in NaOH solution under the condition of 90+/-3 degrees C for 1-9h with different H(2)O/SiO2 ratios. The result shows that higher H(2)O/SiO2 ratio increases the rate of crystallization. The largest amount of crystallinity for Na-A was found at 3h. In the second method, alkaline hydrothermal treatment without fusion was carried out in the same condition as the first method. No Na-A zeolite was obtained by this method. The changes of the dissolved amounts of Si(4+) and Al(3+) in 3M NaOH were investigated during the hydrothermal reaction.

  11. Investigation on the coprecipitation of transuranium elements from alkaline solutions by the method of appearing reagents. Study of the effects of waste components on decontamination from Np(IV) and Pu(IV)

    SciTech Connect

    Bessonov, A.A.; Budantseva, N.A.; Gelis, A.V.; Nikonov, M.V.; Shilov, V.P.

    1997-09-01

    The third stage of the study on the homogeneous coprecipitation of neptunium and plutonium from alkaline high-level radioactive waste solutions by the Method of Appearing Reagents has been completed. Alkaline radioactive wastes exist at the U.S. Department of Energy Hanford Site. The recent studies investigated the effects of neptunium chemical reductants, plutonium(IV) concentration, and the presence of bulk tank waste solution components on the decontamination from tetravalent neptunium and plutonium achieved by homogeneous coprecipitation. Data on neptunium reduction to its tetravalent state in alkaline solution of different NaOH concentrations are given. Eleven reductants were tested to find those most suited to remove neptunium, through chemical reduction, from alkaline solution by homogeneous coprecipitation. Hydrazine, VOSO{sub 4}, and Na{sub 2}S{sub 2}O{sub 4} were found to be the most effective reductants. The rates of reduction with these reductants were comparable with the kinetics of carrier formation. Solution decontamination factors of about 400 were attained for 10{sup -6}M neptunium. Coprecipitation of plutonium(IV) with carriers obtained as products of thermal hydrolysis, redox transformations, and catalytic decomposition of [Co(NH{sub 3}){sub 6}]{sup 3+}, [Fe(CN){sub 5}NO]{sup 2-}, Cr(NO{sub 3}){sub 3}, KMnO{sub 4}, and Li{sub 4}UO{sub 2}(O{sub 2}){sub 3} was studied and results are described. Under optimum conditions, a 100-fold decrease of plutonium concentration was possible with each of these reagents.

  12. Ecology of mixed biofilms subjected daily to a chlorinated alkaline solution: spatial distribution of bacterial species suggests a protective effect of one species to another.

    PubMed

    Leriche, V; Briandet, R; Carpentier, B

    2003-01-01

    Three bacterial strains (Kocuria sp. C714.1, Brevibacterium linens B337.1 and Staphylococcus sciuri CCL101) were grown together on stainless steel and were subjected daily to a commercial alkaline chlorine solution (22 mg l-1 of free chlorine, pH 11) over a period of 4 weeks. After the daily chemical shock, culture madia [1:20 dilution of tryptic soy broth (TSB-YE/20) or diluted whey] was deposited on the biofilms. The chemical shocks led first to a drop in the culturable population, followed by an increase and finally stabilization at around 106-107 CFU cm-2 by day 11 of the experiment. These changes in the microbial population can be attributed to a decreasing susceptibility to the antimicrobial agent with biofilm age, and to the consumption of free chlorine by biofilm exoproteins. The microbial composition appeared to be linked to the free chlorine concentration that depended on exoprotein production. At the end of the experiment, exoprotein production was greater for biofilms grown in TSBYE/20 than in whey. As a consequence, biofilms grown in whey did not neutralize the chlorine and the dominant strain was the one having the highest resistance to chlorine: K. varians. When biofilm were grown in TSBYE/20, chlorine was neutralized and the dominant strain was the one having the highest growth rate: S. sciuri. The presence of chlorine may also explain the distribution of S. sciuri cells as a ring around Kocuria sp. microcolonies. When chlorine was totally consumed by the biofilm during the chemical shock, S. sciuri was no longer grouped around Kocuria sp. microcolonies but was evenly scattered over the substratum as single cells or in small clusters, as it was before any chemical treatment. These findings strongly suggest protection of S. sciuri by Kocuria sp. microcolonies against the chlorinated solution. This phenomenon, added to the low susceptibility phenotype of the biofilm cells, could at least partly explain the survival of microbial cells in an adverse

  13. Hydrothermal Growth of Polyscale Crystals

    NASA Astrophysics Data System (ADS)

    Byrappa, Kullaiah

    In this chapter, the importance of the hydrothermal technique for growth of polyscale crystals is discussed with reference to its efficiency in synthesizing high-quality crystals of various sizes for modern technological applications. The historical development of the hydrothermal technique is briefly discussed, to show its evolution over time. Also some of the important types of apparatus used in routine hydrothermal research, including the continuous production of nanosize crystals, are discussed. The latest trends in the hydrothermal growth of crystals, such as thermodynamic modeling and understanding of the solution chemistry, are elucidated with appropriate examples. The growth of some selected bulk, fine, and nanosized crystals of current technological significance, such as quartz, aluminum and gallium berlinites, calcite, gemstones, rare-earth vanadates, electroceramic titanates, and carbon polymorphs, is discussed in detail. Future trends in the hydrothermal technique, required to meet the challenges of fast-growing demand for materials in various technological fields, are described. At the end of this chapter, an Appendix 18.A containing a more or less complete list of the characteristic families of crystals synthesized by the hydrothermal technique is given with the solvent and pressure-temperature (PT) conditions used in their synthesis.

  14. Coastal submarine hydrothermal activity of Northern Baja California 2. Evolutionary history and isotope geochemistry

    SciTech Connect

    Vidal, V.M.V.; Vidal, F.V.; Isaacs, J.D.

    1981-10-10

    A geochemical model of the Punta Banda submarine hydrothermal system (PBSHS) and Ensenada quadrangle subaerial hot springs is developed using /sup 18/O//sup 16/O, D/H, /sup 34/S//sup 32/S, /sup 3/H, water and gas chemistry. The PBSHS water is a primary high temperature, acid, reducing fluid of old seawater origin which has been titrated by cold, alkaline groundwater of meteoric origin. The final exiting solutions represent a 1:1 mixture of the two primary mixing components. In contrast, the subaerial hot spring waters are of unmixed meteoric origin. The subaerial hot spring gas is predominantly atmospheric N/sub 2/, while the PBSHS contains large amounts of CH/sub 4/ and N/sub 2/ derived from trapped marine sediments of Cretaceous age, deltaS/sup 34/ values of sampled hydrothermal waters are similar to Cretaceous marine sulfate values and suggest that the waters contacted Cretaceous marine sedimentary strata. The presence of the Alisitos and Rosario marine sedimentary formations of Cretaceous age within the Ensenada-Punta Banda quadrangel renders support to the above hypothesis. The data also demonstrate the pyrite mineralization and deposition in submarine hydrothermal environments result from the complexing of ferrous iron with elemental sulfur and sulfide and that submarine hydrothermal activity acts as a major source of silica, Ca/sup 2 +/, and trace metals and as a major sink for seawater Mg/sup 2 +/ and SO/sub 4//sup 2 -/.

  15. Efficient and durable oxygen reduction and evolution of a hydrothermally synthesized La(Co0.55Mn0.45)0.99O3-δ nanorod/graphene hybrid in alkaline media

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoming; Goh, F. W. Thomas; Li, Bing; Hor, T. S. Andy; Zhang, Jie; Xiao, Peng; Wang, Xin; Zong, Yun; Liu, Zhaolin

    2015-05-01

    The increasing global energy demand and the depletion of fossil fuels have stimulated intense research on fuel cells and batteries. Oxygen electrocatalysis plays essential roles as the electrocatalytic reduction and evolution of di-oxygen are always the performance-limiting factors of these devices relying on oxygen electrochemistry. A novel perovskite with the formula La(Co0.55Mn0.45)0.99O3-δ (LCMO) is designed from molecular orbital principles. The hydrothermally synthesized LCMO nanorods have unique structural and chemical properties and possess high intrinsic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergic covalent coupling between LCMO and NrGO enhances the bifunctional ORR and OER activities of the novel LCMO/NrGO hybrid catalyst. The ORR activity of LCMO/NrGO is comparable to the state-of-the-art Pt/C catalyst and its OER activity is competitive to the state-of-the-art Ir/C catalyst. LCMO/NrGO generally outperforms Pt/C and Ir/C with better bifunctional ORR and OER performance and operating durability. LCMO/NrGO represents a new class of low-cost, efficient and durable electrocatalysts for fuel cells, water electrolysers and batteries.The increasing global energy demand and the depletion of fossil fuels have stimulated intense research on fuel cells and batteries. Oxygen electrocatalysis plays essential roles as the electrocatalytic reduction and evolution of di-oxygen are always the performance-limiting factors of these devices relying on oxygen electrochemistry. A novel perovskite with the formula La(Co0.55Mn0.45)0.99O3-δ (LCMO) is designed from molecular orbital principles. The hydrothermally synthesized LCMO nanorods have unique structural and chemical properties and possess high intrinsic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergic covalent coupling between LCMO and NrGO enhances the bifunctional ORR and OER activities of the novel LCMO/NrGO hybrid

  16. Solute fluxes from Tacaná volcano-hydrothermal system, Mexico-Guatemala. Implications for estimation of geothermal potential of the deep aquifer.

    NASA Astrophysics Data System (ADS)

    Collard, N.; Taran, Y.; Jácome Paz, M. P.; Campion, R.

    2014-12-01

    Tacaná (4100 m asl) is the northernmost volcano of the Central America Volcanic Arc. The volcano hosts a volcano-hydrothermal system that is manifested as a low-temperature fumarolic field at 3600 m asl and several groups of thermal springs principally located at the northwestern slopes of the volcanic edifice, at altitudes 1500 - 2000 m asl. These thermal springs discharge SO4-HCO3-enriched water (up to 1 g/kg of each one) with temperatures in the 25-63°C range. There are two distinct groups of springs with a different chloride-temperature and chloride-sulfate correlations but with the same 87Sr/86Sr ratio (~0.7046±0.0002) indicating the same wall rock composition for different aquifers. On April 2014, we found a cold spring (Manantial Nuevo), located at an elevation ~500 m lower than the others and with a different chemical composition, that discharges Na-Cl-type water with Cl concentration of 1.4 g/l and Na+K concentration up to 1.5 g/l. This new spring forms a fourth group, representing a stratified geothermal aquifer. Each thermal spring feeds a thermal stream that flows into the main drainage of the area, Río Coatán. Solute and heat fluxes from thermal springs of Tacaná volcano are estimated by the chloride-inventory method. The total observed chloride discharge from the thermal springs is estimated as 14.8 g/s and the total measured heat output of ~9.5 MW. Considering a deep fluid temperature of 250°C, the corresponding advective heat transport from the deep reservoirs that feed these springs may be estimate as 26 MW. However, the total chloride output measured in the main drainage (Coatán river) is 4 times higher (~59 g/s) than the measured Cl output of all known thermal springs. This means that other, undiscovered, thermal discharges exist in the area and that the natural heat output through thermal springs at Tacaná is significantly higher and depends on the Cl content and temperatures of the unknown thermal water discharges. If chloride

  17. Efficient and durable oxygen reduction and evolution of a hydrothermally synthesized La(Co0.55Mn0.45)0.99O3-δ nanorod/graphene hybrid in alkaline media.

    PubMed

    Ge, Xiaoming; Goh, F W Thomas; Li, Bing; Hor, T S Andy; Zhang, Jie; Xiao, Peng; Wang, Xin; Zong, Yun; Liu, Zhaolin

    2015-05-21

    The increasing global energy demand and the depletion of fossil fuels have stimulated intense research on fuel cells and batteries. Oxygen electrocatalysis plays essential roles as the electrocatalytic reduction and evolution of di-oxygen are always the performance-limiting factors of these devices relying on oxygen electrochemistry. A novel perovskite with the formula La(Co0.55Mn0.45)0.99O3-δ (LCMO) is designed from molecular orbital principles. The hydrothermally synthesized LCMO nanorods have unique structural and chemical properties and possess high intrinsic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergic covalent coupling between LCMO and NrGO enhances the bifunctional ORR and OER activities of the novel LCMO/NrGO hybrid catalyst. The ORR activity of LCMO/NrGO is comparable to the state-of-the-art Pt/C catalyst and its OER activity is competitive to the state-of-the-art Ir/C catalyst. LCMO/NrGO generally outperforms Pt/C and Ir/C with better bifunctional ORR and OER performance and operating durability. LCMO/NrGO represents a new class of low-cost, efficient and durable electrocatalysts for fuel cells, water electrolysers and batteries.

  18. Zinc electrode in alkaline electrolyte

    SciTech Connect

    McBreen, J.

    1995-12-31

    The zinc electrode in alkaline electrolyte is unusual in that supersaturated zincate solutions can form during discharge and spongy or mossy zinc deposits can form on charge at low overvoltages. The effect of additives on regular pasted ZnO electrodes and calcium zincate electrodes is discussed. The paper also reports on in situ x-ray absorption (XAS) results on mossy zinc deposits.

  19. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: I. The origin of thiosulfate in hot spring waters

    USGS Publications Warehouse

    Xu, Y.; Schoonen, M.A.A.; Nordstrom, D.K.; Cunningham, K.M.; Ball, J.W.

    1998-01-01

    Thiosulfate (S2O2-3), polythionate (SxO2-6), dissolved sulfide (H2S), and sulfate (SO2-4) concentrations in thirty-nine alkaline and acidic springs in Yellowstone National Park (YNP) were determined. The analyses were conducted on site, using ion chromatography for thiosulfate, polythionate, and sulfate, and using colorimetry for dissolved sulfide. Thiosulfate was detected at concentrations typically less than 2 ??mol/L in neutral and alkaline chloride springs with low sulfate concentrations (C1-/SO2-4 > 25). The thiosulfate concentration levels are about one to two orders of magnitude lower than the concentration of dissolved sulfide in these springs. In most acid sulfate and acid sulfate-chloride springs (Cl-/SO2-4 < 10), thiosulfate concentrations were also typically lower than 2 ??mol/L. However, in some chloride springs enriched with sulfate (Cl-/SO2-4 between 10 to 25), thiosulfate was found at concentrations ranging from 9 to 95 ??mol/L, higher than the concentrations of dissolved sulfide in these waters. Polythionate was detected only in Cinder Pool, Norris Geyser basin, at concentrations up to 8 ??mol/L, with an average S-chain-length from 4.1 to 4.9 sulfur atoms. The results indicate that no thiosulfate occurs in the deeper parts of the hydrothermal system. Thiosulfate may form, however, from (1) hydrolysis of native sulfur by hydrothermal solutions in the shallower parts (<50 m) of the system, (2) oxidation of dissolved sulfide upon mixing of a deep hydrothermal water with aerated shallow groundwater, and (3) the oxidation of dissolved sulfide by dissolved oxygen upon discharge of the hot spring. Upon discharge of a sulfide-containing hydrothermal water, oxidation proceeds rapidly as atmospheric oxygen enters the water. The transfer of oxygen is particularly effective if the hydrothermal discharge is turbulent and has a large surface area.

  20. Hydrothermal synthesis of Na(0.5)La(0.5)TiO3-LaCrO3 solid-solution single-crystal nanocubes for visible-light-driven photocatalytic H2 evolution.

    PubMed

    Shi, Jinwen; Ye, Jinhua; Zhou, Zhaohui; Li, Mingtao; Guo, Liejin

    2011-07-04

    Cubic perovskite structure photocatalysts of Na(0.5)La(0.5)TiO(3) and (Na(0.5)La(0.5)TiO(3))(1.00)(LaCrO(3))(0.08) solid solution that consisted of well-defined single-crystal nanocubes were successfully prepared by means of facile and surfactant-free hydrothermal reactions for the first time. The results from different instrumental characterizations and theoretical calculations consistently confirmed the formation of nanocubic single-crystal solid solution of (Na(0.5)La(0.5)TiO(3))(1.00)(LaCrO(3))(0.08), and clearly revealed the modification of its physicochemical properties compared with those of Na(0.5)La(0.5)TiO(3). In particular, the effective narrowing of the bandgap (from 3.19 to 2.25 eV) by Cr(3+) in the solid solution made it possible to utilize visible light. The solid-solution configuration maintained the charge balance to preserve the valence of Cr(3+) rather than Cr(6+), and accommodated Cr(3+) with high content to form new energy bands instead of localized impurity levels. The hydrothermal preparation strategy ensured the formation of single crystals with high purity, few defects, and regulated morphology; it also guaranteed the valences of Ti(4+) and Cr(3+) in the solid solution. Consequently, the recombination of photogenerated carriers could be effectively suppressed to benefit photocatalytic H(2) evolution. (Na(0.5)La(0.5)TiO(3))(1.00)(LaCrO(3))(0.08) nanocubic single-crystal solid solution showed stable photocatalytic activity, and thus was proved to be a promising candidate for visible-light-driven photocatalytic H(2) evolution.

  1. Hydrothermal treatment of electric arc furnace dust.

    PubMed

    Yu, Bing-Sheng; Wang, Yuh-Ruey; Chang, Tien-Chin

    2011-06-15

    In this study, ZnO crystals were fabricated from electric arc furnace dust (EAFD) after alkaline leaching, purification and hydrothermal treatment. The effects of temperature, duration, pH, and solid/liquid ratio on ZnO crystal morphology and size were investigated. Results show a high reaction temperature capable of accelerating the dissolution of ZnO precursor, expediting the growth of 1D ZnO, and increasing the L/D ratio in the temperature range of 100-200°C. ZnO crystals with high purity can also be obtained, using the one-step hydrothermal treatment with a baffle that depends on the different solubility of zincite and franklinite in the hydrothermal conditions.

  2. Hydrothermal Biogeochemistry

    NASA Astrophysics Data System (ADS)

    Shock, E.; Havig, J.; Windman, T.; Meyer-Dombard, D.; Michaud, A.; Hartnett, H.

    2006-12-01

    Life in hot spring ecosystems is confronted with diverse challenges, and the responses to those challenges have dynamic biogeochemical consequences over narrow spatial and temporal scales. Within meters along hot spring outflow channels at Yellowstone, temperatures drop from boiling, and the near-boiling conditions of hot chemolithotrophic communities, to those that permit photosynthesis and on down to conditions where nematodes and insects graze on the edges of photosynthetic mats. Many major and trace element concentrations change only mildly in the water that flows through the entire ecosystem, while concentrations of other dissolved constituents (oxygen, sulfide, ammonia, total organic carbon) increase or decrease dramatically. Concentrations of metals and micronutrients range from toxic to inadequate for enzyme synthesis depending on the choice of hot spring. Precipitation of minerals may provide continuous growth of microbial niches, while dissolution and turbulent flow sweeps them away. Consequently, microbial communities change at the meter scale, and even more abruptly at the photosynthetic fringe. Isotopic compositions of carbon and nitrogen in microbial biomass reflect dramatic and continuous changes in metabolic strategies throughout the system. Chemical energy sources that support chemolithotrophic communities can persist at abundant or useless levels, or change dramatically owing to microbial activity. The rate of temporal change depends on the selection of hot spring systems for study. Some have changed little since our studies began in 1999. Others have shifted by two or more units in pH over several years, with corresponding changes in other chemical constituents. Some go through daily or seasonal desiccation cycles, and still others exhibit pulses of changing temperature (up to 40°C) within minutes. Taken together, hydrothermal ecosystems provide highly manageable opportunities for testing how biogeochemical processes respond to the scale of

  3. Direct formation of new, phase-stable, and photoactive anatase-type Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} solid solution nanoparticles by hydrothermal method

    SciTech Connect

    Hirano, Masanori Ito, Takaharu

    2008-08-04

    A new anatase phase of photoactive Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} (X = 0-0.2) solid solutions was directly formed as nanoparticles from precursor solutions of TiOSO{sub 4}, NbCl{sub 5}, and Sc(NO{sub 3}){sub 3} under mild hydrothermal conditions at 180 deg. C for 5 h using the hydrolysis of urea. With the increase of the content of niobium and scandium from X = 0 to 0.2, the lattice parameters a{sub 0} and c{sub 0}, the crystallite size, and the optical band gap of anatase gradually increased. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The anatase-type Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} (X = 0.05) showed approximately two times and three times as high photocatalytic activity as those of the hydrothermal anatase-type pure TiO{sub 2} and commercially available reference pure TiO{sub 2} (ST-01), respectively. The anatase phase of Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} (X = 0-0.2) existed stably up to 900 deg. C during heat treatment in air. New rutile-type Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} solid solutions are formed through the phase transformation. The starting temperature of anatase-to-rutile phase transformation for Ti{sub 1-2X}Nb{sub X}Sc{sub X}O{sub 2} (X = 0-0.2) solid solutions was delayed but its completing temperature was accelerated.

  4. Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

    USGS Publications Warehouse

    Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

    1988-01-01

    Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

  5. Performed surfactant-optimized aqueous alkaline flood

    SciTech Connect

    Thigpen, D.R.; Lawson, J.B.; Nelson, R.C.

    1991-11-26

    This paper describes improvement in a process for recovering oil from an acidic oil reservoir by injecting an aqueous alkaline solution comprising water, sodium chloride, and alkaline material for reacting with the reservoir oil forming a petroleum acid soap to form an in-situ surfactant system. The improvement comprises: selecting a preformed cosurfactant which is soluble in both the aqueous solution and the reservoir oil and has a solubility ratio which is grater than the solubility ratio of the petroleum acid soap where the solubility ratio is the ratio of solubility in the aqueous alkaline solution to the solubility in the reservoir oil; combining with the alkaline solution an amount of the preformed cosurfactant which will result in the in-situ surfacant system having a salinity about equal to a salinity which results in minimal interfacial tension between the oil in the reservoir and the in-situ surfactant system at reservoir temperature, wherein the amount of the preformed cosurfactant is about 0.3 percent by weight in the aqueous alkaline solution; and injecting the cosurfactant-aqueous alkaline solution mixture into the reservoir to displace oil toward a fluid production location.

  6. Direct measurement of CO2 solubility and pH in NaCl hydrothermal solutions by combining in-situ potentiometry and Raman spectroscopy up to 280 °C and 150 bar

    NASA Astrophysics Data System (ADS)

    Truche, Laurent; Bazarkina, Elena F.; Berger, Gilles; Caumon, Marie-Camille; Bessaque, Gilles; Dubessy, Jean

    2016-03-01

    The in-situ monitoring of aqueous solution chemistry at elevated temperatures and pressures is a major challenge in geochemistry. Here, we combined for the first time in-situ Raman spectroscopy for concentration measurements and potentiometry for pH measurement in a single hydrothermal cell equipped with sampling systems and operating under controlled conditions of temperature and pressure. Dissolved CO2 concentration and pH were measured at temperatures up to 280 °C and pressures up to 150 bar in the H2O-CO2 and H2O-CO2-NaCl systems. A Pitzer specific-ion-interaction aqueous model was developed and confirmed the accuracy and consistency of the measurements, at least up to 250 °C. The revised Pitzer parameters for the H2O-CO2-NaCl system were formatted for the Phreeqc geochemical software. Significant changes with respect to the Pitzer.dat database currently associated with Phreeqc were observed. The new model parameters are now available for further applications. The Raman and pH probes tested here may also be applied to field monitoring of hydrothermal springs, geothermal wells, and oil and gas boreholes.

  7. High pH (and not free ammonia) is responsible for Anammox inhibition in mildly alkaline solutions with excess of ammonium.

    PubMed

    Puyol, D; Carvajal-Arroyo, J M; Li, G B; Dougless, A; Fuentes-Velasco, M; Sierra-Alvarez, R; Field, J A

    2014-10-01

    Ammonium is a substrate of the anaerobic ammonium oxidation (Anammox) process but it has been suggested as a substrate-inhibitor because of the action of its unionized form, free ammonia. High pH of the medium is also an important limiting factor of the Anammox bacteria. Both effects are difficult to discriminate. In this work the inhibitory effects of high pH, total ammonia (TA) and NH3 on the Anammox process were investigated simultaneously. Results confirmed that TA caused no inhibition and high pH is a much more important inhibiting factor than NH3 in mildly alkaline conditions, based on a multi-factorial analysis. Values of pH higher than 7.6 caused Anammox inhibition >10 % and should be avoided during the application of the Anammox process in practice.

  8. Solvothermal Synthesis and Formation Mechanism of Potassium Sodium Niobate Mesocrystals Under Low Alkaline Conditions.

    PubMed

    Gu, QiLin; Zhu, Kongjun; Liu, Jinsong; Wang, Jing; Qiu, Jinhao; Cao, Yang; Liu, Pengcheng; Yao, Linlin

    2015-07-01

    Pure-phase (K, Na)NbO3 (KNN) powders with orthorhombic symmetry were successfully synthesized by solvothermal method using isopropanol as solvent, without the addition of water. The as-prepared powders were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometry to show the variation of phase, morphology, size distribution and chemical composition under different synthetic conditions, such as fill factors (FF) of the solvothermal system and alkalinity of the starting solution. Compared with the traditional hydrothermal method and the so-called solvothermal method (water aided in fact), small grains with well crystallinity were obtained using 100% isopropanol as reaction medium. The results indicate that both fill factor and alkalinity have significant effects on the phase structure and size distribution of the as-obtained KNN powders. Pure orthorhombic perovskite-structured KNN powders with a grain size of 100 nm were synthesized at the following condition: reaction time, 16 h; reaction temperature, 240 °C; fill factor, 70%; and alkalinity, 1 M. Small grains (~100 nm) tend to form mesocrystals (~10 µm) with tetrakaidecahedron structures, and the possible formation mechanism was proposed. The solvothermal method without the addition of water is a promising alternative to synthesize pure and refined powders under mild reaction conditions.

  9. Extraction of edingtonite from a natural zeolite under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Tutti, F.; Kamyab, S. M.; Barghi, M. A.; Badiei, A.

    2013-01-01

    In the present study, edingtonite has been extracted from natural zeolite clinoptilolite by simulating the natural hydrothermal conditions in the laboratory, under the influence of solutions with different concentrations of Ba+2 and Na+, varying from 0.5 to 2.8 mol/L, at 150 °C. In this work, the essential hydrothermal conditions have been provided by hydrothermal autoclaves. The natural and laboratory prepared samples were characterized by XRD, XRF and SEM methods.

  10. Hydrothermal Conditions and the Origin of Cellular Life.

    PubMed

    Deamer, David W; Georgiou, Christos D

    2015-12-01

    The conditions and properties of hydrothermal vents and hydrothermal fields are compared in terms of their ability to support processes related to the origin of life. The two sites can be considered as alternative hypotheses, and from this comparison we propose a series of experimental tests to distinguish between them, focusing on those that involve concentration of solutes, self-assembly of membranous compartments, and synthesis of polymers. Key Word: Hydrothermal systems.

  11. In situ observations of liquid-liquid phase separation in aqueous ZnSO4 solutions at temperatures up to 400 °C: Implications for Zn2+-SO42- association and evolution of submarine hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Wang, Xiaolin; Wan, Ye; Hu, Wenxuan; Chou, I.-Ming; Cao, Jian; Wang, Xiaoyu; Wang, Meng; Li, Zhen

    2016-05-01

    Liquid-liquid immiscibility is gaining recognition as an important process in hydrothermal fluid activity. However, studies of this complex process are relatively limited. We examined liquid-liquid immiscibility in aqueous ZnSO4 solutions at temperatures above ∼266.5 °C and at vapor-saturation pressures. The homogeneous aqueous ZnSO4 solution separated into ZnSO4-rich (L1) and ZnSO4-poor (L2) liquid phases coexisting with the vapor phase. The L1-L2 phase separation temperature decreased with increasing ZnSO4 concentration up to 1.0 mol/kg, and then increased at greater ZnSO4 concentrations, showing a typical lower critical solution temperature (LCST) of ∼266.5 °C. Gunningite (ZnSO4·H2O) precipitated in 2.0 mol/kg ZnSO4 solution at 360 °C. The L1-L2 phase separation resulted mainly from the strong Zn2+-SO42- association at high temperatures. The major results of this study are: (1) the discovery of the LCST in these systems, a macroscale property associated with polymeric mixtures; (2) analyses of the peak area ratios of the v1(SO42-) and OH stretching bands, which suggest that the sulfate concentration increases with increasing temperature in L1, especially above 375 °C; (3) a new Raman v1(SO42-) mode at ∼1005 cm-1 observed only in the L1 phase, whose fraction increases with increasing temperature; and (4) the shape of the OH Raman stretching band, which indicates that water molecules and solute interact much more strongly in L1 than in the coexisting L2 phase, suggesting that water molecules fit into the framework formed by various Zn2+-SO42- pairs and chain structures in L1. These results have potential implications for understanding transport and reduction of seawater-derived sulfate in submarine hydrothermal systems. The formation of an immiscible sulfate-rich liquid phase can favor the circulation of sulfate within mid-ocean ridge basalt because the sulfate-rich liquid density is higher than that of the coexisting fluid. The reduction of sulfate

  12. Capillary electrophoretic study of the degradation pathways and kinetics of the aspartyl model tetrapeptide Gly-Phe-Asp-GlyOH in alkaline solution.

    PubMed

    Brückner, Christin; Imhof, Diana; Scriba, Gerhard K E

    2013-03-25

    The aim of the present study was the investigation of the isomerization and epimerization kinetics of the aspartyl tetrapeptide Gly-Phe-Asp-GlyOH at alkaline conditions. Incubations of the model tetrapeptide in sodium borate buffer, pH 10 and ionic strength 0.2M, at 25°C and 80°C were analyzed by a validated CE-UV assay and fitted according to a pharmacokinetic model. CE-ESI-MS was used for peptide identification. Enantiomerization and isomerization of the aspartyl residue of the model tetrapeptide was observed under all experimental conditions applied. Differences in the velocity and the ratios of the rates of the degradation reactions indicated different effects of temperature on the individual reactions. At 80°C, a rapid formation of β-Asp and d-Asp containing isomers from Gly-l-Phe-α-l-Asp-GlyOH was monitored. Rate constants of the hydrolysis of the succinimide (Asu) intermediate generally exceeded the formation of the intermediate from α/β-Asp peptides. A higher rate constant was observed for the enantiomerization from l-configured Asu compared to d-Asu. At 25°C, epimerization and isomerization equilibrium was not reached within 5208h. Compared to 80°C different ratios of the individual reaction rates were noted. Moreover, inversion of the sequence of the first 2 amino acids was noted as a minor side reaction at 80°C.

  13. METEORIC-HYDROTHERMAL SYSTEMS.

    USGS Publications Warehouse

    Criss, Robert E.; Taylor, Hugh P.

    1986-01-01

    This paper summarizes the salient characteristics of meteoric-hydrothermal systems, emphasing the isotopic systematics. Discussions of permeable-medium fluid dynamics and the geology and geochemistry of modern geothermal systems are also provided, because they are essential to any understanding of hydrothermal circulation. The main focus of the paper is on regions of ancient meteoric-hydrothermal activity, which give us information about the presently inaccessible, deep-level parts of modern geothermal systems. It is shown oxygen and hydrogen isotopes provide a powerful method to discover and map fossil hydrothermal systems and to investigate diverse associated aspects of rock alteration and ore deposition.

  14. Hydrothermal organic synthesis experiments

    NASA Technical Reports Server (NTRS)

    Shock, Everett L.

    1992-01-01

    Ways in which heat is useful in organic synthesis experiments are described, and experiments on the hydrothermal destruction and synthesis of organic compounds are discussed. It is pointed out that, if heat can overcome kinetic barriers to the formation of metastable states from reduced or oxidized starting materials, abiotic synthesis under hydrothermal conditions is a distinct possibility. However, carefully controlled experiments which replicate the descriptive variables of natural hydrothermal systems have not yet been conducted with the aim of testing the hypothesis of hydrothermal organic systems.

  15. QM/MM analysis suggests that Alkaline Phosphatase (AP) and Nucleotide pyrophosphatase/phosphodiesterase slightly tighten the transition state for phosphate diester hydrolysis relative to solution: implication for catalytic promiscuity in the AP superfamily

    PubMed Central

    Hou, Guanhua

    2011-01-01

    Several members of the Alkaline Phosphatase (AP) superfamily exhibit a high level of catalytic proficiency and promiscuity in structurally similar active sites. A thorough characterization of the nature of transition state for different substrates in these enzymes is crucial for understanding the molecular mechanisms that govern those remarkable catalytic properties. In this work, we study the hydrolysis of a phosphate diester, MpNPP−, in solution, two experimentally well-characterized variants of AP (R166S AP, R166S/E322Y AP) and wild type Nucleotide pyrophosphatase/phosphodiesterase (NPP) by QM/MM calculations in which the QM method is an approximate density functional theory previously parameterized for phosphate hydrolysis (SCC-DFTBPR). The general agreements found between these calculations and available experimental data for both solution and enzymes support the use of SCC-DFTBPR/MM for a semi-quantitative analysis of the catalytic mechanism and nature of transition state in AP and NPP. Although phosphate diesters are cognate substrates for NPP but promiscuous substrates for AP, the calculations suggest that their hydrolysis reactions catalyzed by AP and NPP feature similar synchronous transition states that are slightly tighter in nature compared to that in solution, due in part to the geometry of the bimetallic zinc motif. Therefore, this study provides the first direct computational support to the hypothesis that enzymes in the AP superfamily catalyze cognate and promiscuous substrates via similar transition states to those in solution. Our calculations do not support the finding of recent QM/MM studies by López-Canut and coworkers, who suggested that the same diester substrate goes through a much looser transition state in NPP/AP than in solution, a result likely biased by the large structural distortion of the bimetallic zinc site in their simulations. Finally, our calculations for different phosphate diester orientations and phosphorothioate diesters

  16. QM/MM analysis suggests that Alkaline Phosphatase (AP) and nucleotide pyrophosphatase/phosphodiesterase slightly tighten the transition state for phosphate diester hydrolysis relative to solution: implication for catalytic promiscuity in the AP superfamily.

    PubMed

    Hou, Guanhua; Cui, Qiang

    2012-01-11

    Several members of the Alkaline Phosphatase (AP) superfamily exhibit a high level of catalytic proffciency and promiscuity in structurally similar active sites. A thorough characterization of the nature of transition state for different substrates in these enzymes is crucial for understanding the molecular mechanisms that govern those remarkable catalytic properties. In this work, we study the hydrolysis of a phosphate diester, MpNPP(-), in solution, two experimentally well-characterized variants of AP (R166S AP, R166S/E322Y AP) and wild type Nucleotide pyrophosphatase/phosphodiesterase (NPP) by QM/MM calculations in which the QM method is an approximate density functional theory previously parametrized for phosphate hydrolysis (SCC-DFTBPR). The general agreements found between these calculations and available experimental data for both solution and enzymes support the use of SCC-DFTBPR/MM for a semiquantitative analysis of the catalytic mechanism and nature of transition state in AP and NPP. Although phosphate diesters are cognate substrates for NPP but promiscuous substrates for AP, the calculations suggest that their hydrolysis reactions catalyzed by AP and NPP feature similar synchronous transition states that are slightly tighter in nature compared to that in solution, due in part to the geometry of the bimetallic zinc motif. Therefore, this study provides the first direct computational support to the hypothesis that enzymes in the AP superfamily catalyze cognate and promiscuous substrates via similar transition states to those in solution. Our calculations do not support the finding of recent QM/MM studies by López-Canut and co-workers, who suggested that the same diester substrate goes through a much looser transition state in NPP/AP than in solution, a result likely biased by the large structural distortion of the bimetallic zinc site in their simulations. Finally, our calculations for different phosphate diester orientations and phosphorothioate diesters

  17. Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

    NASA Astrophysics Data System (ADS)

    Shironosova, G. P.; Kolonin, G. R.; Borovikov, A. A.; Borisenko, A. S.

    2016-08-01

    Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride-sulfide-chloride-carbonate-sulfate-system in the presence of Na, Ca, and P with fluids of various acidities-alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500-100°C and 2000-125 bar. Among other solid phases, REEs-fluorite, monazite, and REE-F-apatite were formed as CaF2-(Ln,Y)F3, LnPO4, and Ca5(PO4)3F-(Ln,Y)3(PO4)3 ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.

  18. Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} and its defect chemistry

    SciTech Connect

    Harunsani, Mohammad H.; Woodward, David I.; Peel, Martin D.; Ashbrook, Sharon E.; Walton, Richard I.

    2013-11-15

    Perovskites of nominal composition NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3-bar c. Ce L{sub III}-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce{sup 3+} there is evidence for Ce{sup 4+}. The paramagnetic Ce{sup 3+} affects the chemical shift and line width of {sup 23}Na MAS NMR spectra, which also show with no evidence for A-site ordering. {sup 2}H MAS NMR of samples prepared in D{sub 2}O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D{sub 2}O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce{sup 4+} to provide charge balance of A-site water. - Graphical abstract: A multi-element A-site perovskite crystallises directly from aqueous, basic solutions at 240 °C; while the paramagnetic effect of Ce{sup 3+} on the {sup 23}Na NMR shows a homogeneous solid-solution, the incorporation of A-site water is also found from {sup 2}H NMR and IR, with oxidation of some cerium to charge balance proved by XANES spectroscopy. Display Omitted - Highlights: • Direct hydrothermal synthesis allows crystallisation of a perovskite solid-solution. • XANES spectroscopy shows some oxidation of Ce{sup 3+} to Ce{sup 4+}. • The paramagnetism of Ce{sup 3+} shifts and broadens the {sup 23}Na solid-state NMR. • The perovskite materials incorporate water as an A-site defect.

  19. The effects of acid and alkaline solutions on cut marks and on the structure of bone: An experimental study on porcine ribs.

    PubMed

    Amadasi, Alberto; Camici, Arianna; Sironi, Luca; Profumo, Antonella; Merli, Davide; Mazzarelli, Debora; Porta, Davide; Duday, Henri; Cattaneo, Cristina

    2015-11-01

    Among taphonomical modifications during decomposition processes, little is known about the action of high or low pH to human tissues and bones. Moreover, acid or basic solutions are seldom used to ease decomposition and wrecking of the body. In this study a total of 60 samples of porcine bones on which two cut marks were produced before the beginning of the experiment, were put in six different solutions with different pH (1, 3, 5, 9, 12, 14) and analyzed every five days over a period of 70 days. Surveys were carried out macroscopically, with stereomicroscopy and with light microscopy on thin sections. Only the specimens exposed to extremely acid (<1) or basic (>12) pH showed evident modifications of the bone's structure, as witnessed by the analyses with stereomicroscopy as well. Many samples showed a detachment of the periosteum; cut marks became soon unrecognizable with pH 14 but still detectable in all the other samples. The information gained from the present study can be of great help in detecting the exposure of human tissues to high or low environmental pH and in understanding the effects that these solutions can exert on human bones.

  20. Alkaline detergent recycling via ultrafiltration

    SciTech Connect

    Steffani, C.; Meltzer, M.

    1995-06-01

    The metal finishing industry uses alkaline cleaners and detergents to remove oils and dirt from manufactured parts, often before they are painted or plated. The use of these cleaners has grown because environmental regulations are phasing out ozone depleting substances and placing restrictions on the use and disposal of many hazardous solvents. Lawrence Livermore National Laboratory is examining ultrafiltration as a cleaning approach that reclaims the cleaning solutions and minimizes wastes. The ultrafiltration membrane is made from sheets of polymerized organic film. The sheets are rolled onto a supporting frame and installed in a tube. Spent cleaning solution is pumped into a filter chamber and filtered through the membrane that captures oils and dirt and allows water and detergent to pass. The membrane is monitored and when pressure builds from oil and dirt, an automatic system cleans the surface to maintain solution flow and filtration quality. The results show that the ultrafiltration does not disturb the detergent concentration or alkalinity but removed almost all the oils and dirt leaving the solution in condition to be reused.

  1. Anodes for alkaline electrolysis

    DOEpatents

    Soloveichik, Grigorii Lev

    2011-02-01

    A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

  2. Alkaline battery, separator therefore

    NASA Technical Reports Server (NTRS)

    Schmidt, George F. (Inventor)

    1980-01-01

    An improved battery separator for alkaline battery cells has low resistance to electrolyte ion transfer and high resistance to electrode ion transfer. The separator is formed by applying an improved coating to an electrolyte absorber. The absorber, preferably, is a flexible, fibrous, and porous substrate that is resistant to strong alkali and oxidation. The coating composition includes an admixture of a polymeric binder, a hydrolyzable polymeric ester and inert fillers. The coating composition is substantially free of reactive fillers and plasticizers commonly employed as porosity promoting agents in separator coatings. When the separator is immersed in electrolyte, the polymeric ester of the film coating reacts with the electrolyte forming a salt and an alcohol. The alcohol goes into solution with the electrolyte while the salt imbibes electrolyte into the coating composition. When the salt is formed, it expands the polymeric chains of the binder to provide a film coating substantially permeable to electrolyte ion transfer but relatively impermeable to electrode ion transfer during use.

  3. Kinetic study of the α-tocopherol-regeneration reaction of ubiquinol-10 in methanol and acetonitrile solutions: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    PubMed

    Mukai, Kazuo; Oi, Masanori; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-03-01

    A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt < NaClO(4) ~ NaI < LiClO(4) < Mg(ClO(4))(2) at the same concentration of metal salts in methanol. On the other hand, in acetonitrile, the k(r) values decreased in the order of no metal salt > NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

  4. The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2009-01-01

    X-ray absorption spectroscopy (XAS) measurements were made at the Nd L3-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500????C and up to 520??MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07??m Nd/0.16??m HNO3 aqueous solution reveals a contraction of the Nd-O distance of the Nd3+ aqua ion at a uniform rate of ~ 0.013????/100????C and a uniform reduction of the number of coordinated H2O molecules from 10.0 ?? 0.9 to 7.4 ?? 0.9 over the range from 25 to 500????C and up to 370??MPa. The rate of reduction of the first-shell water molecules with temperature for Nd3+ (26%) is intermediate between the rate for the Gd3+ aqua ion (22% from 25 to 500????C) and the rates for the Eu3+ (29% from 25 to 400????C) and the Yb3+ aqua ions (42% from 25 to 500????C) indicating an intermediate stability of the Nd3+ aqua ion consistent with the tetrad effect. Nd L3-edge XAS measurements of 0.05??m NdCl3 aqueous solution at 25 to 500????C and up to 520??MPa show that stepwise inner-sphere complexes most likely of the type Nd(H2O)?? - nCln+3 - n occur in the solution at elevated temperatures, where ?? ??? 9 at 150????C decreasing to ~ 6 at 500????C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 ?? 0.2 to 2.0 ?? 0.2 in the solution upon increase of temperature from 150 to 500????C. Conversely, the number of H2O ligands of Nd(H2O)?? - nCln+3 - n complexes is uniformly reduced with temperature from 7.5 ?? 0.8 to 3.7 ?? 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than that of heavy REE chloride complexes in low pH fluids at elevated temperatures consistent with REE analysis of fluids from deep

  5. Controlled synthesis of BiVO{sub 4} with multiple morphologies via an ethylenediamine-assisted hydrothermal method

    SciTech Connect

    Qi, Xuemei; Zhu, Xinyuan; Wu, Jiang; Wu, Qiang; Li, Xian; Gu, Miaoli

    2014-11-15

    Graphical abstract: BiVO{sub 4} samples with various morphologies were synthesized via a simple ethylenediamine (EN) assisted hydrothermal route. One of the mixed crystal phase with spherical and porous morphology showed excellent photocatalytic activity and about 90% Rhodamine B was degraded after 140 min visible light irradiation. - Highlights: • BiVO{sub 4} samples with various morphologies were synthesized by hydrothermal method. • Ethylenediamine mainly acts as alkaline source to adjust pH values of precursor. • BiVO{sub 4} with spherical morphology has excellent photocatalytic activity. - Abstract: In this work, BiVO{sub 4} particles with different crystal structures and morphologies including hexahedral, spherical porous and hyperbranched ones were fabricated in the presence of ethylenediamine by hydrothermal process. The as-fabricated samples were well characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and ultraviolet–visible absorption spectroscopy. The results showed that the morphology and crystal structure of BiVO{sub 4} particles could be well controlled by only changing the ethylenediamine content in the deionized water solution. Photocatalytic activity of the samples was evaluated by the degradation of Rhodamine B under visible-light irradiation. It was shown that BiVO{sub 4} sample with spherical porous morphology and mixed crystal phase exhibited the best photocatalytic performance after optimizing the ethylenediamine content. The best degradation ratio of Rhodamine B could reach about 87% after 140 min visible-light irradiation.

  6. Nanocrystalline spinel ferrite (MFe{sub 2}O{sub 4}, M = Ni, Co, Mn, Mg, Zn) powders prepared by a simple aloe vera plant-extracted solution hydrothermal route

    SciTech Connect

    Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan; Amornkitbamrung, Vittaya; Maensiri, Santi

    2013-06-01

    Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates and aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the

  7. Alkaline battery operational methodology

    DOEpatents

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

    2016-08-16

    Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

  8. Synthesis, crystal structure and investigation of mononuclear copper(II) and zinc(II) complexes of a new carboxylate rich tripodal ligand and their interaction with carbohydrates in alkaline aqueous solution.

    PubMed

    Stewart, Christopher D; Pedraza, Mayra; Arman, Hadi; Fan, Hua-Jun; Schilling, Eduardo Luiz; Szpoganicz, Bruno; Musie, Ghezai T

    2015-08-01

    A new carboxylate rich asymmetric tripodal ligand, N-[2-carboxybenzomethyl]-N-[carboxymethyl]-β-alanine (H3camb), and its di-copper(II), (NH4)2[1]2, and di-zinc(II), ((CH3)4N)2[2]2, complexes have been synthesized as carbohydrate binding models in aqueous solutions. The ligand and complexes have been fully characterized using several techniques, including single crystal X-ray diffraction. The interactions of (NH4)2[1]2 and ((CH3)4N)2[2]2 with D-glucose, D-mannose, D-xylose and xylitol in aqueous alkaline media were investigated using UV-Vis and (13)C-NMR spectroscopic techniques, respectively. The molar conductance, NMR and ESI-MS studies indicate that the complexes dissociate in solution to produce the respective complex anions, 1(-) and 2(-). Complexes 1(-) and 2(-) showed chelating ability towards the naturally abundant and biologically relevant sugars, D-glucose, D-mannose, D-xylose, and xylitol. The complex ions bind to one molar equivalent of the sugars, even in the presence of stoichiometric excess of the substrates, in solution. Experimentally obtained spectroscopic data and computational results suggest that the substrates bind to the metal center in a bidentate fashion. Apparent binding constant values, pK(app), between the complexes and the substrates were determined and a specific mode of substrate binding is proposed. The pK(app) and relativistic density functional theory (DFT) calculated Gibbs free energy values indicate that D-mannose displayed the strongest interaction with the complexes. Syntheses, characterizations, detailed substrate binding studies using spectroscopic techniques, single crystal X-ray diffraction and geometry optimizations of the complex-substrates with DFT calculations are also reported.

  9. Determination of bisphenol A in thermal printing papers treated by alkaline aqueous solution using the combination of single-drop microextraction and HPLC.

    PubMed

    Gao, Leihong; Zou, Jing; Liu, Haihong; Zeng, Jingbin; Wang, Yiru; Chen, Xi

    2013-04-01

    A method for the quantitative determination of bisphenol A in thermal printing paper was developed and validated. Bisphenol A was extracted from the paper samples using 2% NaOH solution, then the extracted analyte was enriched using single-drop microextraction followed by HPLC analysis. Several parameters relating to the single-drop microextraction efficiency including extraction solvent, extraction temperature and time, stirring rate, and pH of donor phase were studied and optimized. Spiked recovery of bisphenol A at 20 and 5 mg/g was found to be 95.8 and 108%, and the method detection limit and method quantification limit was 0.03 and 0.01 mg/g, respectively. Under the optimized conditions, the proposed method was applied to the determination of bisphenol A in seven types of thermal printing paper samples, and the concentration of bisphenol A was found in the range of 0.53-20.9 mg/g. The considerably minimum usage of organic solvents (5 μL 1-octanol) and high enrichment factor (189-197) in the sample preparation are the two highlighted advantages in comparison with previously published works.

  10. SrCo1−xTixO3−δ perovskites as excellent catalysts for fast degradation of water contaminants in neutral and alkaline solutions

    PubMed Central

    Miao, Jie; Sunarso, Jaka; Su, Chao; Zhou, Wei; Wang, Shaobin; Shao, Zongping

    2017-01-01

    Perovskite-like oxides SrCo1−xTixO3−δ (SCTx, x = 0.1, 0.2, 0.4, 0.6) were used as heterogeneous catalysts to activate peroxymonosulfate (PMS) for phenol degradation under a wide pH range, exhibiting more rapid phenol oxidation than Co3O4 and TiO2. The SCT0.4/PMS system produced a high activity at increased initial pH, achieving optimized performance at pH ≥ 7 in terms of total organic carbon removal, the minimum Co leaching and good catalytic stability. Kinetic studies showed that the phenol oxidation kinetics on SCT0.4/PMS system followed the pseudo-zero order kinetics and the rate on SCT0.4/PMS system decreased with increasing initial phenol concentration, decreased PMS amount, catalyst loading and solution temperature. Quenching tests using ethanol and tert-butyl alcohol demonstrated sulfate and hydroxyl radicals for phenol oxidation. This investigation suggested promising heterogeneous catalysts for organic oxidation with PMS, showing a breakthrough in the barriers of metal leaching, acidic pH, and low efficiency of heterogeneous catalysis. PMID:28281656

  11. SrCo1‑xTixO3‑δ perovskites as excellent catalysts for fast degradation of water contaminants in neutral and alkaline solutions

    NASA Astrophysics Data System (ADS)

    Miao, Jie; Sunarso, Jaka; Su, Chao; Zhou, Wei; Wang, Shaobin; Shao, Zongping

    2017-03-01

    Perovskite-like oxides SrCo1‑xTixO3‑δ (SCTx, x = 0.1, 0.2, 0.4, 0.6) were used as heterogeneous catalysts to activate peroxymonosulfate (PMS) for phenol degradation under a wide pH range, exhibiting more rapid phenol oxidation than Co3O4 and TiO2. The SCT0.4/PMS system produced a high activity at increased initial pH, achieving optimized performance at pH ≥ 7 in terms of total organic carbon removal, the minimum Co leaching and good catalytic stability. Kinetic studies showed that the phenol oxidation kinetics on SCT0.4/PMS system followed the pseudo-zero order kinetics and the rate on SCT0.4/PMS system decreased with increasing initial phenol concentration, decreased PMS amount, catalyst loading and solution temperature. Quenching tests using ethanol and tert-butyl alcohol demonstrated sulfate and hydroxyl radicals for phenol oxidation. This investigation suggested promising heterogeneous catalysts for organic oxidation with PMS, showing a breakthrough in the barriers of metal leaching, acidic pH, and low efficiency of heterogeneous catalysis.

  12. Predictive Microbiology in Hydrothermal Ecosystems

    NASA Astrophysics Data System (ADS)

    Shock, E. L.; Holland, M. E.; Meyer-Dombard, D.; Amend, J. P.

    2004-12-01

    Metabolisms of high-temperature microorganisms are not revealed by molecular phylogenies, but, if known, could connect microbial and geochemical processes in hydrothermal ecosystems. Disequilibria among oxidation-reduction reactions, established by kinetic barriers to electron-transfer reactions, provide energy, and life provides the catalyst. In more-or-less closed systems, such as slowly-accumulating detrital sediments, life taps as much energy as conversion efficiency will allow, and many redox couples are driven to near-equilibrium states. In contrast, open systems like hot springs maintain persistent states of redox disequilibria that support highly diverse communities of microorganisms. In Yellowstone National Park hot springs, the magnitude of these redox disequilibria can be predicted based solely on pH, guided by past measurements of hot spring geochemistry. Geochemical diversity at Yellowstone National Park produces hydrothermal ecosystems over a pH range from less than 2 to greater than 8, with associated major and trace element concentration changes. We have assessed the supply of chemical energy in the form of redox reactions that are far from equilibrium in the Fe-S-C-O-H-N system. Field measurements of temperature, pH, dissolved oxygen, total sulfide, nitrate, nitrite, total ammonia, ferrous iron, and bicarbonate alkalinity are combined with lab analyses of sulfate, iron mineralogy, and gas composition (hydrogen, carbon dioxide, methane, carbon monoxide) in a thermodynamic analysis of the state of redox disequilibria in more than 50 hot spring habitats. Initial results (using only inorganic forms of C) yield nearly 200 reactions that are out of redox equilibrium, and which could supply energy if catalyzed. Some of these reactions, such as hydrogen oxidation, are pH independent, and the energy supply is nearly constant at about 24 kcal per mole of electrons over the entire pH range. Other reactions, which are pH dependent, show greater or lesser

  13. Toxicity of alkalinity to Hyalella azteca

    USGS Publications Warehouse

    Lasier, P.J.; Winger, P.V.; Reinert, R.E.

    1997-01-01

    Toxicity testing and chemical analyses of sediment pore water have been suggested for use in sediment quality assessments and sediment toxicity identification evaluations. However, caution should be exercised in interpreting pore-water chemistry and toxicity due to inherent chemical characteristics and confounding relationships. High concentrations of alkalinity, which are typical of sediment pore waters from many regions, have been shown to be toxic to test animals. A series of tests were conducted to assess the significance of elevated alkalinity concentrations to Hyalella azteca, an amphipod commonly used for sediment and pore-water toxicity testing. Toxicity tests with 14-d old and 7-d old animals were conducted in serial dilutions of sodium bicarbonate (NaHCO3) solutions producing alkalinities ranging between 250 to 2000 mg/L as CaCO3. A sodium chloride (NaCl) toxicity test was also conducted to verify that toxicity was due to bicarbonate and not sodium. Alkalinity was toxic at concentrations frequently encountered in sediment pore water. There was also a significant difference in the toxicity of alkalinity between 14-d old and 7-d old animals. The average 96-h LC50 for alkalinity was 1212 mg/L (as CaCO3) for 14-d old animals and 662 mg/L for the younger animals. Sodium was not toxic at levels present in the NaHCO3 toxicity tests. Alkalinity should be routinely measured in pore-water toxicity tests, and interpretation of toxicity should consider alkalinity concentration and test-organism tolerance.

  14. Alkaline electrochemical cells and method of making

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1970-01-01

    Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

  15. An experimental study of zinc chloride speciation from 300 to 600 °C and 0.5 to 2.0 kbar in buffered hydrothermal solutions

    USGS Publications Warehouse

    Cygan, G.L.; Hemley, J.J.; d'Angelo, W. M.

    1994-01-01

    The solubility of sphalerite (ZnS) was measured in KCl-HCl-H2O solutions at 300-600??C and 0.5-2.0 kbar. The silicate assemblage K-feldspar-muscovite (or andalusite)-quartz was used to buffer the solution to acid conditions, resulting in the total solubility reaction 2K+ + KAl2AlSi3O10(OH)2 + 6SiO2 + ZnS + nCl- = ZnCln(2-n) + 3KAlSi3O8 + H2S. (muscovite) (quartz) (sphalerite) (K-feldspar) A computer retrieval technique was used to derive average chloride ligand numbers for chlorozinc species at 0.25-2.0 molal total chloride. This technique mathematically solves for the average ligand number using a series of pertinent chemical relations at P and T. Mono- and di-chlorozinc species were found to predominate throughout the pressure-temperature-composition range investigated. The logarithms of the first and second dissociation constants for ZnCl20 were evaluated over the P-T range; for example, at 1 kbar, the values -0.41 and -1.42 were computed for the logarithm of the first dissociation constant, while -7.62 and -10.57 were computed for the logarithm of the second dissociation constant, for 400 and 500??C, respectively. Results are compared to past studies conducted at subcritical conditions and differ in that we find no evidence for more highly coordinated chloro-zinc species except possibly for ZnCl3- at 600??C, 1 and 2 kbar. Our results are consistent with electrostatic theory, which favors lower charged to neutral molecules in low dielectric-constant media. ?? 1994.

  16. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park. 1: The origin of thiosulfate in hot spring waters

    SciTech Connect

    Xu, Y.; Schoonen, M.A.A.; Nordstrom, D.K.; Cunningham, K.M.; Ball, J.W.

    1998-12-01

    Thiosulfate (S{sub 2}O{sub 3}{sup 2{minus}}), polythionate (S{sub x}O{sub 6}{sup 2{minus}}), dissolved sulfide (H{sub 2}S), and sulfate (SO{sub 4}{sup 2{minus}}) concentrations in thirty-nine alkaline and acidic springs in Yellowstone National Park (YNP) were determined. The analyses were conducted on site, using ion chromatography for thiosulfate, polythionate, and sulfate, and using colorimetry for dissolved sulfide. Thiosulfate was detected at concentrations typically less than 2 {micro}mol/L in neutral and alkaline chloride springs with low sulfate concentrations (Cl{sup {minus}}/SO{sub 4}{sup 2{minus}} > 25). The thiosulfate concentration levels are about one to two orders of magnitude lower than the concentration of dissolved sulfide in these springs. In most acid sulfate and acid sulfate-chloride springs (Cl{sup {minus}}/SO{sub 4}{sup 2{minus}} < 10), thiosulfate concentrations were also typically lower than 2 {micro}mol/L. However, in some chloride springs enriched with sulfate (Cl{sup {minus}}/SO{sub 4}{sup 2{minus}} between 10 and 25), thiosulfate was found at concentrations ranging from 9 to 95 {micro}mol/L, higher than the concentrations of dissolved sulfide in these waters. Polythionate was detected only in Cinder Pool, Norris Geyser basin, at concentrations up to 8 {micro}mol/L, with an average S-chain-length from 4.1 to 4.9 sulfur atoms. The results indicate that no thiosulfate occurs in the deeper parts of the hydrothermal system. Thiosulfate may form, however, from (1) hydrolysis of native sulfur by hydrothermal solutions in the shallower parts (<50 m) of the system, (2) oxidation of dissolved sulfide upon mixing of a deep hydrothermal water with aerated shallow groundwater, and (3) the oxidation of dissolved sulfide by dissolved oxygen upon discharge of the hot spring. Upon discharge of a sulfide-containing hydrothermal water, oxidation proceeds rapidly as atmospheric oxygen enters the water. The transfer of oxygen is particularly effective if the

  17. Pyrophosphate synthesis in iron mineral films and membranes simulating prebiotic submarine hydrothermal precipitates

    NASA Astrophysics Data System (ADS)

    Barge, Laura M.; Doloboff, Ivria J.; Russell, Michael J.; VanderVelde, David; White, Lauren M.; Stucky, Galen D.; Baum, Marc M.; Zeytounian, John; Kidd, Richard; Kanik, Isik

    2014-03-01

    Cells use three main ways of generating energy currency to drive metabolism: (i) conversion of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) by the proton motive force through the rotor-stator ATP synthase; (ii) the synthesis of inorganic phosphate˜phosphate bonds via proton (or sodium) pyrophosphate synthase; or (iii) substrate-level phosphorylation through the direct donation from an active phosphoryl donor. A mechanism to produce a pyrophosphate bond as “energy currency” in prebiotic systems is one of the most important considerations for origin of life research. Baltscheffsky (1996) suggests that inorganic pyrophosphate (PO74-; PPi) may have preceded ATP/ADP as an energy storage molecule in earliest life, produced by an H+ pyrophosphatase. Here we test the hypothesis that PPi could be synthesized in inorganic precipitates simulating hydrothermal chimney structures transected by thermal and/or ionic gradients. Appreciable yields of PPi were obtained via substrate phosphorylation by acetyl phosphate within the iron sulfide/silicate precipitates at temperatures expected for an alkaline hydrothermal system. The formation of PPi only occurred in the solid phase, i.e. when both Pi and the phosphoryl donor were precipitated with Fe-sulfides or Fe-silicates. The amount of Ac-Pi incorporated into the precipitate was a significant factor in the amount of PPi that could form, and phosphate species were more effectively incorporated into the precipitate at higher temperatures (⩾50 to >85 °C). Thus, we expect that the hydrothermal precipitate would be more enriched in phosphate (and especially, Ac-Pi) near the inner margins of a hydrothermal mound where PPi formation would be at a maximum. Iron sulfide and iron silicate precipitates effectively stabilized Ac-Pi and PPi against hydrolysis (relative to hydrolysis in aqueous solution). Thus it is plausible that PPi could accumulate as an energy currency up to useful concentrations for early life in a

  18. Useful Ingredients Recovery from Sewage Sludge by using Hydrothermal Reaction

    NASA Astrophysics Data System (ADS)

    Suzuki, Koichi; Moriyama, Mika; Yamasaki, Yuki; Takahashi, Yui; Inoue, Chihiro

    2006-05-01

    Hydrothermal treatment of sludge from a sewage treatment plant was conducted to obtain useful ingredients for culture of specific microbes which can reduce polysulfide ion into sulfide ion and/or hydrogen sulfide. Several additives such as acid, base, and oxidizer were added to the hydrothermal reaction of excess sludge to promote the production of useful materials. After hydrothermal treatment, reaction solution and precipitation were qualitatively and quantitatively analyzed and estimated the availability as nutrition in cultural medium. From the results of product analysis, most of organic solid in sewage was basically decomposed by hydrothermal hydrolysis and transformed into oily or water-soluble compounds. Bacterial culture of sulfate-reducing bacteria (SRB) showed the good results in multiplication with medium which was obtained from hydrothermal treatment of sewage sludge with magnesium or calcium hydroxide and hydrogen peroxide.

  19. Interactions Between Serpentinization, Hydrothermal Activity and Microbial Community at the Lost City Hydrothermal Field

    NASA Astrophysics Data System (ADS)

    Delacour, A.; Frueh-Green, G. L.; Bernasconi, S. M.; Schaeffer, P.; Frank, M.; Gutjahr, M.; Kelley, D. S.

    2008-12-01

    Seafloor investigations of slow- and ultraslow-spreading ridges have reported many occurrences of exposed mantle peridotites and gabbroic rocks on the ocean floor. Along the Mid-Atlantic Ridge, these uplifted portions of oceanic crust host high-temperature black smoker-type hydrothermal systems (e.g., Rainbow, Logatchev, Saldanha), and the more distinct low-temperature Lost City Hydrothermal Field (LCHF). Built on a southern terrace of the Atlantis Massif, the LCHF is composed of carbonate-brucite chimneys that vent alkaline and low-temperature (40-90°C) hydrothermal fluids. These fluids are related to serpentinization of mantle peridotites, which together with minor gabbroic intrusions form the basement of the LCHF. Long-lived hydrothermal activity at Lost City led to extensive seawater-rock interaction in the basement rocks, as indicated by seawater-like Sr- and mantle to unradiogenic Nd-isotope compositions of the serpentinites. These high fluid fluxes in the southern part of the massif influenced the conditions of serpentinization and have obliterated the early chemical signatures in the serpentinites, especially those of carbon and sulfur. Compared to reducing conditions commonly formed during the first stages of serpentinization, serpentinization at Lost City is characterized by relatively oxidizing conditions resulting in a predominance of magnetite, the mobilization/dissolution and oxidation of igneous sulfides to secondary pyrite, and the incorporation of seawater sulfate, all leading to high bulk-rock S-isotope compositions. The Lost City hydrothermal fluids contain high concentrations in methane, hydrogen, and low-molecular weight hydrocarbons considered as being produced abiotically. In contrast, organic compounds in the serpentinites are dominated by the occurrences of isoprenoids (pristane, phytane, and squalane), polycyclic compounds (hopanes and steranes), and higher abundances of C16 to C20 n-alkanes indicative of a marine organic input. We

  20. Geochemistry of hydrothermal plume in the Suiyo Seamount Caldera.

    NASA Astrophysics Data System (ADS)

    Shitashima, K.; Maeda, Y.

    2002-12-01

    samples were collected by taking the distance from the chimney gradually and pH change was monitored during the sampling and observing at the hydrothermal active areas. Alkalinity, pH, hydrogen sulfide, total dissolved inorganic carbon (DIC), chemical species of trace metals (particulate, dissolved and organic form) and nutrients in the hydrothermal plume samples were analyzed. Though DIC concentration in the hydrothermal plume sample gradually decreased with dilution and diffusion of the plume, DIC concentration in the caldera was higher than that in the seawater around the seamount. These results indicate that many chemical compounds discharged by hydrothermal activity have been remained in the caldera. According to the pH mapping of the hydrothermal area in the caldera, low pH areas in the patch state were located in each hydrothermal area. The low pH areas seem to have been formed by getting together with some hydrothermal plume. During long-term monitoring of pH at the hydrothermal active area in the caldera, the decreases of 0.3_`0.4pH in 24 hours periods correspond with the results of water current were detected.

  1. Catalytic Hydrothermal Gasification

    SciTech Connect

    Elliott, Douglas C.

    2015-05-31

    The term “hydrothermal” used here refers to the processing of biomass in water slurries at elevated temperature and pressure to facilitate the chemical conversion of the organic structures in biomass into useful fuels. The process is meant to provide a means for treating wet biomass materials without drying and to access ionic reaction conditions by maintaining a liquid water processing medium. Typical hydrothermal processing conditions are 523-647K of temperature and operating pressures from 4-22 MPa of pressure. The temperature is sufficient to initiate pyrolytic mechanisms in the biopolymers while the pressure is sufficient to maintain a liquid water processing phase. Hydrothermal gasification is accomplished at the upper end of the process temperature range. It can be considered an extension of the hydrothermal liquefaction mechanisms that begin at the lowest hydrothermal conditions with subsequent decomposition of biopolymer fragments formed in liquefaction to smaller molecules and eventually to gas. Typically, hydrothermal gasification requires an active catalyst to accomplish reasonable rates of gas formation from biomass.

  2. Kinetics of the alkaline hydrolysis of nitrocellulose.

    PubMed

    Christodoulatos, C; Su, T L; Koutsospyros, A

    2001-01-01

    Cellulose nitrate (nitrocellulose) is an explosive solid substance used in large quantities in various formulations of rocket and gun propellants. Safe destruction of nitrocellulose can be achieved by alkaline hydrolysis, which converts it to biodegradable products that can then be treated by conventional biological processes. The kinetics of the alkaline hydrolysis of munitions-grade nitrocellulose in sodium hydroxide solutions were investigated in completely mixed batch reactors. Experiments were conducted using solutions of alkaline strength ranging from 0.1 to 15% by mass and temperatures in the range of 30 to 90 degrees C. Regression analysis of the kinetic data revealed that alkaline hydrolysis of nitrocellulose is of the order 1.0 and 1.5 with respect to nitrocellulose and hydroxide concentration, respectively. The activation energy of the hydrolysis reaction was found to be 100.9 kJ/mol with a preexponential Arrhenius constant of 4.73 x 10(13). Nitrite and nitrate, in a 3:1 ratio, were the primary nitrogen species present in the posthydrolysis solution. The kinetic information is pertinent to the development and optimization of nitrocellulose chemical-biological treatment systems.

  3. The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

    SciTech Connect

    Mayanovic, R.A.; Anderson, A.J.; Bassett, W.A.; Chou, I.-M.

    2009-02-04

    X-ray absorption spectroscopy (XAS) measurements were made at the Nd L{sub 3}-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500 C and up to 520 MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07 m Nd/0.16 m HNO{sub 3} aqueous solution reveals a contraction of the Nd-O distance of the Nd{sup 3+} aqua ion at a uniform rate of {approx} 0.013 {angstrom}/100 C and a uniform reduction of the number of coordinated H{sub 2}O molecules from 10.0 {+-} 0.9 to 7.4 {+-} 0.9 over the range from 25 to 500 C and up to 370 MPa. The rate of reduction of the first-shell water molecules with temperature for Nd{sup 3+} (26%) is intermediate between the rate for the Gd{sup 3+} aqua ion (22% from 25 to 500 C) and the rates for the Eu{sup 3+} (29% from 25 to 400 C) and the Yb{sup 3+} aqua ions (42% from 25 to 500 C) indicating an intermediate stability of the Nd{sup 3+} aqua ion consistent with the tetrad effect. Nd L{sub 3}-edge XAS measurements of 0.05 m NdCl{sub 3} aqueous solution at 25 to 500 C and up to 520 MPa show that stepwise inner-sphere complexes most likely of the type Nd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} occur in the solution at elevated temperatures, where {delta} {approx} 9 at 150 C decreasing to {approx} 6 at 500 C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 {+-} 0.2 to 2.0 {+-} 0.2 in the solution upon increase of temperature from 150 to 500 C. Conversely, the number of H{sub 2}O ligands of Nd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} complexes is uniformly reduced with temperature from 7.5 {+-} 0.8 to 3.7 {+-} 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than

  4. pH-specific hydrothermal assembly of binary and ternary Pb(II)-(O,N-carboxylic acid) metal organic framework compounds: correlation of aqueous solution speciation with variable dimensionality solid-state lattice architecture and spectroscopic signatures.

    PubMed

    Gabriel, C; Perikli, M; Raptopoulou, C P; Terzis, A; Psycharis, V; Mateescu, C; Jakusch, T; Kiss, T; Bertmer, M; Salifoglou, A

    2012-09-03

    Hydrothermal pH-specific reactivity in the binary/ternary systems of Pb(II) with the carboxylic acids N-hydroxyethyl-iminodiacetic acid (Heida), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined crystalline compounds [Pb(Heida)](n)·nH(2)O(1), [Pb(Phen)(Heida)]·4H(2)O(2), and [Pb(3)(NO(3))(Dpot)](n)(3). All compounds were characterized by elemental analysis, FT-IR, solution or/and solid-state NMR, and single-crystal X-ray diffraction. The structures in 1-2 reveal the presence of a Pb(II) center coordinated to one Heida ligand, with 1 exhibiting a two-dimensional (2D) lattice extending to a three-dimensional (3D) one through H-bonding interactions. The concurrent aqueous speciation study of the binary Pb(II)-Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb(II)-Heida/Phen systems. The involvement of Phen in 2 projects the significance of nature and reactivity potential of N-aromatic chelators, disrupting the binary lattice in 1 and influencing the nature of the ultimately arising ternary 3D lattice. 3 is a ternary coordination polymer, where Pb(II)-Dpot coordination leads to a 2D metal-organic-framework material with unique architecture. The collective physicochemical properties of 1-3 formulate the salient features of variable dimensionality metal-organic-framework lattices in binary/ternary Pb(II)-(hydroxy-carboxylate) structures, based on which new Pb(II) materials with distinct architecture and spectroscopic signature can be rationally designed and pursued synthetically.

  5. Alkaline flooding injection strategy

    SciTech Connect

    French, T.R.; Josephson, C.B.

    1992-03-01

    The objective of this project is to improved alkali-surfactant flooding methods, and this includes determining the proper design of injection strategy. Several different injection strategies have been used or suggested for recovering heavy oils with surfactant-enhanced alkaline flooding methods. Oil recovery was compared for four different injection strategies: (1) surfactant followed by polymer, (2) surfactant followed by alkaline polymer, (3) alkaline surfactant followed by polymer, and (4) alkali, surfactant, and polymer mixed in a single formulation. The effect of alkaline preflush was also studied under two different conditions. All of the oil recovery experiments were conducted under optimal conditions with a viscous, non-acidic oil from Hepler (KS) oil field. The coreflood experiments were conducted with Berea sandstone cores since field core was not available in sufficient quantity for coreflood tests. The Tucker sand of Hepler field is a Class I fluvial dominated deltaic reservoir, as classified by the Department of Energy, which has been selected as the site of a DOE-sponsored field pilot test.

  6. Recent progress in hydrothermal synthesis of zinc oxide nanomaterials.

    PubMed

    Djurisic, A B; Chen, X Y; Leung, Y H

    2012-06-01

    Hydrothermal synthesis is of considerable interest due to its low cost, simplicity and relatively low growth temperature (typically below 200 °C). Since the synthesis is performed in aqueous solutions (no organic solvents), it can also be safe and environmentally friendly (depending on precursor chemicals). Consequently, it has been a subject of intense research in recent years. In this article, we review recent progress in hydrothermal synthesis of zinc oxide nanomaterials, with focus on practical relevance for a variety of applications.

  7. Hyperbaric hydrothermal atomic force microscope

    DOEpatents

    Knauss, Kevin G.; Boro, Carl O.; Higgins, Steven R.; Eggleston, Carrick M.

    2002-01-01

    A hyperbaric hydrothermal atomic force microscope (AFM) is provided to image solid surfaces in fluids, either liquid or gas, at pressures greater than normal atmospheric pressure. The sample can be heated and its surface imaged in aqueous solution at temperatures greater than 100.degree. C. with less than 1 nm vertical resolution. A gas pressurized microscope base chamber houses the stepper motor and piezoelectric scanner. A chemically inert, flexible membrane separates this base chamber from the sample cell environment and constrains a high temperature, pressurized liquid or gas in the sample cell while allowing movement of the scanner. The sample cell is designed for continuous flow of liquid or gas through the sample environment.

  8. Hyperbaric Hydrothermal Atomic Force Microscope

    DOEpatents

    Knauss, Kevin G.; Boro, Carl O.; Higgins, Steven R.; Eggleston, Carrick M.

    2003-07-01

    A hyperbaric hydrothermal atomic force microscope (AFM) is provided to image solid surfaces in fluids, either liquid or gas, at pressures greater than normal atmospheric pressure. The sample can be heated and its surface imaged in aqueous solution at temperatures greater than 100.degree. C. with less than 1 nm vertical resolution. A gas pressurized microscope base chamber houses the stepper motor and piezoelectric scanner. A chemically inert, flexible membrane separates this base chamber from the sample cell environment and constrains a high temperature, pressurized liquid or gas in the sample cell while allowing movement of the scanner. The sample cell is designed for continuous flow of liquid or gas through the sample environment.

  9. The Lassen hydrothermal system

    USGS Publications Warehouse

    Ingebritsen, Steven E.; Bergfeld, Deborah; Clor, Laura; Evans, William C.

    2016-01-01

    The active Lassen hydrothermal system includes a central vapor-dominated zone or zones beneath the Lassen highlands underlain by ~240 °C high-chloride waters that discharge at lower elevations. It is the best-exposed and largest hydrothermal system in the Cascade Range, discharging 41 ± 10 kg/s of steam (~115 MW) and 23 ± 2 kg/s of high-chloride waters (~27 MW). The Lassen system accounts for a full 1/3 of the total high-temperature hydrothermal heat discharge in the U.S. Cascades (140/400 MW). Hydrothermal heat discharge of ~140 MW can be supported by crystallization and cooling of silicic magma at a rate of ~2400 km3/Ma, and the ongoing rates of heat and magmatic CO2 discharge are broadly consistent with a petrologic model for basalt-driven magmatic evolution. The clustering of observed seismicity at ~4–5 km depth may define zones of thermal cracking where the hydrothermal system mines heat from near-plastic rock. If so, the combined areal extent of the primary heat-transfer zones is ~5 km2, the average conductive heat flux over that area is >25 W/m2, and the conductive-boundary length <50 m. Observational records of hydrothermal discharge are likely too short to document long-term transients, whether they are intrinsic to the system or owe to various geologic events such as the eruption of Lassen Peak at 27 ka, deglaciation beginning ~18 ka, the eruptions of Chaos Crags at 1.1 ka, or the minor 1914–1917 eruption at the summit of Lassen Peak. However, there is a rich record of intermittent hydrothermal measurement over the past several decades and more-frequent measurement 2009–present. These data reveal sensitivity to climate and weather conditions, seasonal variability that owes to interaction with the shallow hydrologic system, and a transient 1.5- to twofold increase in high-chloride discharge in response to an earthquake swarm in mid-November 2014.

  10. Hydrothermal mineralization at seafloor spreading centers

    NASA Astrophysics Data System (ADS)

    Rona, Peter A.

    1984-01-01

    The recent recognition that metallic mineral deposits are concentrated by hydrothermal processes at seafloor spreading centers constitutes a scientific breakthrough that opens active sites at seafloor spreading centers as natural laboratories to investigate ore-forming processes of such economically useful deposits as massive sulfides in volcanogenic rocks on land, and that enhances the metallic mineral potential of oceanic crust covering two-thirds of the Earth both beneath ocean basins and exposed on land in ophiolite belts. This paper reviews our knowledge of processes of hydrothermal mineralization and the occurrence and distribution of hydrothermal mineral deposits at the global oceanic ridge-rift system. Sub-seafloor hydrothermal convection involving circulation of seawater through fractured rocks of oceanic crust driven by heat supplied by generation of new lithosphere is nearly ubiquitous at seafloor spreading centers. However, ore-forming hydrothermal systems are extremely localized where conditions of anomalously high thermal gradients and permeability increase hydrothermal activity from the ubiquitous low-intensity background level (⩽ 200°C) to high-intensity characterized by high temperatures ( > 200-c.400°C), and a rate and volume of flow sufficient to sustain chemical reactions that produce acid, reducing, metal-rich primary hydrothermal solutions. A series of mineral phases with sulfides and oxides as high- and low-temperature end members, respectively, are precipitated along the upwelling limb and in the discharge zone of single-phase systems as a function of increasing admixture of normal seawater. The occurrence of hydrothermal mineral deposits is considered in terms of spatial and temporal frames of reference. Spatial frames of reference comprise structural features along-axis (linear sections that are the loci of seafloor spreading alternating with transform faults) and perpendicular to axis (axial zone of volcanic extrusion and marginal

  11. Novel molecular fossils of bacteria: insights into hydrothermal origin of life.

    PubMed

    Dai, Jianghong

    2012-10-07

    Hydrothermal vents, in particular, alkaline submarine vents, are potential systems for the origin of life. Early hydrothermal vents may have imprinted on biochemical processes and housekeeping proteins of life and have hallmarked key molecules. This essay introduces new information to this discussion by focusing on newly identified sulfur-modified DNA and a heretofore ignored anhydro bond of the cell wall peptidoglycan in bacteria. It is suggested that they are novel molecular fossils that are relevant to the settings of alkaline submarine vents and harbor clues of early life. As DNA and the cell wall are bound up with genetic information and the integrity of cell, respectively, these two molecular fossils may provide insights into hydrothermal origin of life from a new angle.

  12. Alkaline quinone flow battery.

    PubMed

    Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

    2015-09-25

    Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.

  13. Peptide synthesis under Enceladus hydrothermal condition

    NASA Astrophysics Data System (ADS)

    Fujishima, Kosuke; Takano, Yoshinori; Takai, Ken; Takahagi, Wataru; Adachi, Keito; Shibuya, Takazo; Tomita, Masaru

    2016-07-01

    Enceladus is one of the moons of Saturn, and it has been known to harbor interior ocean beneath the icy crust. The mass spectrometry data obtained by Cassini spacecraft indicates the presence of salty, and most likely alkaline ocean containing various organic compounds. While geochemical and other radiation related processes for in situ production of organics remain elusive, thermally unaltered carbonaceous chondrites, consisting the main body of Enceladus are known to be enriched with organic matters potentially including the building blocks of life (e.g., amino acids and amino acid precursors). Assuming that abiotic amino acids exist in the Enceladus alkaline seawater, we hypothesized that water-rock interaction may contribute to condensation of localized amino acids leading to peptide formation. In order to test this hypothesis, we have developed the Enceladus hydrothermal reactor based on the chemical constraints obtained through previous experimental and theoretical studies. We have added six different amino acids and introduced a thermal fluctuation system simulating the periodic tidal heating of the interior chondritic core. Total, eight sea water samples were obtained over the course of 147 days of experiment. While detection of peptide using Capillary Electrophoresis Time-of-Flight Mass Spectrometry (CE-TOF/MS) is still at the preliminary stage, so far pH monitoring and H2 and CO2 Gas Chromatography Mass Spectrometry (GC-MS) data clearly indicated the occurrence of serpentinization/carbonation reaction. Here, we discuss the interaction between aqueous alteration reactions and thermal cycling processes for the role of abiotic peptide formation under the Enceladus hydrothermal condition.

  14. Hydrothermal reactions of fly ash. Final report

    SciTech Connect

    Brown, P.W.

    1995-12-31

    The emphasis of the work done has been to determine the reactivities of two ashes believed to be representative of those generated. A bituminous ash and a lignitic ash have been investigated. The reactions of these ashes undergo when subjected to mild hydrothermal conditions were explored. The nature of the reactions which the ashes undergo when alkaline activators, calcium hydroxide and calcium sulfate are present was also investigated. It was determined that calcium silicate hydrate, calcium aluminate hydrate, and the calcium sulfoaluminate hydrate ettringite form under these conditions. It appears 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}3CaSO{sub 4}{center_dot}32H{sub 2}O (ettringite) formation needs to be considered in ashes which contain significant amounts of sulfate. Therefore the stability region for ettringite was established. It was also determined that calcium silicate hydrate, exhibiting a high internal surface area, will readily form with hydrothermal treatment between 50{degrees} and 100{degrees}C. This phase is likely to have a significant capacity to take up heavy metals and oxyanions and this ability is being explored.

  15. Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor.

    PubMed

    Hu, Keshui; Xiao, Xin; Cao, Xiufang; Hao, Rong; Zuo, Xiaoxi; Zhang, Xiaojing; Nan, Junmin

    2011-08-30

    Titanate nanotube powders (TNTPs) with the twofold removal ability, i.e. adsorptive separation and photocatalytic degradation, are synthesized under hydrothermal conditions using metal Ti particles as a precursor in the concentrated alkaline solution, and their morphology, structure, adsorptive and photocatalytic properties are investigated. Under hydrothermal conditions, the titanate nanotubes (TNTs) with pore diameter of 3-4nm are produced on the surface of metal Ti particles, and stacked together to form three-dimensional (3D) network with porous structure. The TNTPs synthesized in the autoclave at 130°C for 24h exhibits a maximum adsorption capability of about 197mg g(-1) in the neutral methylene blue (MB) solution (40mg L(-1)) within 90min, the adsorption process can be described by pseudo second-order kinetics model. Especially, in comparison with the adsorptive and the photocatalytic processes are performed in turn, about 50min can be saved through synchronously utilizing the double removal ability of TNTPs when the removal ratio of MB approaches 95% in MB solution (40mg L(-1)) at a solid-liquid (S/L) ratio of 1:8 under ultraviolet (UV) light irradiation. These 3D TNTPs with the twofold removal properties and easier separation ability for recycling use show promising prospect for the treatment of dye pollutants from wastewaters in future industrial application.

  16. Synthesis of alpha'L-C2S cement from fly-ash using the hydrothermal method at low temperature and atmospheric pressure.

    PubMed

    Kacimi, Larbi; Cyr, Martin; Clastres, Pierre

    2010-09-15

    The objective of this study was the synthesis of alpha'(L)-C(2)S (Ca(2)SiO(4)) belite cement, starting from fly-ash of system CaO-SiO(2)-Al(2)O(3)-SO(3), and using the hydrothermal method in alkaline solution. The lime deficit in these ashes was compensated by the addition of slaked lime from lime bagging workshops. The hydrothermal treatment of the mixture was carried out in demineralized water, NaOH or KOH solution, continually stirred at a temperature below 100 degrees C and atmospheric pressure. The dehydration and calcination of the mixtures at temperatures between 800 and 1100 degrees C allowed alpha'(L)-C(2)S-rich cement to be obtained. The optimization of the synthesis parameters (temperature and time of stirring, pH of solution, temperature and duration of mixture burning) was also studied. The phase formation during various synthesis stages was studied by X-ray diffraction (XRD). Other techniques, such as SEM and EDX, were used to characterize the cement minerals. The results obtained showed that these ashes could form belite cement composed of only one dicalcium silicate phase (alpha'(L)-C(2)S).

  17. Hydrothermal synthesis of lutetium disilicate nanoparticles

    SciTech Connect

    Tang Xiaoping; Gao Yanfeng; Chen Hongfei; Luo Hongjie

    2012-04-15

    A simple, low-cost hydrothermal method was developed to synthesize irregular-and rod-shaped lutetium disilicate (Lu{sub 2}Si{sub 2}O{sub 7}) powders with sizes ranging from 71 to 340 nm. The synthesis temperature was 260 Degree-Sign C, which is nearly 1300 Degree-Sign C lower than that required for the solid-state reaction. The results indicated that both the hydrothermal temperature and pH values had great influences on the composition, crystalline phase and morphology of the powders. The formation mechanism, basic thermophysical properties, stability and anticorrosion properties of the Lu{sub 2}Si{sub 2}O{sub 7} powders were also investigated. The obtained powders possessed low thermal conductivity, a suitable thermal expansion coefficient (3.92-5.17 Multiplication-Sign 10{sup -6} K{sup -1}) with the silicon-based substrate and excellent thermal and structural stability. During hot corrosion testing, the surfaces of the samples appeared to react with the water and molten salt vapors, but no serious failure occurred. - Graphical abstract: An image for the as-prepared Lu{sub 2}Si{sub 2}O{sub 7} powders (left) and XRD pattern (right) (inset shows the SEM graph of powders). Highlights: Black-Right-Pointing-Pointer We synthesized Lu{sub 2}Si{sub 2}O{sub 7} powders via a hydrothermal process at 260 Degree-Sign C. Black-Right-Pointing-Pointer Crystalline phase and morphology of the powders changed with experimental parameter. Black-Right-Pointing-Pointer Hot corrosion was determined in an airflow environment containing alkaline vapor.

  18. Base hydrolysis and hydrothermal processing of PBX-9404 explosive

    SciTech Connect

    Sanchez, J.A.; Flesner, R.L.; Spontarelli, T.; Dell`Orco, P.C.; Kramer, J.F.

    1995-04-01

    Base hydrolysis in combination with hydrothermal processing has been proposed as an environmentally acceptable alternative to open burning/open detonation for degradation and destruction of high explosives. In this report, the authors examine gaseous and aqueous products of base hydrolysis of the HMX-based plastic bonded explosive, PBX-9404. The authors also examine products from the subsequent hydrothermal treatment of the base hydrolysate. The gases produced from hydrolysis of PBX-9404 are ammonia, nitrous oxide, and nitrogen. Major aqueous products are sodium formate, acetate, nitrate, and nitrite, but not all carbon products have been identified. Hydrothermal processing of base hydrolysate destroyed up to 98% of the organic carbon in solution, and higher destruction efficiencies are possible. Major gas products detected from hydrothermal processing were nitrogen and nitrous oxide.

  19. Hydrothermal reactivity of saponite.

    USGS Publications Warehouse

    Whitney, G.

    1983-01-01

    The nature and extent of the reactions of synthetic Fe-free saponite have been investigated under experimental hydrothermal conditions as a first step towards understanding saponite reactivity under relatively simple conditions. Saponite crystallizes from amorphous gel of ideal saponite composition within 7 days at 300o-550oC under P = 1 kbar. Reactions subsequent to this initial crystallization depend on reaction T and interlayer cations. Saponite is found to react hydrothermally, over a period of 200 days, at T down to 400oC, at least 150oC lower than previously reported, but showed no signs of reaction below 400oC. At 450oC, a mixture of talc/saponite and saponite/phlogopite clays forms from K-saponite via intracrystalline layer transformations, while above 450oC the initial K-saponite dissolves, with talc and phlogopite forming as discrete phases. After 200 days reactions at 400-450oC were not complete, so that given sufficient time to reach equilibrium, a lower hydrothermal stability limit for saponite is possible. Further study of the Fe-bearing saponite system will be required before experimental results can be applied to natural systems.-D.F.B.

  20. The onset of life in a natural submarine hydrothermal fractionation reactor

    NASA Astrophysics Data System (ADS)

    Russell, M. J.; Martin, W.

    There was a strong disequilibrium between the carbon dioxide in the early atmosphere and hydrothermal hydrogen. Such a disequilibrium tends to increase at lower temperatures but so do the kinetic barriers to reaction. Ignoring these kinetic barriers the strongest thermodynamic drive is to the production of methane as carbon dioxide reacts with hydrogen. But kinetic barriers prevent this reaction below 500C. In its stead Shock et al. (1998) demonstrate that metastable acetate is overwhelmingly the best represented carbon compound produced theoretically on the mixing of hydrothermal solution with seawater between 10 and 65C. The minor sticky by-product of this reaction, which involves other reactants, can be considered as evolving to protolife. Thus we argue that the organic building modules of life could be generated from the simplest entities within the hydrothermal mound. And the main waste products would be acetate and water: {407H2+10NH3+HS-hydroth'l +{210CO2+H2PO4- + [Fe,Ni,Co]2+ocean → gC70H129O65N10P(Fe,Ni,Co)Sprotolife+{70H3C.COOH+219H2Owaste We suggest that protolife emerged at ˜ 40C where chemical gradients were steep in a hydrothermal mound which developed where alkaline waters seeped into the Hadean ocean. The mound acted as a fractionation reactor. Reactions were catalysed by such sulfide clusters as would produce greigite (NiFe5S8) in membranes also composed of sulfides (Martin and Russell 2003). A greigite cluster was the precursor to the active sites of carbon monoxide dehydrogenase (NiFe4S5) and acetyl coenzyme-A synthase ([Fe4S4]cysNicys2Ni) (Svetlitchnyi et al. 2004). Activation energy was supplied by reaction between photolytic ferric iron and H2 across the membranes comprising FeS compartments at the mound's surface. Small quantities of amino acids, metal-bearing clusters (Milner-White and Russell 2004), and eventually RNA precursors, self-organised to become involved in the more efficient generation of acetate waste, a thermodynamic

  1. Energetics of amino acid synthesis in hydrothermal ecosystems

    NASA Technical Reports Server (NTRS)

    Amend, J. P.; Shock, E. L.

    1998-01-01

    Thermodynamic calculations showed that the autotrophic synthesis of all 20 protein-forming amino acids was energetically favored in hot (100 degrees C), moderately reduced, submarine hydrothermal solutions relative to the synthesis in cold (18 degrees C), oxidized, surface seawater. The net synthesis reactions of 11 amino acids were exergonic in the hydrothermal solution, but all were endergonic in surface seawater. The synthesis of the requisite amino acids of nine thermophilic and hyperthermophilic proteins in a 100 degreesC hydrothermal solution yielded between 600 and 8000 kilojoules per mole of protein, which is energy that is available to drive the intracellular synthesis of enzymes and other biopolymers in hyperthermophiles thriving in these ecosystems.

  2. Numerical simulation of magmatic hydrothermal systems

    USGS Publications Warehouse

    Ingebritsen, S.E.; Geiger, S.; Hurwitz, S.; Driesner, T.

    2010-01-01

    The dynamic behavior of magmatic hydrothermal systems entails coupled and nonlinear multiphase flow, heat and solute transport, and deformation in highly heterogeneous media. Thus, quantitative analysis of these systems depends mainly on numerical solution of coupled partial differential equations and complementary equations of state (EOS). The past 2 decades have seen steady growth of computational power and the development of numerical models that have eliminated or minimized the need for various simplifying assumptions. Considerable heuristic insight has been gained from process-oriented numerical modeling. Recent modeling efforts employing relatively complete EOS and accurate transport calculations have revealed dynamic behavior that was damped by linearized, less accurate models, including fluid property control of hydrothermal plume temperatures and three-dimensional geometries. Other recent modeling results have further elucidated the controlling role of permeability structure and revealed the potential for significant hydrothermally driven deformation. Key areas for future reSearch include incorporation of accurate EOS for the complete H2O-NaCl-CO2 system, more realistic treatment of material heterogeneity in space and time, realistic description of large-scale relative permeability behavior, and intercode benchmarking comparisons. Copyright 2010 by the American Geophysical Union.

  3. Hydrothermal synthesis of nanostructured manganese oxide as cathodic catalyst in a microbial fuel cell fed with leachate.

    PubMed

    Haoran, Yuan; Lifang, Deng; Tao, Lu; Yong, Chen

    2014-01-01

    Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM) was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM), accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m(2) was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment.

  4. Hydrothermal Synthesis of Nanostructured Manganese Oxide as Cathodic Catalyst in a Microbial Fuel Cell Fed with Leachate

    PubMed Central

    Haoran, Yuan; Lifang, Deng; Tao, Lu; Yong, Chen

    2014-01-01

    Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM) was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM), accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m2 was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment. PMID:24723824

  5. Rational synthesis of multifunctional mixed metal oxides by hydrothermal techniques

    NASA Astrophysics Data System (ADS)

    Stampler, Evan Scott

    Low temperature (<350°C) and pressure (<20 atm) hydrothermal methods have been developed for the synthesis of bismuth copper oxide chalcogenides, hexagonal rare-earth manganites, and silver delafossites with mixed cations on the B-site. These materials are of particular interest because they combine multiple functional properties, such as transparency and conductivity, or magnetism and ferroelectricity, in a single-phase material, thus enabling innovative technological applications. Phase-pure products were achieved by the appropriate combination of starting reagents, pH, and reaction temperature to control the solubility of the reactants. Phase-pure BiCuOS and BiCuOSe have been synthesized in high yield by a single-step hydrothermal reaction at low temperature (250°C) and pressure (< 20 atm). A reaction temperature of 250°C was sufficiently high to solubilize both Bi2O3 ([Bi3+] ≈ 10 -3 M) and Cu2O ([Cu+] ≈ 10-4 M) and stabilize monovalent copper species in solution, yet remains low enough to prevent the oxidation of sulfide and selenide. BiCuOS (Eg = 1.09 eV) and BiCuOSe (Eg = 0.75 eV) have smaller band gaps compared to the p-type transparent conductor LaCuOS (Eg = 3.1 eV) but have significantly higher room temperature conductivities (sigma ≈ 0.08 S cm-1 and 3.3 S cm-1, respectively). The high molar solubility of Mn2O3 ([Mn 3+] ≈ 10-3 M) and the slightly amphoteric character of the late rare-earth sesquioxides were exploited in the hydrothermal synthesis of rare-earth manganites, LnMnO3 (Ln=Ho-Lu and Y). While alkaline conditions were necessary for the solubilization of manganese, a reaction temperature approximately 50°C above the transition temperature of the respective rare-earth trihydroxide (100-300°C) accelerated the transition to the more reactive and soluble rare-earth oxide hydroxide and the subsequent reaction to yield the LnMnO3 phase. The high solubility of Ag2O, [Ag+] ≈ 10 -2.5 M, enabled the synthesis of two new silver delafossite

  6. Hydrothermal mixing: Fuel for life in the deep-sea

    NASA Astrophysics Data System (ADS)

    Hentscher, M.; Bach, W.; Amend, J.; McCollom, T.

    2009-04-01

    Deep-sea hydrothermal vent systems show a wide range of fluid compositions and temperatures. They reach from highly alkaline and reducing, like the Lost City hydrothermal field, to acidic and reducing conditions, (e. g., the Logatchev hydrothermal field) to acidic and oxidizing conditions (e. g., island arc hosted systems). These apparently hostile vent systems are generally accompanied by high microbial activity forming the base of a food-web that often includes higher organisms like mussels, snails, or shrimp. The primary production is boosted by mixing of chemically reduced hydrothermal vent fluids with ambient seawater, which generates redox disequilibria that serve as energy source for chemolithoautotrophic microbial life. We used geochemical reaction path models to compute the affinities of catabolic (energy-harvesting) and anabolic (biosynthesis) reactions along trajectories of batch mixing between vent fluids and 2 °C seawater. Geochemical data of endmember hydrothermal fluids from 12 different vent fields (Lost City, Rainbow, Logatchev, TAG, EPR 21 °N, Manus Basin, Mariana Arc, etc.) were included in this reconnaissance study of the variability in metabolic energetics in global submarine vent systems. The results show a distinction between ultramafic-hosted and basalt-hosted hydrothermal systems. The highest energy yield for chemolithotrophic catabolism in ultramafic-hosted hydrothermal systems is reached at low temperature and under slightly aerobic to aerobic conditions. The dominant reactions, for example at Rainbow or Lost City, are the oxidation of H2, Fe2+ and methane. At temperatures >60 °C, anaerobic metabolic reactions, e. g., sulphate reduction and methanogenesis, become more profitable. In contrast, basalt-hosted systems, such as TAG and 21 °N EPR uniformly indicate H2S oxidation to be the catabolically dominant reaction over the entire microbial-relevant temperature range. Affinities were calculated for the formation of individual cellular

  7. Lead recovery from scrap cathode ray tube funnel glass by hydrothermal sulphidisation.

    PubMed

    Yuan, Wenyi; Meng, Wen; Li, Jinhui; Zhang, Chenglong; Song, Qingbin; Bai, Jianfeng; Wang, Jingwei; Li, Yingshun

    2015-10-01

    This research focused on the application of the hydrothermal sulphidisation method to separate lead from scrap cathode ray tube funnel glass. Prior to hydrothermal treatment, the cathode ray tube funnel glass was pretreated by mechanical activation. Under hydrothermal conditions, hydroxyl ions (OH(-)) were generated through an ion exchange reaction between metal ions in mechanically activated funnel glass and water, to accelerate sulphur disproportionation; no additional alkaline compound was needed. Lead contained in funnel glass was converted to lead sulphide with high efficiency. Temperature had a significant effect on the sulphidisation rate of lead in funnel glass, which increased from 25% to 90% as the temperature increased from 100 °C to 300 °C. A sulphidisation rate of 100% was achieved at a duration of 8 h at 300 °C. This process of mechanical activation and hydrothermal sulphidisation is efficient and promising for the treatment of leaded glass.

  8. Organic matter in hydrothermal metal ores and hydrothermal fluids

    USGS Publications Warehouse

    Orem, W.H.; Spiker, E. C.; Kotra, R.K.

    1990-01-01

    Massive polymetallic sulfides are currently being deposited around active submarine hydrothermal vents associated with spreading centers. Chemoautolithotrophic bacteria are responsible for the high production of organic matter also associated with modern submarine hydrothermal activity. Thus, there is a significant potential for organic matter/metal interactions in these systems. We have studied modern and ancient hydrothermal metal ores and modern hydrothermal fluids in order to establish the amounts and origin of the organic matter associated with the metal ores. Twenty-six samples from modern and ancient hydrothermal systems were surveyed for their total organic C contents. Organic C values ranged from 0.01% to nearly 4.0% in these samples. Metal ores from modern and ancient sediment-covered hydrothermal systems had higher organic C values than those from modern and ancient hydrothermal systems lacking appreciable sedimentary cover. One massive pyrite sample from the Galapagos spreading center (3% organic C) had stable isotope values of -27.4% (??13C) and 2.1% (??15N), similar to those in benthic siphonophors from active vents and distinct from seep sea sedimentary organic matter. This result coupled with other analyses (e.g. 13C NMR, pyrolysis/GC, SEM) of this and other samples suggests that much of the organic matter may originate from chemoautolithotrophic bacteria at the vents. However, the organic matter in hydrothermal metal ores from sediment covered vents probably arises from complex sedimentary organic matter by hydrothermal pyrolysis. The dissolved organic C concentrations of hydrothermal fluids from one site (Juan de Fuca Ridge) were found to be the same as that of background seawater. This result may indicate that dissolved organic C is effectively scavenged from hydrothermal fluids by biological activity or by co-precipitation with metal ores. ?? 1990.

  9. The hydrothermal reaction kinetics of aspartic acid

    NASA Astrophysics Data System (ADS)

    Cox, Jenny S.; Seward, Terry M.

    2007-02-01

    Experimental data on the hydrothermal reaction kinetics of aspartic acid were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. The results of this study indicate that the reaction kinetics of dilute aspartic acid solutions are significantly different depending on the presence or absence of catalytic surfaces such as standard metal alloys. The spectroscopic data presented here represent the first direct observations, in situ and in real time, of an amino acid reacting in a hydrothermal solution. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a chemometric approach based on factor analysis/principle component analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Identification of the products was confirmed where possible by high pressure anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The reaction kinetics of aspartic acid under hydrothermal conditions was observed to be highly complex, in contrast to previous studies which indicated almost exclusively deamination. At lower temperatures (120-170 °C), several different reaction pathways were observed, including decarboxylation and polymerization, and the catalytic effects of reactor surfaces on the aspartic acid system were clearly demonstrated. At higher temperatures (above 170 °C), aspartic acid exhibited highly complex behaviour, with evidence indicating that it can simultaneously dimerize and cyclize, deaminate (by up to two pathways), and decarboxylate (by up to two pathways). These higher temperature kinetics were not fully resolvable in a quantitative manner due to the complexity of the system and the constraints of UV spectroscopy. The results of this study provide strong evidence that the reaction

  10. Alkaline and ultrasound assisted alkaline pretreatment for intensification of delignification process from sustainable raw-material.

    PubMed

    Subhedar, Preeti B; Gogate, Parag R

    2014-01-01

    Alkaline and ultrasound-assisted alkaline pretreatment under mild operating conditions have been investigated for intensification of delignification. The effect of NaOH concentration, biomass loading, temperature, ultrasonic power and duty cycle on the delignification has been studied. Most favorable conditions for only alkaline pretreatment were alkali concentration of 1.75 N, solid loading of 0.8% (w/v), temperature of 353 K and pretreatment time of 6 h and under these conditions, 40.2% delignification was obtained. In case of ultrasound-assisted alkaline approach, most favorable conditions obtained were alkali concentration of 1N, paper loading of 0.5% (w/v), sonication power of 100 W, duty cycle of 80% and pretreatment time of 70 min and the delignification obtained in ultrasound-assisted alkaline approach under these conditions was 80%. The material samples were characterized by FTIR, SEM, XRD and TGA technique. The lignin was recovered from solution by precipitation method and was characterized by FTIR, GPC and TGA technique.

  11. A ubiquitous thermoacidophilic archaeon from deep-sea hydrothermal vents

    USGS Publications Warehouse

    Reysenbach, A.-L.; Liu, Yajing; Banta, A.B.; Beveridge, T.J.; Kirshtein, J.D.; Schouten, S.; Tivey, M.K.; Von Damm, Karen L.; Voytek, M.A.

    2006-01-01

    Deep-sea hydrothermal vents are important in global biogeochemical cycles, providing biological oases at the sea floor that are supported by the thermal and chemical flux from the Earth's interior. As hot, acidic and reduced hydrothermal fluids mix with cold, alkaline and oxygenated sea water, minerals precipitate to form porous sulphide-sulphate deposits. These structures provide microhabitats for a diversity of prokaryotes that exploit the geochemical and physical gradients in this dynamic ecosystem. It has been proposed that fluid pH in the actively venting sulphide structures is generally low (pH < 4.5), yet no extreme thermoacidophile has been isolated from vent deposits. Culture-independent surveys based on ribosomal RNA genes from deep-sea hydrothermal deposits have identified a widespread euryarchaeotal lineage, DHVE2 (deep-sea hydrothermal vent euryarchaeotic 2). Despite the ubiquity and apparent deep-sea endemism of DHVE2, cultivation of this group has been unsuccessful and thus its metabolism remains a mystery. Here we report the isolation and cultivation of a member of the DHVE2 group, which is an obligate thermoacidophilic sulphur- or iron-reducing heterotroph capable of growing from pH 3.3 to 5.8 and between 55 and 75??C. In addition, we demonstrate that this isolate constitutes up to 15% of the archaeal population, providing evidence that thermoacidophiles may be key players in the sulphur and iron cycling at deep-sea vents. ?? 2006 Nature Publishing Group.

  12. Hydrothermal Liquefaction of Biomass

    SciTech Connect

    Elliott, Douglas C.

    2010-12-10

    Hydrothermal liquefaction technology is describes in its relationship to fast pyrolysis of biomass. The scope of work at PNNL is discussed and some intial results are presented. HydroThermal Liquefaction (HTL), called high-pressure liquefaction in earlier years, is an alternative process for conversion of biomass into liquid products. Some experts consider it to be pyrolysis in solvent phase. It is typically performed at about 350 C and 200 atm pressure such that the water carrier for biomass slurry is maintained in a liquid phase, i.e. below super-critical conditions. In some applications catalysts and/or reducing gases have been added to the system with the expectation of producing higher yields of higher quality products. Slurry agents ('carriers') evaluated have included water, various hydrocarbon oils and recycled bio-oil. High-pressure pumping of biomass slurry has been a major limitation in the process development. Process research in this field faded away in the 1990s except for the HydroThermal Upgrading (HTU) effort in the Netherlands, but has new resurgence with other renewable fuels in light of the increased oil prices and climate change concerns. Research restarted at Pacific Northwest National Laboratory (PNNL) in 2007 with a project, 'HydroThermal Liquefaction of Agricultural and Biorefinery Residues' with partners Archer-Daniels-Midland Company and ConocoPhillips. Through bench-scale experimentation in a continuous-flow system this project investigated the bio-oil yield and quality that could be achieved from a range of biomass feedstocks and derivatives. The project was completed earlier this year with the issuance of the final report. HydroThermal Liquefaction research continues within the National Advanced Biofuels Consortium with the effort focused at PNNL. The bench-scale reactor is being used for conversion of lignocellulosic biomass including pine forest residue and corn stover. A complementary project is an international collaboration with

  13. Process of treating cellulosic membrane and alkaline with membrane separator

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1970-01-01

    The improvement of water-soluble cellulose ether membranes for use as separators in concentrated alkaline battery cells is discussed. The process of contacting membranes with an aqueous alkali solution of concentration less than that of the alkali solution to be used in the battery but above that at which the membrane is soluble is described.

  14. Does Hydrothermal Circulation Matter?

    NASA Astrophysics Data System (ADS)

    Stein, C. A.; Stein, S.; von Herzen, R. P.; Fisher, A. T.

    2006-05-01

    Determining Earth's energy budget and the sources and mechanisms for heat transfer within it depends largely on assumptions of the heat loss from the formation and cooling of oceanic lithosphere, which covers about 60% of Earth's surface. Recently Hofmeister and Criss (2005) have suggested that the total global heat flow is about 30 TW, about 25% less than previously estimated by Pollack et al. (1993). The main difference between the two estimates is whether the effects of heat transfer by hydrothermal circulation are included. Thermal models describe the evolution of the lithosphere by the conductive cooling of hot material as it moves away from spreading centers. The frequently used half-space (boundary layer) and "plate" models generally successfully represent heat flow, depth, and geoid values with age, and depth-dependent properties such as flexural thickness, maximum depth of intraplate earthquakes, and lithospheric thickness. However, such models overpredict the measured heat flow from ridge crest to about 65 Myr crust. This difference is generally assumed to reflect water flow in the crust transporting heat, as shown by the spectacular hot springs at midocean ridges. If so, the observed heat flow is lower than the model's predictions, which assume that all heat is transferred by conduction. Because hydrothermal heat transport is hard to quantify, heat flow is about 50% larger than directly measured. This estimate is consistent with observations of hydrothermal circulation which indicate that the discrepancy is largely a result of the water fluxing along the oceanic basement and upwelling at isolated basement highs and outcrops. Detailed studies at such areas often show high heat flow near these outcrops and low heat flow in the surrounding areas. Hence isolated measurements are biased towards lower values and underpredict the total heat flow.

  15. Modelling magmatic gas scrubbing in hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Di Napoli, Rossella; Aiuppa, Alessandro; Valenza, Mariano; Bergsson, Baldur; Ilyinskaya, Evgenia; Pfeffer, Melissa Anne; Rakel Guðjónsdóttir, Sylvía

    2015-04-01

    In volcano-hosted hydrothermal systems, the chemistry of deeply rising magmatic gases is extensively modified by gas-water-rock interactions taking place within the hydrothermal reservoir, and/or at shallow groundwaters conditions. These reactions can scrub reactive, water-soluble species (S, halogens) from the magmatic gas phase, so that their quantitative assessment is central to understanding the chemistry of surface gas manifestations, and brings profound implications to the interpretation of volcanic-hydrothermal unrests. Here, we present the results of numerical simulations of magmatic gas scrubbing, in which the reaction path modelling approach (Helgeson, 1968) is used to reproduce hydrothermal gas-water-rock interactions at both shallow (temperature up to 109°C; low-T model runs) and deep reservoir (temperature range: 150-250 °C; high-T model runs) conditions. The model was built based upon the EQ3/6 software package (Wolery and Daveler, 1992), and consisted into a step by step addition of a high-temperature magmatic gas to an initial meteoric water, in the presence of a dissolving aquifer rock. The model outputted, at each step of gas addition, the chemical composition of a new aqueous solution formed after gas-water-rock interactions; which, upon reaching gas over-pressuring (PgasTOT > Psat(H2O) at run T), is degassed (by single-step degassing) to separate a scrubbed gas phase. As an application of the model results, the model compositions of the separated gases are finally compared with compositions of natural gas emissions from Hekla volcano (T< 100°C) and from Krisuvik geothermal system (T> 100°C), resulting into an excellent agreement. The compositions of the model solutions are also in fair agreement with compositions of natural thermal water samples. We conclude that our EQ3/6-based reaction path simulations offer a realistic representation of gas-water-rock interaction processes occurring underneath active magmatic-hydrothermal systems

  16. Abiotic Organic Chemistry in Hydrothermal Systems.

    NASA Astrophysics Data System (ADS)

    Simoneit, B. R.; Rushdi, A. I.

    2004-12-01

    Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

  17. Refractory Organic Compounds in Enceladus' Ice Grains and Hydrothermal Activity

    NASA Astrophysics Data System (ADS)

    Postberg, F.; Khawaja, N.; Hsu, H. W.; Sekine, Y.; Shibuya, T.

    2015-12-01

    Cassini's Cosmic Dust Analyzer (CDA) generates time-of-flight mass spectra of individual grains impinging on the instruments target-plate. Following the analysis of salt rich ice grains emitted by Enceladus that indicated a salt-water ocean in contact with the moon's rocky core [1,2] a recent CDA analysis of nano-phase silica particles pointed at hydrothermal activity at the moon's rock/water interface [3]. The results imply temperatures above 80 - 90°C and alkaline pH values around 10 reminiscent of alkaline hydrothermal vents on Earth like the Lost City Hydrothermal Field. In this context the compositional analysis of organic components in CDA mass spectra of the ejected ice grains is of particular relevance. A multitude of volatile organic species has already been identified in the gas component of the plume [4]. As expected, we find more complex organic molecules in ice grains than in the gas indicating aromatic species, amines, and carbonyl group species. The composition of organic-bearing ice grains displays a great diversity indicating a variety of different organic species in varying concentrations. Recent spatially resolved CDA in situ measurements inside Enceladus' plume indicate that these organic compounds are especially frequent in 'young' ice grains that have just been ejected by high velocity jets. We investigate the implications of our findings with respect to ice grain formation at the water surface and inside the icy vents. We constrain the generation of organic compounds at the rock/water interface in the light of hydrothermal activity and the potential for the formation of life precursor molecules in Enceladus' ocean. Ref:[1] Postberg et al., Nature 459, 1098-1101 (2009). [2] Postberg et al., Nature 474, 620-622 (2011). [3]. Hsu, Postberg, Sekine et al., Nature, 519, 207-210 (2015). [4] Waite et al., Nature 460, 487-490 (2009).

  18. Cody hydrothermal system

    SciTech Connect

    Heasler, H.P.

    1982-01-01

    The hot springs of Colter's Hell are the surface manifestations of a much larger hydothermal system. That system has been studied to define its extent, maximum temperature, and mechanism of operation. The study area covers 2700 km/sup 2/ (1040 mi/sup 2/) in northwest Wyoming. Research and field work included locating and sampling the hot springs, geologic mapping, thermal logging of available wells, measuring thermal conductivities, analyzing over 200 oil and gas well bottom-hole temperatures, and compiling and analyzing hydrologic data. These data were used to generate a model for the hydrothermal system.

  19. Enceladus: Starting Hydrothermal Activity

    NASA Technical Reports Server (NTRS)

    Matson, D. L.; Castillo-Rogez, J. C.; Johnson, T. V.; Lunine, J. I.; Davies, A. G.

    2011-01-01

    We describe a process for starting the hydrothermal activity in Enceladus' South Polar Region. The process takes advantage of fissures that reach the water table, about 1 kilometer below the surface. Filling these fissures with fresh ocean water initiates a flow of water up from an ocean that can be self-sustaining. In this hypothesis the heat to sustain the thermal anomalies and the plumes comes from a slightly warm ocean at depth. The heat is brought to the surface by water that circulates up, through the crust and then returns to the ocean.

  20. Metal concentrations in the tissues of the hydrothermal vent mussel Bathymodiolus: reflection of different metal sources.

    PubMed

    Koschinsky, Andrea; Kausch, Matteo; Borowski, Christian

    2014-04-01

    Hydrothermal vent mussels of the genus Bathymodiolus are ideally positioned for the use of recording hydrothermal fluxes at the hydrothermal vent sites they inhabit. Barium, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Pb, Sr, and U concentrations in tissue sections of Bathymodiolus mussels from several hydrothermal fields between 15°N and 9°S at the Mid-Atlantic Ridge were determined and compared to the surrounding fluids and solid substrates in the habitats. Elements generally enriched in hydrothermal fluids, such as Fe, Cu, Zn, Pb and Cd, were significantly enriched in the gills and digestive glands of the hydrothermal mussels. The rather small variability of Zn (and Mn) and positive correlation with K and earth alkaline metals may indicate a biological regulation of accumulation. Enrichments of Mo and U in many tissue samples indicate that particulate matter such as hydrothermal mineral particles from the plumes can play a more important role as a metal source than dissolved metals. Highest enrichments of Cu in mussels from the Golden Valley site indicate a relation to the ≥400 °C hot heavy-metal rich fluids emanating in the vicinity. In contrast, mussels from the low-temperature Lilliput field are affected by the Fe oxyhydroxide sediment of their habitat. In a comparison of two different sites within the Logatchev field metal distributions in the tissues reflected small-scale local variations in the metal content of the fluids and the particulate material.

  1. Impact-generated hydrothermal systems on Earth and Mars

    NASA Astrophysics Data System (ADS)

    Osinski, Gordon R.; Tornabene, Livio L.; Banerjee, Neil R.; Cockell, Charles S.; Flemming, Roberta; Izawa, Matthew R. M.; McCutcheon, Jenine; Parnell, John; Preston, Louisa J.; Pickersgill, Annemarie E.; Pontefract, Alexandra; Sapers, Haley M.; Southam, Gordon

    2013-06-01

    It has long been suggested that hydrothermal systems might have provided habitats for the origin and evolution of early life on Earth, and possibly other planets such as Mars. In this contribution we show that most impact events that result in the formation of complex impact craters (i.e., >2-4 and >5-10 km diameter on Earth and Mars, respectively) are potentially capable of generating a hydrothermal system. Consideration of the impact cratering record on Earth suggests that the presence of an impact crater lake is critical for determining the longevity and size of the hydrothermal system. We show that there are six main locations within and around impact craters on Earth where impact-generated hydrothermal deposits can form: (1) crater-fill impact melt rocks and melt-bearing breccias; (2) interior of central uplifts; (3) outer margin of central uplifts; (4) impact ejecta deposits; (5) crater rim region; and (6) post-impact crater lake sediments. We suggest that these six locations are applicable to Mars as well. Evidence for impact-generated hydrothermal alteration ranges from discrete vugs and veins to pervasive alteration depending on the setting and nature of the system. A variety of hydrothermal minerals have been documented in terrestrial impact structures and these can be grouped into three broad categories: (1) hydrothermally-altered target-rock assemblages; (2) primary hydrothermal minerals precipitated from solutions; and (3) secondary assemblages formed by the alteration of primary hydrothermal minerals. Target lithology and the origin of the hydrothermal fluids strongly influences the hydrothermal mineral assemblages formed in these post-impact hydrothermal systems. There is a growing body of evidence for impact-generated hydrothermal activity on Mars; although further detailed studies using high-resolution imagery and multispectral information are required. Such studies have only been done in detail for a handful of martian craters. The best example so

  2. Evidence for Hydrothermal Vents as "Biogeobatteries" (Invited)

    NASA Astrophysics Data System (ADS)

    Nielsen, M. E.; Girguis, P. R.

    2010-12-01

    Hydrothermal vents are unique systems that play an important role in oceanic biogeochemical cycles. As chemically reduced hydrothermal fluid mixes with cold oxic seawater, minerals precipitate out of solution resulting in chimney structures composed largely of metal sulfides and anhydrite. Pyrite, which is a natural semi-conductor, is the primary sulfide mineral, but other minerals within chimneys are also conductive (e.g. chalcopyrite, wurtzite, and some iron oxides). Sulfide chimneys are also known to host an extensive endolithic microbial community. Accordingly, submarine hydrothermal systems appear to be examples of biogeobatteries, wherein conductive mineral assemblages span naturally occuring redox gradients and enable anaerobic microbes to access oxygen as an oxidant via extracellular electron transfer (or EET). To test this hypothesis, we ran a series of electrochemical laboratory experiments in which pyrite was used as an anode (in a vessel flushed with hydrothermal-like fluid). When placed in continuity with a carbon fiber cathode, pyrite was found to accept and conduct electrons from both abiotic and biological processes (microbial EET). Specifically, electrical current increased 4-fold (5 nA/m2 to 20 nA/m2) in response to inoculation with a slurry prepared from a hydrothermal vent sample. Inspection of the pyrite anode with SEM revealed ubiquitous coverage by microbes. DNA was extracted from the anodes and the inoculum, and was subjected to pyrosequencing to examine prokaryotic diversity. These data suggest that key microbial phylotypes were enriched upon the pyrite, implicating them in EET. In addition, we deployed an in situ experiment based on microbial fuel cell architecture with a graphite anode inserted into a vent wall coupled to a carbon fiber cathode outside the vent. We observed current production over the course of one year, implying microbial EET in situ. Via pyrosequencing, we observed that the microbial community on the anode was

  3. Hydrothermal processes above the Yellowstone magma chamber: Large hydrothermal systems and large hydrothermal explosions

    USGS Publications Warehouse

    Morgan, L.A.; Shanks, W.C. Pat; Pierce, K.L.

    2009-01-01

    Hydrothermal explosions are violent and dramatic events resulting in the rapid ejection of boiling water, steam, mud, and rock fragments from source craters that range from a few meters up to more than 2 km in diameter; associated breccia can be emplaced as much as 3 to 4 km from the largest craters. Hydrothermal explosions occur where shallow interconnected reservoirs of steam- and liquid-saturated fluids with temperatures at or near the boiling curve underlie thermal fields. Sudden reduction in confi ning pressure causes fluids to fl ash to steam, resulting in signifi cant expansion, rock fragmentation, and debris ejection. In Yellowstone, hydrothermal explosions are a potentially signifi cant hazard for visitors and facilities and can damage or even destroy thermal features. The breccia deposits and associated craters formed from hydrothermal explosions are mapped as mostly Holocene (the Mary Bay deposit is older) units throughout Yellowstone National Park (YNP) and are spatially related to within the 0.64-Ma Yellowstone caldera and along the active Norris-Mammoth tectonic corridor. In Yellowstone, at least 20 large (>100 m in diameter) hydrothermal explosion craters have been identifi ed; the scale of the individual associated events dwarfs similar features in geothermal areas elsewhere in the world. Large hydrothermal explosions in Yellowstone have occurred over the past 16 ka averaging ??1 every 700 yr; similar events are likely in the future. Our studies of large hydrothermal explosion events indicate: (1) none are directly associated with eruptive volcanic or shallow intrusive events; (2) several historical explosions have been triggered by seismic events; (3) lithic clasts and comingled matrix material that form hydrothermal explosion deposits are extensively altered, indicating that explosions occur in areas subjected to intense hydrothermal processes; (4) many lithic clasts contained in explosion breccia deposits preserve evidence of repeated fracturing

  4. Modeling of the fault-controlled hydrothermal ore-forming systems

    SciTech Connect

    Pek, A.A.; Malkovsky, V.I.

    1993-07-01

    A necessary precondition for the formation of hydrothermal ore deposits is a strong focusing of hydrothermal flow as fluids move from the fluid source to the site of ore deposition. The spatial distribution of hydrothermal deposits favors the concept that such fluid flow focusing is controlled, for the most part, by regional faults which provide a low resistance path for hydrothermal solutions. Results of electric analog simulations, analytical solutions, and computer simulations of the fluid flow, in a fault-controlled single-pass advective system, confirm this concept. The influence of the fluid flow focusing on the heat and mass transfer in a single-pass advective system was investigated for a simplified version of the metamorphic model for the genesis of greenstone-hosted gold deposits. The spatial distribution of ore mineralization, predicted by computer simulation, is in reasonable agreement with geological observations. Computer simulations of the fault-controlled thermoconvective system revealed a complex pattern of mixing hydrothermal solutions in the model, which also simulates the development of the modern hydrothermal systems on the ocean floor. The specific feature of the model considered, is the development under certain conditions of an intra-fault convective cell that operates essentially independently of the large scale circulation. These and other results obtained during the study indicate that modeling of natural fault-controlled hydrothermal systems is instructive for the analysis of transport processes in man-made hydrothermal systems that could develop in geologic high-level nuclear waste repositories.

  5. Hydrothermal synthesis map of bismuth titanates

    SciTech Connect

    Sardar, Kripasindhu; Walton, Richard I.

    2012-05-15

    The hydrothermal synthesis of four bismuth titanate materials from common bismuth and titanium precursors under hydrothermal conditions is described. Reaction of NaBiO{sub 3}{center_dot}2H{sub 2}O and anatase TiO{sub 2} in concentrated NaOH solution at 240 Degree-Sign C is shown to produce perovskite and sillenite phases Na{sub 0.5}Bi{sub 0.5}TiO{sub 3} and Bi{sub 12}TiO{sub 20}, depending on the ratio of metal precursors used. When KOH solution is used and a 1:1 ratio of the same precursors, a pyrochlore Bi{sub 1.43}Ti{sub 2}O{sub 6}(OH){sub 0.29}(H{sub 2}O){sub 0.66} is formed. The use of a mixture of HNO{sub 3} and NaOH is shown to facilitate the formation of the Aurivillius-type bismuth titanate Bi{sub 4}Ti{sub 3}O{sub 12}. The phases have been isolated separately as phase-pure powders and profile refinement of powder X-ray diffraction data allows comparisons with comparable materials reported in the literature. Analysis of Bi L{sub III}-edge X-ray absorption near edge structure (XANES) spectra of the materials shows the oxidation state of bismuth is +3 in all of the hydrothermally derived products. - Graphical abstract: Use of NaBiO{sub 3}{center_dot}2H{sub 2}O and TiO{sub 2} as reagents under hydrothermal conditions allows the phase-pure preparation of four crystalline bismuth titanate materials. Highlights: Black-Right-Pointing-Pointer NaBiO{sub 3} and TiO{sub 2} under hydrothermal conditions allow formation of bismuth titanates. Black-Right-Pointing-Pointer Synthesis of four distint phases has been mapped. Black-Right-Pointing-Pointer Bi LIII-edge XANES shows Bi is reduced to oxidation state +3 in all materials. Black-Right-Pointing-Pointer A new hydrated bismuth titanate pyrochlore has been isolated.

  6. Cation exchange properties of zeolites in hyper alkaline aqueous media.

    PubMed

    Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

    2015-02-03

    Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

  7. Hydrothermal synthesis of bismuth germanium oxide

    SciTech Connect

    Boyle, Timothy J.

    2016-12-13

    A method for the hydrothermal synthesis of bismuth germanium oxide comprises dissolving a bismuth precursor (e.g., bismuth nitrate pentahydrate) and a germanium precursor (e.g., germanium dioxide) in water and heating the aqueous solution to an elevated reaction temperature for a length of time sufficient to produce the eulytite phase of bismuth germanium oxide (E-BGO) with high yield. The E-BGO produced can be used as a scintillator material. For example, the air stability and radioluminescence response suggest that the E-BGO can be employed for medical applications.

  8. Microbial community development in deep-sea hydrothermal vents in the Earth and the Enceladus (Invited)

    NASA Astrophysics Data System (ADS)

    Takai, K.; Shibuya, T.; Sekine, Y.; Russell, M. J.

    2013-12-01

    Over the past 35 years, researchers have explored seafloor deep-sea hydrothermal vent environments around the globe and studied a number of microbial ecosystems. Bioinformatics and interdisciplinary geochemistry-microbiology approaches have provided new ideas on the diversity and community composition of microbial life living in deep-sea vents. In particular, recent investigations have revealed that the community structure and productivity of chemolithotrophic microbial communities in the deep-sea hydrothermal environments are controlled primarily by variations in the geochemical composition of hydrothermal fluids. This was originally predicted by a thermodynamic calculation of energy yield potential of various chemolithotrophic metabolisms in a simulated hydrothermal mixing zone. The prediction has been finally justified by the relatively quantitative geomicrobiological characterizations in various deep-sea hydrothermal vent environments all over the world. Thus, there should be a possible principle that the thermodynamic estimation of chemolithotrophic energy yield potentials could predict the realistic chemolithotrophic living community in any of the deep-sea hydrothermal vent environments in this planet. In 2005, a spacecraft Cassini discovered a water vapour jet plume from the sole pole area of the Saturnian moon Enceladus. The chemical composition analyses of Cassini's mass spectrometer strongly suggested that the Enceladus could host certain extent of extraterrestrial ocean beneath the surface ice sheet and possible ocean-rock hydrothermal systems. In addition, a recent research has suggests that there is silica nanoparticles in Saturn's E-ring derived from the Enceladus plume. An experimental study simulating the reaction between chondritic material and alkaline seawater reveals that the formation of silica nanoparticles requires hydrothermal reaction at high temperatures. Based on these findings, we attempt to built a model of possible hydrothermal fluid

  9. En Echelon Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Ryan, M. P.; Carr, P. M.; Daniels, D. L.; Sutphin, D. M.

    2005-12-01

    En echelon hydrothermal systems develop within the porous rocks that surround, in three-dimensions, their distinctive plan-form and cross-sectional basaltic intrusion geometry. Examples that span several (self-similar) spatial scales include the en echelon off-set area of the East Rift Zone of Kilauea Volcano, Hawaii; the Northeast Rift Zone of Mauna Loa Volcano; the intrusive-eruptive fissures of the Krafla Central Volcano, Northeast Iceland; the ensemble of the three Icelandic central volcanoes Theistarekir-Krafla-Fremrinamur; major segments of the East Pacific Rise and the Mid-Atlantic Ridge; and several paleo-hydrothermal systems of the Mesozoic basins of eastern North America, including the Culpeper Basin. An en echelon hydrothermal system comprises two or more en echelon--arranged magma-filled fractures enclosed in a fluid-saturated porous matrix. Blocks of country rock between individual offset fracture segments are similarly porous and fluid-saturated. In 3-D, the system resembles the fan blades of a turbine rotor, with blades (dikes) emanating from a deep "master" fracture and turning smoothly in response to the local variations in the least compressive regional stress component. The primary geometric, hydrologic and thermal attributes of the system (on a horizontal plane) include dike thickness, dike-to-dike offset and overlap, the (initial) intrusion temperature, duration of magma flow, dike widths and lengths, the mean seepage velocity of regional subsurface aqueous fluid flow, and the mean flow azimuth in relationship to the plan-form geometry of the en echelon array. Finite element single phase models in horizontal cross-section have been developed for dike widths of 100 m, dike lengths of 1,500 m, overlaps of 500 m, dike-to-dike offsets of 500 m, intrusion temperatures of 1,200 C, horizontal seepage fluxes imposed at the sides of ~ 1,000 g cm-2 yr-1, and a matrix permeability of 10-14 m2. The regional flow field has been parameterized in dike

  10. The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front.

    PubMed

    Russell, M J; Hall, A J

    1997-05-01

    Here we argue that life emerged on Earth from a redox and pH front at c. 4.2 Ga. This front occurred where hot (c. 150 degrees C), extremely reduced, alkaline, bisulphide-bearing, submarine seepage waters interfaced with the acid, warm (c. 90 degrees C), iron-hearing Hadean ocean. The low pH of the ocean was imparted by the ten bars of CO2 considered to dominate the Hadean atmosphere/hydrosphere. Disequilibrium between the two solutions was maintained by the spontaneous precipitation of a colloidal FeS membrane. Iron monosulphide bubbles comprising this membrane were inflated by the hydrothermal solution upon sulphide mounds at the seepage sites. Our hypothesis is that the FeS membrane, laced with nickel, acted as a semipermeable catalytic boundary between the two fluids, encouraging synthesis of organic anions by hydrogenation and carboxylation of hydrothermal organic primers. The ocean provided carbonate, phosphate, iron, nickel and protons; the hydrothermal solution was the source of ammonia, acetate, HS-, H2 and tungsten, as well as minor concentrations of organic sulphides and perhaps cyanide and acetaldehyde. The mean redox potential (delta Eh) across the membrane, with the energy to drive synthesis, would have approximated to 300 millivolts. The generation of organic anions would have led to an increase in osmotic pressure within the FeS bubbles. Thus osmotic pressure could take over from hydraulic pressure as the driving force for distension, budding and reproduction of the bubbles. Condensation of the organic molecules to polymers, particularly organic sulphides, was driven by pyrophosphate hydrolysis. Regeneration of pyrophosphate from the monophosphate in the membrane was facilitated by protons contributed from the Hadean ocean. This was the first use by a metabolizing system of protonmotive force (driven by natural delta pH) which also would have amounted to c. 300 millivolts. Protonmotive force is the universal energy transduction mechanism of life

  11. Hydrothermally prepared inorganic siliceous wastes: Hydrothermal reaction of calcareous and steatite ceramic tile wastes

    SciTech Connect

    Maenami, Hiroki; Yamamoto, Takeyuki; Ishida, Hideki

    1996-12-31

    Possibility of solidification of various ceramic wastes by hydrothermal processing was investigated. The starting materials were feldspathic porcelain tile waste, steatite ceramic tile waste, and calcareous ceramic tile waste. These were mixed with CaO so as to obtain a Ca/Si molar ratio of 0.5. After forming, they were cured for 2 to 20 h under the saturated steam pressure at 200{degrees}C. Although the SiO{sub 2} content of these ceramic wastes was about 70 mass% and they contain various alkaline ions and alkaline earth ions, solidified specimens with flexural strength up to 35MPa were obtained. This is within the range of strengths when quartz or fused silica is used as pure SiO{sub 2} sources. Formation of tobermorite, which was detected in all systems after 2 h of curing, was considered to affect the increase of the strength. It was found that there is a possibility of aluminum and alkali ions being included in the structure of the formed tobermorite. In the case of using steatite ceramic tile waste containing Mg, magnesium silicate hydrates were also formed. The modal pore diameter shifted to 0.01 {mu} m with the formation of these hydrates and there was correlation between the flexural strength and the pore size distribution.

  12. Hydrothermal processes at seafloor spreading centers,

    SciTech Connect

    Sleep, N.H.

    1983-01-01

    This chapter discusses the initial entry of hydrothermal seawater into deep levels of the oceanic crust, the effectiveness of hydrothermal circulation in cooling the crust, the geometry of hydrothermal circulation, the relationship between the hydrothermal circulation and the magma chamber, the reaction of the oceanic crust with the seawater, and the identification of the hydrothermal fluid which alters a rock sample. Topics considered include the crack front, observation relevant to the crack front, the limitations of the crack front hypothesis, the observed pattern of hydrothermal alteration, the nature of the hydrothermal fluid, the physics of large scale convection, and convection through crack zones. Knowledge of hydrothermal circulation at the ridge axis is based on sampling of the hydrothermal fluid, indirect geophysical measurements of the oceanic crust, and studies of rocks which are believed to have undergone hydrothermal alteration at the ridge axis. Includes 2 drawings.

  13. Implementation of model predictive control on a hydrothermal oxidation reactor

    SciTech Connect

    Muske, K.R.; Dell`Orco, P.C.; Le, L.A.; Flesner, R.L.

    1998-12-31

    This paper describes the model-based control algorithm developed for a hydrothermal oxidation reactor at the Pantex Department of Energy facility in Amarillo, Texas. The combination of base hydrolysis and hydrothermal oxidation is used for the disposal of PBX 9404 high explosive at Pantex. The reactor oxidizes the organic compounds in the hydrolysate solutions obtained from the base hydrolysis process. The objective of the model predictive controller is to minimize the total aqueous nitrogen compounds in the effluent of the reactor. The controller also maintains a desired excess oxygen concentration in the reactor effluent to ensure the complete destruction of the organic carbon compounds in the hydrolysate.

  14. Hydrothermally growth of novel hierarchical structures titanium dioxide for high efficiency dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Cheng, Pengfei; Liu, Yang; Sun, Peng; Du, Sisi; Cai, Yaxin; Liu, Fengmin; Zheng, Jie; Lu, Geyu

    2014-12-01

    We report an innovative development of novel double layered photoanodes made of hierarchical TiO2 micro-corollas as the overlayer and TiO2 nanoforest as the underlayer (HTCF), for dye-sensitized solar cells (DSSCs). They are obtained by a facile hydrothermal reaction of TiO2 nanorods array with top microspheres (MS)/FTO (Fluorine-doped tin oxide) glass substrate in an alkaline solution. In this process, the microspheres and nanorods are transformed into micro-corollas and nanotrees, respectively. The photoanodes with HTCF structure can greatly improve the light scattering ability due to their novel structures. Moreover, the enhanced surface area of HTCF can lead to larger dye loading, which achieves the higher light harvesting capacity. Base on the fast electron transport of the interior nanorods, higher light scattering and harvesting capacities, this novel HTCF photoanode realizes tri-functions. The overall power conversion efficiency (PCE) of the HTCF DSSCs are 51% increase in the conversion efficiency compare with those of constructed by bare TiO2 nanorod arrays. In our work, tri-functions of photoanodes are obtained by improving the 1D TiO2 nanostructures (nanorod, nanowire, nanotube et al.). To the best of our knowledge, it is a significant fabrication technology breakthrough for the photoanode of dye-sensitized solar cells.

  15. Net alkalinity and net acidity 2: Practical considerations

    USGS Publications Warehouse

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the

  16. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, David T.

    1992-01-01

    A method for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction.

  17. Hydrothermal conversion of FAU zeolite into LEV zeolite in the presence of non-calcined seed crystals

    NASA Astrophysics Data System (ADS)

    Yashiki, Ayako; Honda, Koutaro; Fujimoto, Ayumi; Shibata, Shohei; Ide, Yusuke; Sadakane, Masahiro; Sano, Tsuneji

    2011-06-01

    Hydrothermal conversion of Faujasite-type (FAU) zeolite into Levynite (LEV) zeolite without the use of an organic structure-directing agent (OSDA) was successfully achieved in the presence of non-calcined seed crystals. The interzeolite conversion depended strongly upon the alkalinity (OH -/SiO 2) of the starting gel, the Si/Al ratio of the starting FAU zeolite and the type of alkaline metal employed. Successful conversion of FAU zeolites into pure LEV zeolite was achieved only for FAU zeolites with Si/Al ratios in the range of 19-26, under highly alkaline conditions (OH -/SiO 2=0.6) by using NaOH as an alkali source. Although the yield of LEV zeolite prepared by this method was lower (18-26%) than that of the conventional hydrothermal synthesis with the use of SDA, the obtained LEV zeolite exhibited a unique core/shell structure.

  18. Lipid Biomarker Preservation in Silica-Depositing Hydrothermal Analogs

    NASA Astrophysics Data System (ADS)

    Jahnke, L. L.; Parenteau, M. N.; Farmer, J. D.

    2010-12-01

    The discovery of extensive silica-rich deposits at Home Plate in the Columbia Hills indicates that hydrothermal conditions once existed on Mars (Squyres et al. 2008). Two types of environments could have been responsible for forming these materials: fumaroles or hydrothermal springs. Examples of both types of these thermal features are found throughout Yellowstone National Park (YNP). The discovery of bona fide microfossils in ancient cherts indicates that silica deposition was an excellent mechanism for organic preservation on the early Earth. Given the importance that organic biomarkers have played in identifying some of the earliest microbial life on Earth and the potential for a similar habitable period on Mars, examination of the preservation of organic biomarkers within various hydrothermal, silica-rich modern analogs is essential for future interpretation of Martian organics. Cyanobacterial mats and biofilms are common inhabitants of hydrothermal spring systems worldwide, at temperatures below 73°C and over a broad range of pH, from acidic to alkaline. Bacteriohopanepolyols (BHPs) are the biological precursors for the abundant fossil hopanes recovered from sedimentary rock (Brocks et al. 1999; Summons et al. 1999). The 2-methyl homologs are generally considered a biomarker for cyanobacterial-dominated paleoecosystems. Some evidence exists that the complex molecular structure of BHP is retained upon entombment in hydrothermal silica and that rapid incorporation into the silica matrix may enhance preservation (Gibson et al. 2008). Here we report on the preservation of microbial lipids in several alkaline and acidic, silica-depositing hotsprings in YNP with particular emphasis on the potential for BHP preservation. Brocks JJ et al (1999) Archaean molecular fossils and the early rise of the eukaryotes. Science 185: 1033-1036 Gibson RA et al (2008) Bacteriohopanepolyol signatures of cyanobacterial and methanotrophic bacterial populations recorded in a geothermal

  19. The alkalinizing effects of metabolizable bases in the healthy calf.

    PubMed Central

    Naylor, J M; Forsyth, G W

    1986-01-01

    The alkalinizing effect of citrate, acetate, propionate, gluconate, L and DL-lactate were compared in healthy neonatal calves. The calves were infused for a 3.5 hour period with 150 mmol/L solutions of the sodium salts of the various bases. Blood pH, base excess, and metabolite concentrations were measured and the responses compared with sodium bicarbonate and sodium chloride infusion. D-gluconate and D-lactate had poor alkalinizing abilities and accumulated in blood during infusion suggesting that they are poorly metabolized by the calf. Acetate, L-lactate and propionate had alkalinizing effects similar to bicarbonate, although those of acetate had a slightly better alkalinizing effect than L-lactate. Acetate was more effectively metabolized because blood acetate concentrations were lower than L-lactate concentrations. There was a tendency for a small improvement in metabolism of acetate and lactate with age. Sodium citrate infusion produced signs of hypocalcemia, presumably because it removed ionized calcium from the circulation. D-gluconate, D-lactate and citrate are unsuitable for use as alkalinizing agents in intravenous fluids. Propionate, acetate and L-lactate are all good alkalinizing agents in healthy calves but will not be as effective in situations where tissue metabolism is impaired. PMID:3024796

  20. Impact-generated Hydrothermal Activity at the Chicxulub Crater

    NASA Astrophysics Data System (ADS)

    Kring, D. A.; Zurcher, L.; Abramov, O.

    2007-05-01

    Borehole samples recovered from PEMEX exploration boreholes and an ICDP scientific borehole indicate the Chicxulub impact event generated hydrothermal alteration throughout a large volume of the Maya Block beneath the crater floor and extending across the bulk of the ~180 km diameter crater. The first indications of hydrothermal alteration were observed in the crater discovery samples from the Yucatan-6 borehole and manifest itself in the form of anhydrite and quartz veins. Continuous core from the Yaxcopoil-1 borehole reveal a more complex and temporally extensive alteration sequence: following a brief period at high temperatures, impact- melt-bearing polymict breccias and a thin, underlying unit of impact melt were subjected to metasomatism, producing alkali feldspar, sphene, apatite, and magnetite. As the system continued to cool, smectite-series phyllosilicates appeared. A saline solution was involved. Stable isotopes suggest the fluid was dominated by a basinal brine created mostly from existing groundwater of the Yucatan Peninsula, although contributions from down-welling water also occurred in some parts of the system. Numerical modeling of the hydrothermal system suggests circulation occurred for 1.5 to 2.3 Myr, depending on the permeability of the system. Our understanding of the hydrothermal system, however, is still crude. Additional core recovery projects, particularly into the central melt sheet, are needed to better evaluate the extent and duration of hydrothermal alteration.

  1. Hydrothermal acid treatment for sugar extraction from Golenkinia sp.

    PubMed

    Choi, Sun-A; Choi, Won-Il; Lee, Jin-Suk; Kim, Seung Wook; Lee, Gye-An; Yun, Jihyun; Park, Ji-Yeon

    2015-08-01

    In this study, hydrothermal acid treatment for efficient recovery of sugar from Golenkinia sp. was investigated. The initial glucose and XMG (xylose, mannose, and galactose) contents of a prepared Golenkinia sp. solution (40g/L) were 15.05 and 5.24g/L, respectively. The microalgal cell walls were hydrolyzed, for sugar recovery, by enzymatic saccharification and/or hydrothermal acid treatment. Among the various hydrothermal acid treatment conditions, the most optimal were the 2.0% H2SO4 concentration at 150°C for 15min, under which the glucose- and XMG-extraction yields were 71.7% and 64.9%, respectively. By pH 4.8, 50°C enzymatic hydrolysis after optimal hydrothermal acid treatment, the glucose- and XMG-extraction yields were additionally increased by 8.3% and 0.8%, respectively. After hydrothermal acid treatment, the combination with the enzymatic hydrolysis process improved the total sugar yield of Golenkinia sp. to 75.4%.

  2. A facile one-pot hydrothermal method to produce SnS2/reduced graphene oxide with flake-on-sheet structures and their application in the removal of dyes from aqueous solution.

    PubMed

    Bian, Xiujie; Lu, Xiaofeng; Xue, Yanpeng; Zhang, Chengcheng; Kong, Lirong; Wang, Ce

    2013-09-15

    In this article, we report a novel one-pot synthesis of SnS2/reduced graphene oxide (rGO) flake-on-sheet nanocomposites via in situ reduction of graphene oxide (GO) by Sn(2+) under hydrothermal conditions. The morphology and structure of the obtained product were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction instrument (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The adsorption characteristics of the SnS2/rGO nanocomposites were examined using an organic dye Rhodamine B (RhB) as adsorbate. SnS2/rGO exhibited superior adsorption behavior for RhB. The adsorption kinetics and adsorption isotherm were investigated. The adsorption of RhB by SnS2/rGO was well fitted to the Langmuir isotherm model, and the resultant kinetic data were well described by pseudo-second-order model.

  3. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  4. Enceladus as a hydrothermal water world

    NASA Astrophysics Data System (ADS)

    Postberg, Frank; Hsu, Hsiang-Wen; Sekine, Yasuhito

    2014-05-01

    The composition of both salty ice grains and nanometer-sized stream particles emitted from Enceladus and measured by Cassini-CDA require require liquid water as a source. Moreover, they provide strong geochemical constraints for their origin inside the active moon. Most stream particles are composed of silica, a unique indicator as nano-silica would only form under quite specific conditions. With high probability on-going or geological recent hydrothermal activity at Enceladus is required to generate these particles. Inferred reaction temperatures at Enceladus ocean floor lie between 100 and 350 °C in a slightly alkaline environment (pH 7.5 - 10.5). The inferred high temperatures at great depth might require heat sources other than tides alone, such as remaining primordial heat and/or serpentinization of a probably porous rocky core. Long-term laboratory experiments were carried out to simulate the conditions at the Enceladus rock/water interface using the constraints derived from CDA measurements. These experiments allow insights into a rock/water chemistry which severely constrains the formation history of the moon and substantially enhances its astrobiological potential. Together with recent results from other Cassini instruments a conclusive picture of Enceladus as an active water world seems to be in reach.

  5. COUPLING THE ALKALINE-SURFACTANT-POLYMER TECHNOLOGY AND THE GELATION TECHNOLOGY TO MAXIMIZE OIL PRODUCTION

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson

    2004-10-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Neither aluminum citrate-polyacrylamide nor silicate-polyacrylamide gel systems produced significant incremental oil in linear corefloods. Both flowing and rigid flowing chromium acetate-polyacrylamide gels produced incremental oil with the rigid flowing gel producing the greatest amount. Higher oil recovery could have been due to higher differential pressures across cores. None of the gels tested

  6. Hydrothermal preparation of tobermorite from blast furnace slag for Cs+ and Sr2+ sorption.

    PubMed

    Tsutsumi, Takuma; Nishimoto, Shunsuke; Kameshima, Yoshikazu; Miyake, Michihiro

    2014-02-15

    Al-substituted 11Å-tobermorite was formed by alkaline hydrothermal treatment of blast furnace slag with sodium silicate added at 180°C for 2-48 h. Effects of the hydrothermal treatment time were characterized by XRD, SEM, and isothermal adsorption of N2. Sorption characteristics of the obtained samples were examined for Cs(+) and Sr(2+). The sample obtained by hydrothermal treatment for 48 h (HT-48 h) consisted of calcium silicate hydrate (C-S-H), and Al-substituted 11Å-tobermorite. The HT-48 h showed the highest performance for Cs(+) and Sr(2+) selectivity in the presence of Na(+). The interlayer Na(+) of Al-substituted 11Å-tobermorite and surface Ca(2+) played an important role in selective Cs(+) and Sr(2+).

  7. Alkaline extraction of phenolic compounds from intact sorghum kernels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An aqueous sodium hydroxide solution was employed to extract phenolic compounds from whole grain sorghum without decortication or grinding as determined by Oxygen Radical Absorbance Capacity (ORAC). The alkaline extract ORAC values were more stable over 32 days compared to neutralized and freeze dri...

  8. The alkaline and alkaline-carbonatite magmatism from Southern Brazil

    NASA Astrophysics Data System (ADS)

    Ruberti, E.; Gomes, C. D. B.; Comin-Chiaramonti, P.

    2015-12-01

    Early to Late Cretaceous lasting to Paleocene alkaline magmatism from southern Brazil is found associated with major extensional structural features in and around the Paraná Basin and grouped into various provinces on the basis of several data. Magmatism is variable in size, mode of occurrence and composition. The alkaline rocks are dominantly potassic, a few occurrences showing sodic affinity. The more abundant silicate rocks are evolved undersaturated to saturated in silica syenites, displaying large variation in igneous forms. Less evolved types are restricted to subvolcanic environments and outcrops of effusive suites occur rarely. Cumulatic mafic and ultramafic rock types are very common, particularly in the alkali-carbonatitic complexes. Carbonatite bodies are represented by Ca-carbonatites and Mg-carbonatites and more scarcely by Fe-carbonatites. Available radiometric ages for the alkaline rocks fit on three main chronological groups: around 130 Ma, subcoveal with the Early Cretaceous flood tholeiites of the Paraná Basin, 100-110 Ma and 80-90 Ma (Late Cretaceous). The alkaline magmatism also extends into Paleocene times, as indicated by ages from some volcanic lavas. Geochemically, alkaline potassic and sodic rock types are distinguished by their negative and positive Nb-Ta anomalies, respectively. Negative spikes in Nb-Ta are also a feature common to the associated tholeiitic rocks. Sr-Nd-Pb systematics confirm the contribution of both HIMU and EMI mantle components in the formation of the alkaline rocks. Notably, Early and Late Cretaceous carbonatites have the same isotopic Sr-Nd initial ratios of the associated alkaline rocks. C-O isotopic Sr-Nd isotopic ratios indicate typical mantle signature for some carbonatites and the influence of post-magmatic processes in others. Immiscibility of liquids of phonolitic composition, derived from mafic alkaline parental magmas, has been responsible for the origin of the carbonatites. Close association of alkaline

  9. Efficiencies of Power Plants Using Hydrothermal Oxidation

    NASA Astrophysics Data System (ADS)

    Hirosaka, Kazuma; Yuvamitra, Korakot; Ishikawa, Akira; Hasegawa, Tatsuya

    Wet biomass is hard to handle as a fuel for power plants because it contains high moisture and its drying process needs more energy input than it produces. Hydrothermal oxidation could be one of the promising technologies to overcome this problem because this process does not need drying process at all. We focus on recovery of thermal energy produced by hydrothermal oxidation of wet biomass. Two kinds of power plant are investigated, a direct type and an indirect type. In the direct type power plant, reactant is oxidized in a reactor and directly flowed into a turbine. In the indirect type power plant, reactant is oxidized in a reactor and the reaction heat is conveyed to the main water, which is flowed into a turbine. The amount of electric power and the energy conversion efficiency are calculated by using ethanol, glucose and peat solutions as reactants. In both type of power plant, one steam turbine is employed for generating electricity with the maximum turbine inlet temperature of 650 °C. As ethanol concentration increased, the amount of electric power and the energy conversion efficiency become higher. The maximum efficiency for the direct type power plant using ethanol solution is about 26.4 % for 17.6 wt% at the reactor pressure of 10 MPa. The efficiency of the indirect type power plant is much lower than that of the direct type, but by pressurizing main water up to 4 MPa, the efficiency becomes higher up to 20.9 %. For glucose solution, the maximum efficiency for the direct type is about 25.5 % for 34.5 wt% at the reactor pressure of 5 MPa. The maximum efficiency of the indirect type at the main water pressure of 4 MPa is about 21.1 % for 40.7 wt%. For peat solution, only the indirect type is investigated. The maximum efficiency at the main water pressure of 4 MPa is about 20.8 % for 36.8 wt%.

  10. Dolomite Dissolution in Alkaline Cementious Media

    NASA Astrophysics Data System (ADS)

    Mittermayr, Florian; Klammer, Dietmar; Köhler, Stephan; Dietzel, Martin

    2010-05-01

    Chemical alteration of concrete has gained much attention over the past years as many cases of deterioration due to sulphate attack, thaumasite formation (TSA) or alkali silica reactions (ASR) have been reported in various constructions (Schmidt et al, 2009). Much less is known about the so called alkali carbonate reaction (ACR). It is believed that dolomite aggregates can react with the alkalis from the cement, dissolve and form calcite and brucite (Katayama, 2004). Due to very low solubility of dolomite in alkaline solutions this reaction seems doubtful. In this study we are trying to gain new insides about the conditions that can lead to the dissolution of dolomite in concrete. Therefore we investigated concrete samples from Austrian tunnels that show partially dissolved dolomite aggregates. Petrological analysis such as microprobe, SEM and Raman spectroscopy as well as a hydrochemical analysis of interstitial solutions and ground water and modelling with PhreeqC (Parkhurst and Appelo, 1999) are carried out. In addition a series of batch experiments is set up. Modelling approaches by PhreeqC show a thermodynamically possibility in the alkaline range when additional Ca2+ in solution causes dolomite to become more and more undersaturated as calcite gets supersaturated. Interacting ground water is enriched in Ca2+and saturated with respect to gypsum as marine evaporites are found in situ rocks. Furthermore it is more likely that Portlandite (Ca(OH)2) plays a more important role than Na and K in the cement. Portlandite acts as an additional Ca2+ source and is much more abundant than the alkalies. Some interstitial solutions are dominated mainly by Na+ and SO42- and reach concentrations up to 30 g/l TDS. It is believed that solutions can even reach thenardite saturation as efflorescences are found on the tunnel walls. In consequence dolomite solubility increases with increasing ionic strength. pH > 11 further accelerate the process of dedolomitization by the removal

  11. COUPLING THE ALKALINE-SURFACTANT-POLYMER TECHNOLOGY AND THE GELATION TECHNOLOGY TO MAXIMIZE OIL PRODUCTION

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; David Stewart; Bill Jones

    2005-04-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Chromium acetate-xanthan gum rigid gels are not stable to subsequent alkaline-surfactant-polymer solution injection. Resorcinol-formaldehyde gels were stable to subsequent alkaline-surfactant-polymer solution injection. When evaluated in a dual core configuration, injected fluid flows into the core with the greatest effective permeability to the injected fluid. The same gel stability trends to subsequent

  12. Net alkalinity and net acidity 1: Theoretical considerations

    USGS Publications Warehouse

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a

  13. Alkaline oxide conversion coatings for aluminum alloys

    SciTech Connect

    Buchheit, R.G.

    1996-02-01

    Three related conversion coating methods are described that are based on film formation which occurs when aluminum alloys are exposed to alkaline Li salt solutions. Representative examples of the processing methods, resulting coating structure, composition and morphology are presented. The corrosion resistance of these coatings to aerated 0.5 M NaCl solution has been evaluated as a function of total processing time using electrochemical impedance spectroscopy (EIS). This evaluation shows that excellent corrosion resistance can be uniformly achieved using no more than 20 minutes of process time for 6061-T6. Using current methods a minimum of 80 minutes of process time is required to get marginally acceptable corrosion resistance for 2024-T3. Longer processing times are required to achieve uniformly good corrosion resistance.

  14. Porosity evolution in Icelandic hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Thien, B.; Kosakowski, G.; Kulik, D. A.

    2014-12-01

    Mineralogical alteration of reservoir rocks, driven by fluid circulation in natural or enhanced hydrothermal systems, is likely to influence the long-term performance of geothermal power generation. A key factor is the change of porosity due to dissolution of primary minerals and precipitation of secondary phases. Porosity changes will affect fluid circulation and solute transport, which, in turn, influence mineralogical alteration. This study is part of the Sinergia COTHERM project (COmbined hydrological, geochemical and geophysical modeling of geotTHERMal systems, grant number CRSII2_141843/1) that is an integrative research project aimed at improving our understanding of the sub-surface processes in magmatically-driven natural geothermal systems. These are typically high enthalphy systems where a magmatic pluton is located at a few kilometers depth. These shallow plutons increase the geothermal gradient and trigger the circulation of hydrothermal waters with a steam cap forming at shallow depth. Field observations suggest that active and fossil Icelandic hydrothermal systems are built from a superposition of completely altered and completely unaltered layers. With help of 1D and 2D reactive transport models (OpenGeoSys-GEM code), we investigate the reasons for this finding, by studying the mineralogical evolution of protoliths with different initial porosities at different temperatures and pressures, different leaching water composition and gas content, and different porosity geometries (i.e. porous medium versus fractured medium). From this study, we believe that the initial porosity of protoliths and volume changes due to their transformation into secondary minerals are key factors to explain the different alteration extents observed in field studies. We also discuss how precipitation and dissolution kinetics can influence the alteration time scales.

  15. Hydrothermal pretreatment of coal

    SciTech Connect

    Ross, D.S.

    1989-12-21

    We have examined changes in Argonne Premium samples of Wyodak coal following 30 min treatment in liquid water at autogenous pressures at 150{degrees}, 250{degrees}, and 350{degrees}C. In most runs the coal was initially dried at 60{degrees}C/1 torr/20 hr. The changes were monitored by pyrolysis field ionization mass spectrometry (py-FIMS) operating at 2.5{degrees}C/min from ambient to 500{degrees}C. We recorded the volatility patterns of the coal tars evolved over that temperature range, and in all cases the tar yields were 25%--30% of the starting coal on mass basis. There was essentially no change after the 150{degrees}C treatment. Small increases in volatility were seen following the 250{degrees}C treatment, but major effects were seen in the 350{degrees} work. The tar quantity remained unchanged; however, the volatility increased so the temperature of half volatility for the as-received coal of 400{degrees}C was reduced to 340{degrees}C. Control runs with no water showed some thermal effect, but the net effect from the presence of liquid water was clearly evident. The composition was unchanged after the 150{degrees} and 250{degrees}C treatments, but the 350{degrees} treatment brought about a 30% loss of oxygen. The change corresponded to loss of the elements of water, although loss of OH'' seemed to fit the analysis data somewhat better. The water loss takes place both in the presence and in the absence of added water, but it is noteworthy that the loss in the hydrothermal runs occurs at p(H{sub 2}O) = 160 atm. We conclude that the process must involve the dehydration solely of chemically bound elements of water, the dehydration of catechol is a specific, likely candidate.

  16. Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

    PubMed Central

    Cruickshank, Dyanne L; Rougier, Natalia M; Vico, Raquel V; Bourne, Susan A

    2013-01-01

    Summary An anhydrous 1:1 crystalline inclusion complex between the organophosphorus insecticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate] and the host compound heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) was prepared and its structure elucidated by single-crystal X-ray diffraction. This revealed two independent host molecules in the asymmetric unit. In one of these, the cavity is occupied by two disordered guest components (distinguishable as rotamers with respect to the P–OAr bond) while in the other, three distinct guest components with site-occupancies 0.44, 0.29 and 0.27 appear, the last having a reversed orientation relative to all the other components. Kinetic studies of the alkaline hydrolysis of fenitrothion in the presence of DIMEB showed a remarkable reduction of 84% in the rate of this reaction relative to that for the free substrate, a value exceeding those previously attained with the native hosts, β- and γ-cyclodextrin, and fully methylated β-cyclodextrin. PMID:23400042

  17. One-pot synthesis of nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle as an efficient metal-free catalyst for oxygen reduction reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Guo, Liping

    2014-12-01

    Nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle (NS-MCV) with multilayer lamellar structure is synthesized as a metal-free catalyst through a convenient and economical procedure. The synthesized materials are systematically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrate that N and S atoms can be successfully doped into the framework of MCV with little impact on the morphology and structure. The NS-MCV manifests a remarkably high electrocatalytic activity as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) with mainly a four-electron transfer pathway. Moreover, in contrast to the commercially available Pt/C catalyst, the NS-MCV shows much better long-term stability and tolerance toward methanol crossover in an alkaline medium. Such excellent performances can be mainly attributed to the synergistic effect arising from the addition of N and S heteroatom, optimized S content and high surface area. The NS-MCV with a simple synthesis method may further exploited as potentially efficient and inexpensive metal-free ORR catalyst materials.

  18. Immobilization of cesium in alkaline activated fly ash matrix

    NASA Astrophysics Data System (ADS)

    Fernandez-Jimenez, A.; Macphee, D. E.; Lachowski, E. E.; Palomo, A.

    2005-11-01

    The immobilization potential of alkaline activated fly ash (AAFA) matrices for cesium has been investigated. The presence of Cs in the AAFA pastes, prepared using 8M NaOH solution as activator, showed no significant adverse effects on mechanical strength or microstructure, nor were significant quantities of Cs leached following application of the Toxic Characteristic Leaching Procedure (TCLP) and American Nuclear Society (ANS) 16.1 leaching protocols. Microstructural analysis shows Cs associated with the main reaction product in the AAFA suggesting that cesium is chemically bound rather than physically encapsulated. It is proposed that cesium is incorporated into the alkaline aluminosilicate gel, a precursor for zeolite formation.

  19. Hydrothermal systems and volcano geochemistry

    USGS Publications Warehouse

    Fournier, R.O.

    2007-01-01

    The upward intrusion of magma from deeper to shallower levels beneath volcanoes obviously plays an important role in their surface deformation. This chapter will examine less obvious roles that hydrothermal processes might play in volcanic deformation. Emphasis will be placed on the effect that the transition from brittle to plastic behavior of rocks is likely to have on magma degassing and hydrothermal processes, and on the likely chemical variations in brine and gas compositions that occur as a result of movement of aqueous-rich fluids from plastic into brittle rock at different depths. To a great extent, the model of hydrothermal processes in sub-volcanic systems that is presented here is inferential, based in part on information obtained from deep drilling for geothermal resources, and in part on the study of ore deposits that are thought to have formed in volcanic and shallow plutonic environments.

  20. Hydrothermal synthesis of ammonium illite

    USGS Publications Warehouse

    Sucha, V.; Elsass, F.; Eberl, D.D.; Kuchta, L'.; Madejova, J.; Gates, W.P.; Komadel, P.

    1998-01-01

    Synthetic gel and glass of illitic composition, natural kaolinite, and mixed-layer illite-smectite were used as starting materials for hydrothermal synthesis of ammonium illite. Ammonium illite was prepared from synthetic gel by hydrothermal treatment at 300??C. The onset of crystallization began within 3 h, and well-crystallized ammonium illite appeared at 24 h. Increasing reaction time (up to four weeks) led to many illite layers per crystal. In the presence of equivalent proportions of potassium and ammonium, the gel was transformed to illite with equimolar contents of K and NH4. In contrast, synthesis using glass under the same conditions resulted in a mixture of mixed-layer ammonium illite-smectite with large expandability and discrete illite. Hydrothermal treatments of the fine fractions of natural kaolinite and illite-smectite produced ammonium illite from kaolinite but the illite-smectite remained unchanged.

  1. Hydrothermal Activity in the Northern Guaymas Basin

    NASA Astrophysics Data System (ADS)

    Berndt, C.; Hensen, C.; Mortera-Gutierrez, C. A.; Sarkar, S.; Geilert, S.; Schmidt, M.; Liebetrau, V.; Kipfer, R.; Scholz, F.; Doll, M.; Muff, S.; Karstens, J.; Böttner, C.; Chi, W. C.; Moser, M.; Behrendt, R.; Fiskal, A.; Evans, T.; Planke, S.; Lizarralde, D.; Lever, M. A.

    2015-12-01

    Rift-related magmatism in the Guaymas Basin, Gulf of California induces hydrothermal activity within the basin sediments. Mobilized fluids migrate to the seafloor where they are emitted into the water column changing ocean chemistry and fuelling chemosynthetic ecosystems. New seismic and geochemical data from the northern rift arm of the Guaymas Basin document the variety of fluid expulsion phenomena from large-scale subsurface sediment mobilization related to contact metamorphosis to focused small-scale structures. The geochemical composition of emitted fluids depends largely on the age of the fluid escape structures with respect to the underlying intrusions. Whereas, old structures are dominated by methane emission, young vent sites are characterized by hot fluids that carry a wide range of minerals in solution. The overall high geothermal gradient within the basin (mainly between 160 and 260 °C/km) leads to a thin gas hydrate stability zone. Thus, deep hydrothermal fluid advection affects the gas hydrate system and makes it more dynamic than in colder sedimentary basins.

  2. The measurement of alkaline phosphatase at nanomolar concentration within 70 s using a disposable microelectrochemical transistor.

    PubMed

    Astier, Y; Bartlett, P N

    2004-08-01

    We report a new approach to the measurement of alkaline phosphatase concentration based on the use of a disposable poly(aniline) microelectrochemical transistor. The measurement is carried out in a two cell configuration in which the poly(aniline) microelectrochemical transistor operates in acid solution and is connected to the alkaline buffer solution containing the analyte by a salt bridge. Disposable microelectrochemical transistors were reproducibly fabricated by electrochemical deposition of poly(aniline) onto photolithographically fabricated gold microband arrays. Using these devices alkaline phosphatase was detected by employing p-aminophenyl phosphate as the substrate for the enzyme and using glucose and glucose oxidase to recycle the p-aminophenol generated upon enzyme catalysed hydrolysis of the phosphate. Recycling the p-aminophenol with glucose and glucose oxidase amplified the detection of alkaline phosphatase approximately tenfold. Using this approach we obtain linear calibration curves for alkaline phosphatase up to 5 nM within 70 s on single use devices.

  3. Comparative assessment of five potential sites for hydrothermal magma systems: geochemistry

    SciTech Connect

    White, A.F.

    1980-08-01

    A brief discussion is given of the geochemical objectives and questions that must be addressed in such an evaluation. A summary of the currently published literature that is pertinent in answering these questions is presented for each of the five areas: The Geysers-Clear Lake region, Long Valley, Rio Grand Rift, Roosevelt Hot Springs, and the Salton Trough. The major geochemical processes associated with proposed hydrothermal sites are categorized into three groups for presentation: geochemistry of magma and associated volcanic rocks, geochemistry of hydrothermal solutions, and geochemistry of hydrothermal alteration. (MHR)

  4. Field measurement of alkalinity and pH

    USGS Publications Warehouse

    Barnes, Ivan

    1964-01-01

    The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

  5. Autonomous in situ measurements of seawater alkalinity.

    PubMed

    Spaulding, Reggie S; DeGrandpre, Michael D; Beck, James C; Hart, Robert D; Peterson, Brittany; De Carlo, Eric H; Drupp, Patrick S; Hammar, Terry R

    2014-08-19

    Total alkalinity (AT) is an important parameter for describing the marine inorganic carbon system and understanding the effects of atmospheric CO2 on the oceans. Measurements of AT are limited, however, because of the laborious process of collecting and analyzing samples. In this work we evaluate the performance of an autonomous instrument for high temporal resolution measurements of seawater AT. The Submersible Autonomous Moored Instrument for alkalinity (SAMI-alk) uses a novel tracer monitored titration method where a colorimetric pH indicator quantifies both pH and relative volumes of sample and titrant, circumventing the need for gravimetric or volumetric measurements. The SAMI-alk performance was validated in the laboratory and in situ during two field studies. Overall in situ accuracy was -2.2 ± 13.1 μmol kg(-1) (n = 86), on the basis of comparison to discrete samples. Precision on duplicate analyses of a carbonate standard was ±4.7 μmol kg(-1) (n = 22). This prototype instrument can measure in situ AT hourly for one month, limited by consumption of reagent and standard solutions.

  6. Rare Earth Oxide Fluoride Nanoparticles And Hydrothermal Method For Forming Nanoparticles

    DOEpatents

    Fulton, John L.; Hoffmann, Markus M.

    2003-12-23

    A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

  7. Rare earth oxide fluoride nanoparticles and hydrothermal method for forming nanoparticles

    DOEpatents

    Fulton, John L [Richland, WA; Hoffmann, Markus M [Richland, WA

    2001-11-13

    A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

  8. Determination of the age of hydrothermal fluids by the kinetic-geochemical method

    SciTech Connect

    Reznikov, A.N.

    1995-03-01

    An estimate of the age of hydrothermal fluids at rift zones of oceans and continents, island arc regions, as well as regions of mud volcanism and occurrences of condensation and solution waters of hydrocarbon accumulations is given on the basis of the chemical, gas, and isotopic compositions and geothermobaric conditions. Correlations between the degree of accumulation of trace elements in hydrothermal fluids and their age were established.

  9. Scanning electron microscopic and X-ray micro analysis on tooth enamel exposed to alkaline agents.

    PubMed

    Taubee, Fabian; Steiniger, Frank; Nietzsche, Sandor; Norén, Jörgen G

    2010-01-01

    The background of this study comprises two clinical cases, where patients exposed to aerosols of an alkaline and surface active cleaning agent developed loss of enamel substance on their teeth, further resulting in loss of teeth and partially destroyed soft tissues. The alkaline cleaning agent consisted of potassium hydroxide and various surfactants. The purpose of this study was to investigate possible changes in morphology and composition in human teeth enamel exposed to alkaline solutions, by means of X-ray micro analysis (XRMA), FTIR-spectroscopic analyses and scanning electron microscopy (SEM). Extracted premolars, exposed to potassium hydroxide solutions and alkaline cleaning solution,were analyzed by means of XRMA and SEM. Enamel powder, exposed to cleaning solution, was analyzed by means of FTIR. The SEM analysis revealed an increased porosity of the enamel surface and partially loss of enamel substance after exposure to alkaline solutions. The XRMA analyses revealed a decrease in carbon concentration while phosphorous and calcium showed no marked changes. The FTIR analyses showed no significant changes in peak heights or peak positions for phosphate, carbonate or hydroxide. It was concluded that human teeth enamel exposed to alkaline solutions showed loss of organic substance, marked pores in enamel surface and loss of substance in the enamel surface.

  10. Stable isotopes in seafloor hydrothermal systems: Vent fluids, hydrothermal deposits, hydrothermal alteration, and microbial processes

    USGS Publications Warehouse

    Shanks, Wayne C.

    2001-01-01

    The recognition of abundant and widespread hydrothermal activity and associated unique life-forms on the ocean floor is one of the great scientific discoveries of the latter half of the twentieth century. Studies of seafloor hydrothermal processes have led to revolutions in understanding fluid convection and the cooling of the ocean crust, the chemical and isotopic mass balance of the oceans, the origin of stratiform and statabound massive-sulfide ore-deposits, the origin of greenstones and serpentinites, and the potential importance of the subseafloor biosphere. Stable isotope geochemistry has been a critical and definitive tool from the very beginning of the modern era of seafloor exploration.

  11. Coupling the Alkaline-Surfactant-Polymer Technology and The Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; Phil Dowling; David Stewart; Bill Jones

    2005-12-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or reservoirs with different sand lenses with high permeability contrast. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more crude oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or reservoirs with high permeability contrast zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. Fluid-fluid interaction with different gel chemical compositions and alkaline-surfactant-polymer solution with pH values ranging from 9.2 to 12.9 have been tested. Aluminum-polyacrylamide gels are not stable to alkaline-surfactant-polymer solutions at any pH. Chromium-polyacrylamide gels with polymer to chromium ion ratios of 25 or greater were stable to alkaline-surfactant-polymer solutions if solution pH was 10.6 or less. When the polymer to chromium ion was 15 or less, chromium-polyacrylamide gels were stable to alkaline-surfactant-polymer solutions with pH values up to 12.9. Chromium-xanthan gum gels were stable to alkaline-surfactant-polymer solutions with pH values of 12.9 at the polymer to chromium ion ratios tested. Silicate-polyacrylamide, resorcinol-formaldehyde, and sulfomethylated resorcinol-formaldehyde gels were also stable to alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Iron-polyacrylamide gels were immediately destroyed when contacted with any of the alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in

  12. Electricity generation from hydrothermal vents

    NASA Astrophysics Data System (ADS)

    Aryadi, Y.; Rizal, I. S.; Fadhli, M. N.

    2016-09-01

    Hydrothermal vent is a kind of manifestation of geothermal energy on seabed. It produces high temperature fluid through a hole which has a diameter in various range between several inches to tens of meters. Hydrothermal vent is mostly found over ocean ridges. There are some 67000 km of ocean ridges, 13000 of them have been already studied discovering more than 280 sites with geothermal vents. Some of them have a thermal power of up to 60 MWt. These big potential resources of energy, which are located over subsea, have a constraint related to environmental impact to the biotas live around when it becomes an object of exploitation. Organic Rankine Cycle (ORC) is a method of exploiting heat energy to become electricity using organic fluid. This paper presents a model of exploitation technology of hydrothermal vent using ORC method. With conservative calculation, it can give result of 15 MWe by exploiting a middle range diameter of hydrothermal vent in deep of 2000 meters below sea level. The technology provided here really has small impact to the environment. With an output energy as huge as mentioned before, the price of constructing this technology is low considering the empty of cost for drilling as what it should be in conventional exploitation. This paper also presents the comparison in several equipment which is more suitable to be installed over subsea.

  13. Structure elucidation of alkaline earth impregnated MCM-41 type mesoporous materials obtained by direct synthesis: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Paz, Gizeuda L.; Silva, Francisco das Chagas M.; Araújo, Maciel M.; Lima, Francisco das Chagas A.; Luz, Geraldo E.

    2014-06-01

    In this work, MCM-41 were synthesized hydrothermally and functionalized with calcium and strontium salts by direct method, using the Si/M = 50 molar ratio, in order to elucidate the way as the alkaline earth is incorporated on MCM-41 molecular sieve. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, nitrogen adsorption-desorption and theoretical calculations by DFT method. Experimental results and computer simulations showed that the alkaline earths were incorporated on MCM-41 through a complex structure, which negatively influences on basic sites formation.

  14. Evaluating experimental artifacts in hydrothermal prebiotic synthesis experiments

    NASA Technical Reports Server (NTRS)

    Smirnov, Alexander; Schoonen, Martin A A.

    2003-01-01

    Control experiments with ultra pure deionized water were conducted to evaluate the organic contamination in hydrothermal prebiotic experiments. Different combinations of reaction vessel material, sampling tubing and stirring were tested and the amounts of organic contaminants determined. All tested types of polymer tubing were proven to introduce organic contaminants (formate, acetate and propionate ions) into the reacting solution. Stainless steel has a catalytic effect on the decomposition of formate, consistent with earlier work at high temperatures and pressures.

  15. Bekki-Nozaki Amplitude Holes in Hydrothermal Nonlinear Waves

    NASA Astrophysics Data System (ADS)

    Burguete, Javier; Chaté, Hugues; Daviaud, François; Mukolobwiez, Nathalie

    1999-04-01

    We present and analyze experimental results on the dynamics of hydrothermal waves occurring in a laterally heated fluid layer. We argue that the large-scale modulations of the waves are governed by a one-dimensional complex Ginzburg-Landau equation (CGLE). We determine quantitatively all the coefficients of this amplitude equation using the localized amplitude holes observed in the experiment, which we show to be well described as Bekki-Nozaki hole solutions of the CGLE.

  16. Evaluating experimental artifacts in hydrothermal prebiotic synthesis experiments.

    PubMed

    Smirnov, Alexander; Schoonen, Martin A A

    2003-04-01

    Control experiments with ultra pure deionized water were conducted to evaluate the organic contamination in hydrothermal prebiotic experiments. Different combinations of reaction vessel material, sampling tubing and stirring were tested and the amounts of organic contaminants determined. All tested types of polymer tubing were proven to introduce organic contaminants (formate, acetate and propionate ions) into the reacting solution. Stainless steel has a catalytic effect on the decomposition of formate, consistent with earlier work at high temperatures and pressures.

  17. REE/Fe variations in hydrothermal sediments: Implications for the REE content of seawater

    SciTech Connect

    Olivarez, A.M.; Owen, R.M. )

    1989-03-01

    Seafloor hydrothermal vent solutions exhibit rare earth element (REE) enrichments ranging between one to three orders of magnitude greater than average seawater. To assess the impact of these hydrothermal inputs on ocean chemistry, the authors have examined he behavior of REEs for hydrothermal sediments collected adjacent to two Pacific spreading ridge sites: the East Pacific Rise at 19{degree}S, and the Southern Juan de Fuca Ridge at 45{degree}N. In general, the REE/Fe ratios for both proximal and distal hydrothermal sediments are greater than vent solutions by a factor of 2 to 500, and these ratios increase with increasing distance away from the ridge axis. An evaluation of these results in the context of previous models of REE behavior indicates that, in fact, seawater experiences a net depletion in REEs as a result of hydrothermal activity. This is due primarily to the large scavenging capacity of iron oxyhydroxides which precipitate from these solutions. Such an interpretation explains why the REE content of seawater collected in the vicinity of hydrothermal vents is anomalously lower than normal seawater sampled from a comparable depth.

  18. Priming effect of abscisic acid on alkaline stress tolerance in rice (Oryza sativa L.) seedlings.

    PubMed

    Wei, Li-Xing; Lv, Bing-Sheng; Wang, Ming-Ming; Ma, Hong-Yuan; Yang, Hao-Yu; Liu, Xiao-Long; Jiang, Chang-Jie; Liang, Zheng-Wei

    2015-05-01

    Saline-alkaline stress is characterized by high salinity and high alkalinity (high pH); alkaline stress has been shown to be the primary factor inhibiting rice seedling growth. In this study, we investigated the potential priming effect of abscisic acid (ABA) on tolerance of rice seedlings to alkaline stress simulated by Na2CO3. Seedlings were pretreated with ABA at concentrations of 0 (control), 10, and 50 μM by root-drench for 24 h and then transferred to a Na2CO3 solution that did not contain ABA. Compared to control treatment, pretreatment with ABA substantially improved the survival rate of rice seedlings and increased biomass accumulation after 7 days under the alkaline condition. ABA application at 10 μM also alleviated the inhibitory effects of alkaline stress on the total root length and root surface area. Physiologically, ABA increased relative water content (RWC) and decreased cell membrane injury degree (MI) and Na(+)/K(+) ratios. In contrast, fluridone (an ABA biosynthesis inhibitor) decreased the RWC and increased MI in shoots under the alkaline conditions. These data suggest that ABA has a potent priming effect on the adaptive response to alkaline stress in rice and may be useful for improving rice growth in saline-alkaline paddy fields.

  19. Carbon and Sulphur Geochemistry of Rift Valley Sediments and Hydrothermal Fluids at the Ultra-Slow Spreading Southern Knipovich Ridge

    NASA Astrophysics Data System (ADS)

    Baumberger, T.; Frueh-Green, G. L.; Pedersen, R. B.; Thorseth, I. H.; Bernasconi, S. M.; Lilley, M. D.

    2008-12-01

    The rift valley of the ultra-slow spreading southern Knipovich Ridge in the Norwegian-Greenland Sea (73°N) is partly buried by a thick sediment cover, as at Middle Valley, Escanaba Trough and Guaymas Basin. These glacial and post-glacial sediments (12000-20000 years) derived from the nearby Bear Island fan likely act as a thermal and hydrogeological boundary to heat and fluid flow and influence hydrothermal fluid compositions. Geochemical studies of the rift valley sediments and the hydrothermal vent fluids of the recently discovered black smoker vent field Loki's Castle provide insights into the influence of the sediment cover on the composition of the hydrothermal fluids at the southern Knipovich Ridge. Here we present an overview of preliminary data on the carbon and sulphur geochemistry of the sedimentary and hydrothermal components at Loki's Castle and compare these with other sedimented and un-sedimented mid-ocean ridge hydrothermal systems. The hydrothermal vent fluids have a pH of 5.5 and are characterized by elevated concentrations of hydrogen, methane, hydrogen sulphide and ammonia, which reflect a strong sedimentary input. Short gravity cores of the rift valley sediments show relatively constant total carbon contents of approximately 1 wt%, but locally reach up to 4 wt%. Varying carbon isotope compositions reflect a mix of marine carbonates with organic carbon. Extracted sediment pore fluids show an increase in alkalinity and dissolved inorganic carbon (DIC) concentrations with increasing burial depth. The corresponding δ13CDIC values show a clear depletion with increasing alkalinity and DIC concentrations. The vent fluid compositions and carbon and sulphur isotope geochemistry provide constraints on redox conditions and thermocatalysis of organic carbon during fluid-sediment interaction, and are distinct from un- sedimented mid-ocean ridge hydrothermal fluids.

  20. Remediation of Former Manufactured Gas Plant Tars Using Alkaline Flushing

    NASA Astrophysics Data System (ADS)

    Hauswirth, S.; Rylander, S.; Birak, P. S.; Miller, C. T.

    2010-12-01

    The remediation of former manufactured gas plant (FMGP) tars in the subsurface is particularly difficult due to the wetting behavior and high viscosities of these dense non-aqueous liquids (DNAPLs). Alkaline flooding is a technique which has proven effective in improving the recovery of crude oils, which share some characteristics with FMGP tars. For this study, we measured the effect of NaOH solutions on interfacial tension and conducted column experiments to investigate the feasibility of applying this technique to FMGP tars. The pendant drop technique was used to measure interfacial tensions for solutions ranging from 0-1% NaOH. Column experiments were conducted by contaminating sands with tars recovered from a FMGP then flushing the columns with NaOH solutions. A final, 70% v/v ethanol cosolvent flush was conducted to investigate the effectiveness of a two-stage remediation approach. The mass removal of tar, as well as 26 individual PAHs, was measured, along with the aqueous phase mass flux of PAHs after each flushing stage. The interfacial tension was reduced from about 20 mN/m with pure water to a minimum of 0.05 mN/m at a concentration of 0.1% NaOH. In the column experiments, alkaline flushing resulted in a 50% reduction of the residual saturation. Aqueous phase PAH concentrations, however, were similar before and after the alkaline flushing stage. The combination of alkaline and cosolvent flushing resulted in an overall reduction of 95% of the total mass of the 16 EPA PAHs. Final aqueous phase concentrations were reduced significantly for lower molecular weight PAHs, but increased slightly for the higher molecular weight compounds, likely due to their increased mole fraction within the remaining tar. Additional work is being conducted to improve the effectiveness of the alkaline flushing through the use of surfactants and polymers.

  1. Hydrothermal processes at seafloor spreading centers,

    SciTech Connect

    Rona, P.A.; Bostrom, K.; Laubier, L.; Smith, K.L.

    1983-01-01

    This book examines research on the description and interpretation of hydrothermal and associated phenomena at seafloor spreading centers. An interdisciplinary overview of the subject is presented, including geological, geophysical, geochemical, and biological discoveries. The implications of the discoveries for understanding the earth's heat transfer, geochemical mass balances and cycles, mineralization, and biological adaptation are discussed. Topics considered include geologic setting (e.g., the four dimensions of the spreading axis, geological processes of the mid-ocean ridge), hydrothermal convection (e.g., oxygen and hydrogen isotope studies, the basic physics of water penetration into hot rock), Iceland and oceanic ridges (e.g., chemical evidence from Icelandic geothermal systems, the physical environment of hydrothermal systems), mass balances and cycles (e.g., reduced gases and bacteria in hydrothermal fluids, the effects of hydrothermal activity on sedimentary organic matter), ferromanganese deposits, hydrothermal mineralization, and the biology of hydrothermal vents.

  2. Nucleotide sequences encoding a thermostable alkaline protease

    DOEpatents

    Wilson, David B.; Lao, Guifang

    1998-01-01

    Nucleotide sequences, derived from a thermophilic actinomycete microorganism, which encode a thermostable alkaline protease are disclosed. Also disclosed are variants of the nucleotide sequences which encode a polypeptide having thermostable alkaline proteolytic activity. Recombinant thermostable alkaline protease or recombinant polypeptide may be obtained by culturing in a medium a host cell genetically engineered to contain and express a nucleotide sequence according to the present invention, and recovering the recombinant thermostable alkaline protease or recombinant polypeptide from the culture medium.

  3. Nucleotide sequences encoding a thermostable alkaline protease

    DOEpatents

    Wilson, D.B.; Lao, G.

    1998-01-06

    Nucleotide sequences, derived from a thermophilic actinomycete microorganism, which encode a thermostable alkaline protease are disclosed. Also disclosed are variants of the nucleotide sequences which encode a polypeptide having thermostable alkaline proteolytic activity. Recombinant thermostable alkaline protease or recombinant polypeptide may be obtained by culturing in a medium a host cell genetically engineered to contain and express a nucleotide sequence according to the present invention, and recovering the recombinant thermostable alkaline protease or recombinant polypeptide from the culture medium. 3 figs.

  4. The Nickel(111)/Alkaline Electrolyte Interface

    NASA Technical Reports Server (NTRS)

    Wang, Kuilong; Chottiner, G. S.; Scherson, D. A.; Reid, Margaret A.

    1991-01-01

    The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.

  5. Determination of As, Cd, Pb and Se in DORM-1 dogfish muscle reference material using alkaline solubilization and electrothermal atomic absorption spectrometry with Ir+Rh as permanent modifiers or Pd+Mg in solution

    NASA Astrophysics Data System (ADS)

    Giacomelli, Maria Bertília Oss; Lima, Maria Carminati; Stupp, Volnei; de Carvalho Júnior, Rui Miguel; Borba da Silva, José Bento; Barrera, Pilar Bermejo

    2002-12-01

    In this work, tetramethylammonium hydroxide (TMAH) was used to solubilize the DORM-1 dogfish muscle certified reference material as a model substance for the determination of As, Cd, Pb and Se by electrothermal atomic absorption spectrometry (ET AAS). The sample was mixed with a small amount of TMAH and heated to 60 °C for 10 min in a water bath. After dissolution, As and Se were determined using palladium and magnesium nitrates as a chemical modifier added in solution. For Cd and Pb, best results were obtained with a mixture of 250 μg of each of iridium and rhodium as permanent modifiers. In both cases, the calibration was performed with aqueous solutions in 0.2% v/v HNO 3. The temperature program for each analyte was optimized using pyrolysis and atomization curves established with the fish reference material. The detection limits in dry samples and the characteristic mass values were: Cd 0.005 μg g -1 and 0.9 pg; Pb 0.04 μg g -1 and 7.6 pg; As 0.4 μg g -1 and 13 pg and Se 0.6 μg g -1 and 20 pg, respectively. Results from the determination of these elements in the DORM-1 certified fish reference material were within the 95% confidence interval of the certified values.

  6. Latest Mesozoic-Early Cenozoic Continental Extension and Related Alkaline Magmatism in Central Anatolia, Turkey

    NASA Astrophysics Data System (ADS)

    Kadioglu, Y. K.

    2009-04-01

    The Central Anatolian crystalline complex (CACC) in Turkey includes a suite of latest Mesozoic-early Cenozoic plutonic rocks intruding the metamorphic and ophiolitic basement rocks. The intrusive rocks consist of three groups of granitoid, syenitoid, and gabbroids plutons. The granitoid units occur around the periphery of the CACC as large plutonic bodies, whereas the syenitoid assemblages crop out in the inner part of the CACC as small plutons. All the felsic plutons are crosscut by the gabbroid rocks in the region. The alkaline rocks of the CACC change in composition from nordmarkite through pulaskite to lusitanite, and are made of silica-saturated and silica-undersaturated magmas. The silica under-saturated alkaline rocks have gradual contacts with the silica-saturated alkaline rocks and constitute the main component of the alkaline rocks in the CACC. Nepheline, pseudoleucite, cancrinite, nosean, melanite and arfvedsonite are the main typical mineral compositions of the silica-undersaturated alkaline rocks. The leucite- and pseudoleucite-bearing rocks have porphyritic textures intruding the other main subunits of the alkaline rocks at high topographic elevations in the region. They are mostly composed of foid syenite, monzosyenite, monzodiorite and include rare amount of monzogabbro and foidolite. Each subunit has a transitional contact with the others and is crosscut by alkali feldspar foid syenite veins. Felsic dykes intrude the alkaline rock units and fluorite-bearing hydrothermal veins, which manifest themselves as alteration zones. The alkaline rocks have an abundance of xenolithic enclaves but lack any magma mixing-mingling produced enclaves. Normalized elemental patterns of the analyzed alkaline rocks show a slight enrichment in large ion lithophile elements (LILE) and light rare earth elements relatively to high field strength elements (HFSE) and heavy rare earth elements (HREE). The less fluid mobile, LILE and LREE concentration in the alkaline rocks

  7. The secondary alkaline zinc electrode

    NASA Astrophysics Data System (ADS)

    McLarnon, Frank R.; Cairns, Elton J.

    1991-02-01

    The worldwide studies conducted between 1975 and 1990 with the aim of improving cell lifetimes of secondary alkaline zinc electrodes are overviewed. Attention is given the design features and characteristics of various secondary alkaline zinc cells, including four types of zinc/nickel oxide cell designs (vented static-electrolyte, sealed static-electrolyte, vibrating-electrode, and flowing-electrolyte); two types of zinc/air cells (mechanically rechargeable consolidated-electrode and mechanically rechargeable particulate-electrode); zinc/silver oxide battery; zinc/manganese dioxide cell; and zinc/ferric cyanide battery. Particular consideration is given to recent research in the fields of cell thermodynamics, zinc electrodeposition, zinc electrodissolution, zinc corrosion, electrolyte properties, mathematical and phenomenological models, osmotic pumping, nonuniform current distribution, and cell cycle-life perforamnce.

  8. Development of alkaline fuel cells.

    SciTech Connect

    Hibbs, Michael R.; Jenkins, Janelle E.; Alam, Todd Michael; Janarthanan, Rajeswari; Horan, James L.; Caire, Benjamin R.; Ziegler, Zachary C.; Herring, Andrew M.; Yang, Yuan; Zuo, Xiaobing; Robson, Michael H.; Artyushkova, Kateryna; Patterson, Wendy; Atanassov, Plamen Borissov

    2013-09-01

    This project focuses on the development and demonstration of anion exchange membrane (AEM) fuel cells for portable power applications. Novel polymeric anion exchange membranes and ionomers with high chemical stabilities were prepared characterized by researchers at Sandia National Laboratories. Durable, non-precious metal catalysts were prepared by Dr. Plamen Atanassovs research group at the University of New Mexico by utilizing an aerosol-based process to prepare templated nano-structures. Dr. Andy Herrings group at the Colorado School of Mines combined all of these materials to fabricate and test membrane electrode assemblies for single cell testing in a methanol-fueled alkaline system. The highest power density achieved in this study was 54 mW/cm2 which was 90% of the project target and the highest reported power density for a direct methanol alkaline fuel cell.

  9. Links between hydrothermal environments, pyrophosphate, na(+), and early evolution.

    PubMed

    Holm, Nils G; Baltscheffsky, Herrick

    2011-10-01

    The discovery that photosynthetic bacterial membrane-bound inorganic pyrophosphatase (PPase) catalyzed light-induced phosphorylation of orthophosphate (Pi) to pyrophosphate (PPi) and the capability of PPi to drive energy requiring dark reactions supported PPi as a possible early alternative to ATP. Like the proton-pumping ATPase, the corresponding membrane-bound PPase also is a H(+)-pump, and like the Na(+)-pumping ATPase, it can be a Na(+)-pump, both in archaeal and bacterial membranes. We suggest that PPi and Na(+) transport preceded ATP and H(+) transport in association with geochemistry of the Earth at the time of the origin and early evolution of life. Life may have started in connection with early plate tectonic processes coupled to alkaline hydrothermal activity. A hydrothermal environment in which Na(+) is abundant exists in sediment-starved subduction zones, like the Mariana forearc in the W Pacific Ocean. It is considered to mimic the Archean Earth. The forearc pore fluids have a pH up to 12.6, a Na(+)-concentration of 0.7 mol/kg seawater. PPi could have been formed during early subduction of oceanic lithosphere by dehydration of protonated orthophosphates. A key to PPi formation in these geological environments is a low local activity of water.

  10. Adsorption of Pb(II) from aqueous solution by a poly-elemental mesoporous adsorbent

    NASA Astrophysics Data System (ADS)

    Wu, Xiu-Wen; Ma, Hong-Wen; Yang, Jing; Wang, Feng-Jiao; Li, Zhi-Hong

    2012-05-01

    A poly-elemental mesoporous adsorbent was hydrothermally prepared from microcline in an alkaline condition with cetyltrimethylammonium bromide as synthesis directing agent. The properties of the mesoporous adsorbent were determined by X-ray powder diffraction, high-resolution transmission electron microscope, N2 adsorption, and solid-state Magic Angle Spinning Nuclear Magnetic Resonance. The pore size distribution was detected by small angle X-ray scattering. The particles size was observed by Scanning electron microscope imagine. The chemical content of SiO2 in the mesoporous adsorbent was determined by spectrometry of the silicone molybdenum and sulfosalicylic acid complexes, and Al2O3 determined by complexometry with ethylene diamine tetraacetic acid in the presence of KF-Zn(Ac)2 tests. The adsorption properties of the mesoporous adsorbent to Pb(II) were studied, and three main factors, the adsorption time, solution pH, and initial concentration of Pb(II), were considered in the adsorption experiments.

  11. Effect of alkalinity on nitrite accumulation in treatment of coal chemical industry wastewater using moving bed biofilm reactor.

    PubMed

    Hou, Baolin; Han, Hongjun; Jia, Shengyong; Zhuang, Haifeng; Zhao, Qian; Xu, Peng

    2014-05-01

    Nitrogen removal via nitrite (the nitrite pathway) is more suitable for carbon-limited industrial wastewater. Partial nitrification to nitrite is the primary step to achieve nitrogen removal via nitrite. The effect of alkalinity on nitrite accumulation in a continuous process was investigated by progressively increasing the alkalinity dosage ratio (amount of alkalinity to ammonia ratio, mol/mol). There is a close relationship among alkalinity, pH and the state of matter present in aqueous solution. When alkalinity was insufficient (compared to the theoretical alkalinity amount), ammonia removal efficiency increased first and then decreased at each alkalinity dosage ratio, with an abrupt removal efficiency peak. Generally, ammonia removal efficiency rose with increasing alkalinity dosage ratio. Ammonia removal efficiency reached to 88% from 23% when alkalinity addition was sufficient. Nitrite accumulation could be achieved by inhibiting nitrite oxidizing bacteria (NOB) by free ammonia (FA) in the early period and free nitrous acid in the later period of nitrification when alkalinity was not adequate. Only FA worked to inhibit the activity of NOB when alkalinity addition was sufficient.

  12. Alkalinity production in intertidal sands intensified by lugworm bioirrigation

    PubMed Central

    Rao, Alexandra M.F.; Malkin, Sairah Y.; Montserrat, Francesc; Meysman, Filip J.R.

    2014-01-01

    Porewater profiles and sediment-water fluxes of oxygen, nutrients, pH, calcium, alkalinity, and sulfide were measured in intertidal sandflat sediments from the Oosterschelde mesotidal lagoon (The Netherlands). The influence of bioturbation and bioirrigation by the deep-burrowing polychaete Arenicola marina on the rates and sources of benthic alkalinity generation was examined by comparing measurements in intact and defaunated sediment cores before and after the addition of A. marina in summer and fall 2011. Higher organic matter remineralization rates, shallower O2 penetration, and greater sediment-water solute fluxes were observed in summer, consistent with higher sediment community metabolic rates at a higher temperature. Lugworm activity stimulated porewater exchange (5.1 × in summer, 1.9 × in fall), organic matter remineralization (6.2 × in summer, 1.9 × in fall), aerobic respiration (2.4 × in summer, 2.1 × in fall), alkalinity release (4.7 × in summer, 4.0 × in fall), nutrient regeneration, and iron cycling. The effects of lugworm activity on net sediment-water fluxes were similar but more pronounced in summer than in fall. Alkalinity release in fall was entirely driven by metabolic carbonate dissolution, while this process explained between 22 and 69% of total alkalinity production in summer, indicating the importance of other processes in this season. By enhancing organic matter remineralization and the reoxidation of reduced metabolites by the sediment microbial community, lugworm activity stimulated the production of dissolved inorganic carbon and metabolic acidity, which in turn enhanced metabolic CaCO3 dissolution efficiency. In summer, evidence of microbial long distance electron transport (LDET) was observed in defaunated sediment. Thus, alkalinity production by net carbonate dissolution was likely supplemented by anaerobic respiration and LDET in summer. PMID:25431515

  13. Surface Characterization and Osteoconductivity Evaluation of Micro/Nano Surface Formed on Titanium Using Anodic Oxidation Combined with H2O2 Etching and Hydrothermal Treatment.

    PubMed

    Park, Eun-Jin; Song, Yo-Han; Hwang, Moon-Jin; Song, Ho-Jun; Park, Yeong-Joon

    2015-08-01

    In this study, surface characteristics and osteoconductivity were investigated for the micro/nanostructured oxide layers fabricated on titanium using anodic oxidation (ANO), chemical etching (Et), and hydrothermal treatment (HT). Commercially pure titanium (CP-Ti) disks were anodic-oxidized using DC-type power supply in 1 M phosphoric acid electrolyte (P-ANO group). These specimens were further chemically etched using 30% H2O2 solution at 60 °C for 10 min (P-ANO-Et group). The P-ANO-Et-HT group was fabricated by hydrothermally treating the P-ANO-Et specimens in phosphorus-containing alkaline solution at 190 °C for 8 hrs. The P-ANO group showed a porous surface that was evenly covered with micro- and sub-micro pores. The size of these pores was decreased in the P-ANO-Et group. The P-ANO-Et-HT group showed a porous surface that was covered with nano-sized crystallites. Anatase TiO2 structure was observed in P-ANO-Et-HT group. The results of XPS demonstrated that the P-ANO-Et-HT group had a well-crystallized TiC2 structure, while the P-ANO and P-ANO-Et groups had an amorphous and phosphate-containing structure. Hydrophilicity of the P-ANO-Et-HT group was the highest. After MG63 osteoblast-like cells were cultured on the specimens for 3 hrs, SEM images of the cells cultured on P-ANO-Et-HT group specimens showed low initial adhesion. However, the osteoconductivity of these specimens increased more rapidly compared to that of the micro-structured surfaces. These results could be applied to fabricate titanium implants with an optimum micro/nano-surface for enhancing their osteoconductivity.

  14. Fabrication and characterization of nanostructured titanate materials by the hydrothermal treatment method.

    PubMed

    Doong, Ruey-an; Kao, I-ling

    2008-01-01

    The synthesis and characterization of one-dimensional (1-D) tubular and fibrous nanostructured materials have recently received highly attention. Various morphologies of 1-D nanostructured titanate materials including nanosheets, nanotubes, nanowires, and nanoribbons have recently been successfully synthesized using the alkaline hydrothermal method. In spite of the controversy of the chemical structures and formation mechanisms, titanate nanostructures have attracted much attention on applications of dye-sensitized solar cell, hydrogen sensing, lithium storage and photocatalysis because of their unique features of high specific surface area, ion-exchange capacity and aspect ratio, and unique optical and electrochemical properties. The morphology and microstructure of titanate nanostructures are highly dependent on the preparation conditions. In this review, we highlight the synthesis of TiO(2)-derived nanomaterials under various hydrothermal conditions. The patents for fabrication of various morphologies of nanostructures are also introduced. Effects of preparation parameters including hydrothermal temperature, duration, alkaline concentration, starting materials, and post-treatment on the morphology and microstructure of titanate nanomaterials are reviewered. In addition, the microwave-assisted method for fabrication of 1-D titanate nanostructures is discussed and compared. The applications of titanate nanomaterials in photocatalysis, ion-exchange, and lithium storages are also introduced.

  15. Boron isotope systematics of hydrothermal fluids from submarine hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Yamaoka, K.; Hong, E.; Ishikawa, T.; Gamo, T.; Kawahata, H.

    2013-12-01

    Boron is highly mobile in submarine hydrothermal systems and useful to trace the process of water-rock reaction. In this study, we measured the boron content and isotopic composition of vent fluids collected from arc-backarc hydrothermal systems in the western Pacific. In sediment-starved hydrothermal systems (Manus Basin, Suiyo Seamount, and Mariana Trough), the boron content and isotopic composition of vent fluids are dependent on type of host rock. The end member fluids from MORB-like basalt-hosted Vienna Woods in the Manus Basin showed low boron content and high δ11B value (0.53 mM, 29.8‰), while dacite-hosted PACMANUS and the Suiyo Seamount showed high boron contents and low δ11B values (1.45 and 1.52 mM, 13.6 and 18.5‰, respectively). The Alice Springs and Forecast Vent field in the Mariana Trough showed values intermediate between them (0.72 and 0.63 mM, 19.9 and 24.0‰, respectively), reflecting reaction of seawater and basalt influenced by slab material. In phase separated hydrothermal systems (North Fiji Basin), boron content and isotopic composition of vent fluids (0.44-0.56 mM, 34.5-35.9‰) were similar to those in the Vienna Woods. Considering little fractionation of boron and boron isotope during phase separation demonstrated by the previous experimental studies, it is suggested that the host rock in the North Fiji Basin is MORB-like basalt. In sediment-hosted hydrothermal system (Okinawa Trough), the reaction with boron-enriched sediment following seawater-rock reaction resulted in significantly high boron contents and low δ11B values of vent fluids (4.4-5.9 mM, 1.5-2.6‰). The water-sediment ratio was estimated to be ~2. In spite of the different geological settings, the end member fuids from all vent fields are enriched in B relative to seawater (0.41 mM, 39.6‰) and the δ11B values are inversely propotional to the boron concentrations. It suggests that boron isotopic composition of vent fluid predominantly depends on the amount of

  16. Zinc stannate nanostructures: hydrothermal synthesis

    PubMed Central

    Baruah, Sunandan; Dutta, Joydeep

    2011-01-01

    Nanostructured binary semiconducting metal oxides have received much attention in the last decade owing to their unique properties rendering them suitable for a wide range of applications. In the quest to further improve the physical and chemical properties, an interest in ternary complex oxides has become noticeable in recent times. Zinc stannate or zinc tin oxide (ZTO) is a class of ternary oxides that are known for their stable properties under extreme conditions, higher electron mobility compared to its binary counterparts and other interesting optical properties. The material is thus ideal for applications from solar cells and sensors to photocatalysts. Among the different methods of synthesizing ZTO nanostructures, the hydrothermal method is an attractive green process that is carried out at low temperatures. In this review, we summarize the conditions leading to the growth of different ZTO nanostructures using the hydrothermal method and delve into a few of its applications reported in the literature. PMID:27877377

  17. Nanohydroxyapatite coating on a titanium-niobium alloy by a hydrothermal process.

    PubMed

    Xiong, Jianyu; Li, Yuncang; Hodgson, Peter D; Wen, Cui'e

    2010-04-01

    A novel one-step hydrothermal coating process was used to produce nanohydroxyapatite (nano-HA) coating on a titanium-niobium (TiNb) alloy substrate in a newly designed solution containing calcium and phosphate ions. The morphology of the coating was studied using scanning electron microscopy. The phase identification of the coating was carried out using X-ray diffraction, attenuated total reflectance Fourier transform infrared spectroscopy and transmission electron microscopy. The reaction between the surface of TiNb alloy and the solution during the hydrothermal process was studied by X-ray photoelectron spectroscopy. Results show that the coating formed on the surface of TiNb alloy was composed of nano-HA particles. During the hydrothermal process, TiO(2) and Nb(2)O(5) formed on the TiNb alloy surface and hydrated to Ti(OH)(4) and Nb(OH)(5), respectively. Calcium phosphate nucleated and grew into a layer of nano-HA particles on the surface of TiNb alloy under the hydrothermal conditions. The crystallinity of the nano-HA coating was improved with the increase in hydrothermal treatment temperature and time duration. Nano-HA coating with good crystallinity was produced on the TiNb alloy via the hydrothermal process at a temperature of 200 degrees C for 12 h.

  18. Entropy Production in Convective Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Boersing, Nele; Wellmann, Florian; Niederau, Jan

    2016-04-01

    Exploring hydrothermal reservoirs requires reliable estimates of subsurface temperatures to delineate favorable locations of boreholes. It is therefore of fundamental and practical importance to understand the thermodynamic behavior of the system in order to predict its performance with numerical studies. To this end, the thermodynamic measure of entropy production is considered as a useful abstraction tool to characterize the convective state of a system since it accounts for dissipative heat processes and gives insight into the system's average behavior in a statistical sense. Solving the underlying conservation principles of a convective hydrothermal system is sensitive to initial conditions and boundary conditions which in turn are prone to uncertain knowledge in subsurface parameters. There exist multiple numerical solutions to the mathematical description of a convective system and the prediction becomes even more challenging as the vigor of convection increases. Thus, the variety of possible modes contained in such highly non-linear problems needs to be quantified. A synthetic study is carried out to simulate fluid flow and heat transfer in a finite porous layer heated from below. Various two-dimensional models are created such that their corresponding Rayleigh numbers lie in a range from the sub-critical linear to the supercritical non-linear regime, that is purely conductive to convection-dominated systems. Entropy production is found to describe the transient evolution of convective processes fairly well and can be used to identify thermodynamic equilibrium. Additionally, varying the aspect ratio for each Rayleigh number shows that the variety of realized convection modes increases with both larger aspect ratio and higher Rayleigh number. This phenomenon is also reflected by an enlarged spread of entropy production for the realized modes. Consequently, the Rayleigh number can be correlated to the magnitude of entropy production. In cases of moderate

  19. Mineralogical-geochemical features of sulfide ores from the Broken Spur hydrothermal vent field

    NASA Astrophysics Data System (ADS)

    Bogdanov, Yu. A.; Lein, A. Yu.; Maslennikov, V. V.; Li, Syaoli; Ul'Yanov, A. A.

    2008-10-01

    A representative collection of hydrothermal sediments was sampled practically from all the hydrothermal mounds of the Broken Spur hydrothermal vent field from the Mir manned submersibles during three cruises of R/V Akademik Mstislav Keldysh. Mineral associations characteristic of different morphological types of sulfide ores from hydrothermal pipes, plates, and diffusers are assessed. Particular attention is paid to the distribution of minor elements and their distribution patterns determined by the mineralogical zonation. The measured isotopic value of the sulfur in the sulfide minerals appeared to vary from 0.4 to 5.2‰, which indicates their similarity with the ores from the Snake Pit vent field and is related to the dilution of hot ore-bearing solutions by seawater and reduction of the water sulfate ions to H2S with a heavy isotopic composition.

  20. Use of natural mordenite to remove chromium (III) and to neutralize pH of alkaline waste waters.

    PubMed

    Córdova-Rodríguez, Valduvina; Rodríguez-Iznaga, Inocente; Acosta-Chávez, Raquel María; Chávez-Rivas, Fernando; Petranovskii, Vitalii; Pestryakov, Alexey

    2016-01-01

    The natural mordenite from Palmarito de Cauto deposit (PZ), Cuba, was studied in this work as an ion exchanger to remove Cr(3+) cations from alkaline aqueous solutions at different pH and chromium concentrations. The mordenite stability under cyclic treatment processes with alkaline solutions and its capacity to decrease the pH of the solutions was also analyzed. It was shown that PZ removes Cr(3+) ions from alkaline solutions, and it happens independently of the starting chromium concentration and the pH of the exchange solution used. This material has an important neutralizing effect on alkaline solutions, expressed in a significant pH decrease from the early stages of the treatments. For solutions with initial pH equal to 11, it decreases to a value of around seven. The stability of this material is not affected significantly after continuous cyclic treatment with NaOH solution, which shows that mordenite, in particular from Palmarito de Cauto deposit, has high stability in alkaline solutions. The results are important as they suggest that natural zeolites may be of interest in treatments of alkaline industrial waste effluents.

  1. Accumulation of formamide in hydrothermal pores to form prebiotic nucleobases.

    PubMed

    Niether, Doreen; Afanasenkau, Dzmitry; Dhont, Jan K G; Wiegand, Simone

    2016-04-19

    Formamide is one of the important compounds from which prebiotic molecules can be synthesized, provided that its concentration is sufficiently high. For nucleotides and short DNA strands, it has been shown that a high degree of accumulation in hydrothermal pores occurs, so that temperature gradients might play a role in the origin of life [Baaske P, et al. (2007)Proc Natl Acad Sci USA104(22):9346-9351]. We show that the same combination of thermophoresis and convection in hydrothermal pores leads to accumulation of formamide up to concentrations where nucleobases are formed. The thermophoretic properties of aqueous formamide solutions are studied by means of Infrared Thermal Diffusion Forced Rayleigh Scattering. These data are used in numerical finite element calculations in hydrothermal pores for various initial concentrations, ambient temperatures, and pore sizes. The high degree of formamide accumulation is due to an unusual temperature and concentration dependence of the thermophoretic behavior of formamide. The accumulation fold in part of the pores increases strongly with increasing aspect ratio of the pores, and saturates to highly concentrated aqueous formamide solutions of ∼85 wt% at large aspect ratios. Time-dependent studies show that these high concentrations are reached after 45-90 d, starting with an initial formamide weight fraction of[Formula: see text]wt % that is typical for concentrations in shallow lakes on early Earth.

  2. Accumulation of formamide in hydrothermal pores to form prebiotic nucleobases

    PubMed Central

    Niether, Doreen; Afanasenkau, Dzmitry; Dhont, Jan K. G.

    2016-01-01

    Formamide is one of the important compounds from which prebiotic molecules can be synthesized, provided that its concentration is sufficiently high. For nucleotides and short DNA strands, it has been shown that a high degree of accumulation in hydrothermal pores occurs, so that temperature gradients might play a role in the origin of life [Baaske P, et al. (2007) Proc Natl Acad Sci USA 104(22):9346−9351]. We show that the same combination of thermophoresis and convection in hydrothermal pores leads to accumulation of formamide up to concentrations where nucleobases are formed. The thermophoretic properties of aqueous formamide solutions are studied by means of Infrared Thermal Diffusion Forced Rayleigh Scattering. These data are used in numerical finite element calculations in hydrothermal pores for various initial concentrations, ambient temperatures, and pore sizes. The high degree of formamide accumulation is due to an unusual temperature and concentration dependence of the thermophoretic behavior of formamide. The accumulation fold in part of the pores increases strongly with increasing aspect ratio of the pores, and saturates to highly concentrated aqueous formamide solutions of ∼85 wt% at large aspect ratios. Time-dependent studies show that these high concentrations are reached after 45–90 d, starting with an initial formamide weight fraction of 10−3 wt % that is typical for concentrations in shallow lakes on early Earth. PMID:27044100

  3. Microscopic examination of volcanic rocks subjected to alkaline leaching

    NASA Astrophysics Data System (ADS)

    Seidlova, Z.; Prikryl, R.; Sachlova, S.

    2012-04-01

    Volcanic rocks supply one third of crushed stone in the Czech Republic. Some of these rocks significantly contribute to concrete damage by alkali silica reaction (ASR) as has been recognised by previous studies in several concrete constructions (dams, highways, bridges). In recent study, volcanic rocks (basalts, spilites, melaphyres, phonolites, rhyolites, diabases) were subjected to several test procedures aiming to evaluate their ASR potential. The experimental study employed accelerated mortar bar test (following the standard ASTM C1260), chemical test (following the standard ASTM C289), and microscopic techniques (polarising microscopy, scanning electron microscopy combined with energy dispersive analysis). The interaction of cement paste and aggregate under high alkaline solution and increasing temperature conditions takes place during the accelerated mortar bar test. Microscopic techniques applied on mortar bar specimens enabled identification of ASR products (alkali-silica gels). Chemical test quantified ASR potential based on the amount of Si4+ leached into the solution within 24 hours testing period and contemporaneous reduction of alkalinity. Volcanic particles leached in alkaline solution were subjected to microscopic analysis with the aim to find minerals (phases) affecting their ASR potential. ASR of volcanic rocks was found highly variable connected to the mineral composition. The highest degree of ASR was found in connection with melaphyres, rhyolites and one sample of spilite. The main factor influencing ASR of investigated aggregates is regarded in the presence of SiO2-rich phases (e.g. SiO2-rich glass).

  4. Basin-scale transport of hydrothermal dissolved metals across the South Pacific Ocean.

    PubMed

    Resing, Joseph A; Sedwick, Peter N; German, Christopher R; Jenkins, William J; Moffett, James W; Sohst, Bettina M; Tagliabue, Alessandro

    2015-07-09

    Hydrothermal venting along mid-ocean ridges exerts an important control on the chemical composition of sea water by serving as a major source or sink for a number of trace elements in the ocean. Of these, iron has received considerable attention because of its role as an essential and often limiting nutrient for primary production in regions of the ocean that are of critical importance for the global carbon cycle. It has been thought that most of the dissolved iron discharged by hydrothermal vents is lost from solution close to ridge-axis sources and is thus of limited importance for ocean biogeochemistry. This long-standing view is challenged by recent studies which suggest that stabilization of hydrothermal dissolved iron may facilitate its long-range oceanic transport. Such transport has been subsequently inferred from spatially limited oceanographic observations. Here we report data from the US GEOTRACES Eastern Pacific Zonal Transect (EPZT) that demonstrate lateral transport of hydrothermal dissolved iron, manganese, and aluminium from the southern East Pacific Rise (SEPR) several thousand kilometres westward across the South Pacific Ocean. Dissolved iron exhibits nearly conservative (that is, no loss from solution during transport and mixing) behaviour in this hydrothermal plume, implying a greater longevity in the deep ocean than previously assumed. Based on our observations, we estimate a global hydrothermal dissolved iron input of three to four gigamoles per year to the ocean interior, which is more than fourfold higher than previous estimates. Complementary simulations with a global-scale ocean biogeochemical model suggest that the observed transport of hydrothermal dissolved iron requires some means of physicochemical stabilization and indicate that hydrothermally derived iron sustains a large fraction of Southern Ocean export production.

  5. Sustainability and dynamics of outcrop-to-outcrop hydrothermal circulation.

    PubMed

    Winslow, Dustin M; Fisher, Andrew T

    2015-06-26

    Most seafloor hydrothermal circulation occurs far from the magmatic influence of mid-ocean ridges, driving large flows of water, heat and solutes through volcanic rock outcrops on ridge flanks. Here we create three-dimensional simulations of ridge-flank hydrothermal circulation, flowing between and through seamounts, to determine what controls hydrogeological sustainability, flow rate and preferred flow direction in these systems. We find that sustaining flow between outcrops that penetrate less-permeable sediment depends on a contrast in transmittance (the product of outcrop permeability and the area of outcrop exposure) between recharging and discharging sites, with discharge favoured through less-transmissive outcrops. Many simulations include local discharge through outcrops at the recharge end of an outcrop-to-outcrop system. Both of these characteristics are observed in the field. In addition, smaller discharging outcrops sustain higher flow rates than larger outcrops, which may help to explain how so much lithospheric heat is extracted globally by this process.

  6. Sustainability and dynamics of outcrop-to-outcrop hydrothermal circulation

    PubMed Central

    Winslow, Dustin M.; Fisher, Andrew T.

    2015-01-01

    Most seafloor hydrothermal circulation occurs far from the magmatic influence of mid-ocean ridges, driving large flows of water, heat and solutes through volcanic rock outcrops on ridge flanks. Here we create three-dimensional simulations of ridge–flank hydrothermal circulation, flowing between and through seamounts, to determine what controls hydrogeological sustainability, flow rate and preferred flow direction in these systems. We find that sustaining flow between outcrops that penetrate less-permeable sediment depends on a contrast in transmittance (the product of outcrop permeability and the area of outcrop exposure) between recharging and discharging sites, with discharge favoured through less-transmissive outcrops. Many simulations include local discharge through outcrops at the recharge end of an outcrop-to-outcrop system. Both of these characteristics are observed in the field. In addition, smaller discharging outcrops sustain higher flow rates than larger outcrops, which may help to explain how so much lithospheric heat is extracted globally by this process. PMID:26113260

  7. Artificial Bee Colony Optimization for Short-Term Hydrothermal Scheduling

    NASA Astrophysics Data System (ADS)

    Basu, M.

    2014-12-01

    Artificial bee colony optimization is applied to determine the optimal hourly schedule of power generation in a hydrothermal system. Artificial bee colony optimization is a swarm-based algorithm inspired by the food foraging behavior of honey bees. The algorithm is tested on a multi-reservoir cascaded hydroelectric system having prohibited operating zones and thermal units with valve point loading. The ramp-rate limits of thermal generators are taken into consideration. The transmission losses are also accounted for through the use of loss coefficients. The algorithm is tested on two hydrothermal multi-reservoir cascaded hydroelectric test systems. The results of the proposed approach are compared with those of differential evolution, evolutionary programming and particle swarm optimization. From numerical results, it is found that the proposed artificial bee colony optimization based approach is able to provide better solution.

  8. Hydrothermal organic synthesis experiments

    NASA Technical Reports Server (NTRS)

    Shock, Everett L.

    1992-01-01

    The serious scientific debate about spontaneous generation which raged for centuries reached a climax in the nineteenth century with the work of Spallanzani, Schwann, Tyndall, and Pasteur. These investigators demonstrated that spontaneous generation from dead organic matter does not occur. Although no aspects of these experiments addressed the issue of whether organic compounds could be synthesized abiotically, the impact of the experiments was great enough to cause many investigators to assume that life and its organic compounds were somehow fundamentally different than inorganic compounds. Meanwhile, other nineteenth-century investigators were showing that organic compounds could indeed be synthesized from inorganic compounds. In 1828 Friedrich Wohler synthesized urea in an attempt to form ammonium cyanate by heating a solution containing ammonia and cyanic acid. This experiment is generally recognized to be the first to bridge the artificial gap between organic and inorganic chemistry, but it also showed the usefulness of heat in organic synthesis. Not only does an increase in temperature enhance the rate of urea synthesis, but Walker and Hambly showed that equilibrium between urea and ammonium cyanate was attainable and reversible at 100 C. Wohler's synthesis of urea, and subsequent syntheses of organic compounds from inorganic compounds over the next several decades dealt serious blows to the 'vital force' concept which held that: (1) organic compounds owe their formation to the action of a special force in living organisms; and (2) forces which determine the behavior of inorganic compounds play no part in living systems. Nevertheless, such progress was overshadowed by Pasteur's refutation of spontaneous generation which nearly extinguished experimental investigations into the origins of life for several decades. Vitalism was dealt a deadly blow in the 1950's with Miller's famous spark-discharge experiments which were undertaken in the framework of the Oparin

  9. Growth of single crystals under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Popolitov, Vladislav Ivanovich; Litvin, Boris Nikolaevich

    The book summarizes the available theoretical, methodological, and experimental data on the hydrothermal growth of inorganic compounds, such as simple and complex oxides, sulfides, silicates, germanates, phosphates, niobates, and tantalates. Attention is given to the physicochemical, hydrodynamic, and kinetic characteristics of the growth of these compounds, as well as hydrothermal growth techniques and equipment. The discussion also covers the morphogenetic characteristics of hydrothermally grown single crystals, their principal physical properties, and X-ray diffraction and structural data.

  10. Coupling the Alkaline-Surfactant-Polymer Technology and the Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; Phil Dowling; David Stewart; Bill Jones

    2005-12-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or reservoirs with different sand lenses with high permeability contrast. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more crude oil than waterflooding froin swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or reservoirs with high permeability contrast zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. Fluid-fluid interaction with different gel chemical compositions and alkaline-surfactant-polymer solution with pH values ranging from 9.2 to 12.9 have been tested. Aluminum-polyacrylamide gels are not stable to alkaline-surfactant-polymer solutions at any pH. Chromium-polyacrylamide gels with polymer to chromium ion ratios of 25 or greater were stable to alkaline-surfactant-polymer solutions if solution pH was 10.6 or less. When the polymer to chromium ion was 15 or less, chromium-polyacrylamide gels were stable to alkaline-surfactant-polymer solutions with pH values up to 12.9. Chromium-xanthan gum gels were stable to alkaline-surfactant-polymer solutions with pH values of 12.9 at the polymer to chromium ion ratios tested. Silicate-polyacrylamide, resorcinol-formaldehyde, and sulfomethylated resorcinol-formaldehyde gels were also stable to alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Iron-polyacrylamide gels were immediately destroyed when contacted with any of the alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in

  11. Selenium Isotopes as Biosignatures in Seafloor Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Rouxel, O.; Ludden, J.; Fouquet, Y.

    2001-12-01

    Chemically similar to sulphur, Se occurs as +6, +4, 0 and -2 valences in a variety of organic compounds and geological settings. This makes the study of Se stable isotope ratios a potential indicator of geological and biological processes. Se isotopes were first determined in the early 60's (Krouse and Thode, 1962; Rashid et al., 1978) using gas-source MS and recently by N-TIMS (Herbel et al., 2000; Johnson et al., 1999) using the double spike technique. The previous results showed that the 82Se/76Se ratio vary by as much as 15‰ and indicate that abiotic and bacterial reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Our isotopic analyses of Se were performed using a continuous flow hydride generation system coupled to a Micromass MC-ICP-MS after chemical purification. The estimated external precision of the 82Se/76Se isotope ratio is 0.25‰ (2σ ) for a quantity of Se per analysis as low as 50 ng and the data are reported relative to our internal standards (MERCK elemental standard solution). In this study we have used Se isotopes in conjunction with S isotopes to provide additional constraints on the fractionation processes in seafloor hydrothermal systems. Several fields were studied along the Mid Atlantic Ridge and include the Lucky Strike field where the setting is in a caldera system with abundant low-permeability layers of cemented breccia which result in fluid cooling and mixing below the hydrothermal vents. Based on vent structures, mineral abundance, and geochemistry, two types of hydrothermal deposits were identified: (1) high-T vents with δ 34S between 1.5 and 4.5‰ and Se values up to 2000 ppm; (2) low-T vents where pyrite and marcasite generally have lower δ 34S values (down to -1.0‰ ) and low concentration of Se (<50ppm). Se-depletion in low temperature hydrothermal deposits is interpreted as a result of subsurface precipitation of sulfides (scavenging Se from the fluid) during the conductive cooling of the

  12. Hydrothermal carbonization of olive mill wastewater.

    PubMed

    Poerschmann, J; Baskyr, I; Weiner, B; Koehler, R; Wedwitschka, H; Kopinke, F-D

    2013-04-01

    Hydrothermal carbonization (HTC) is an emerging technology to treat wet biomasses aimed at producing a biochar material. Herein, olive mill wastewater (OMW) was subjected to HTC. Mass balance considerations provide evidence that the yield of biochar is low (~30%, w/w), which is associated with a low fraction of carbohydrates in OMW. The combination of different preparation schemes, pre-chromatographic derivatization reactions and GC/MS analysis for the analysis of organic compounds in aqueous HTC-solutions allowed to identify and quantify a wide array of analytes which belong either to intrinsic constituents of OMW or to characteristic HTC-breakdown products. Biophenols, such as hydroxyl-tyrosol (OH-Tyr), tyrosol (Tyr) account for the most abundant members of the first group. Most abundant breakdown products include phenol and benzenediols as well as short-chain organic acids. Secoiridoids, such as decarbomethoxy ligostride aglycon and decarbomethoxy oleuropein aglycon, all of them being typical components of OMW, are less abundant in HTC-solutions.

  13. Diclofenac salts. III. Alkaline and earth alkaline salts.

    PubMed

    Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

    2005-11-01

    Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

  14. Alkaline fuel cell performance investigation

    NASA Technical Reports Server (NTRS)

    Martin, R. E.; Manzo, M. A.

    1988-01-01

    An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more that two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

  15. Hydrothermal sulfidation and floatation treatment of heavy-metal-containing sludge for recovery and stabilization.

    PubMed

    Liang, Yan-Jie; Chai, Li-Yuan; Min, Xiao-Bo; Tang, Chong-Jian; Zhang, Hai-Jing; Ke, Yong; Xie, Xian-De

    2012-05-30

    This study focuses on the application of hydrothermal sulfidation and floatation to treat the heavy-metal-containing sludge for recovery and stabilization. After the hydrothermal sulfidation, the sulfidation percentage of zinc and lead reach up to 85.0% and 75.4%, respectively. 33.3% of Zn, 58.9% of Pb and 68.8% of Cu can be recovered from the sludge by floatation. The lower recovery of ZnS attributes to its surface and structural characteristics. To compare these characteristics, three types of synthetic metal sulfide (ZnS, PbS and CuS) were prepared and examined with XRD, SEM and TEM. The poor floatability of the finely dispersed, round shape of ZnS can be improved by crystal modification in hydrothermal condition. With increasing the temperature and reaction time, the grain size of the ZnS increased from 7.95 nm to 44.28 nm and the recovery of Zn increased to from 33.3% to 72.8%. The TCLP results indicate that all the leached heavy metal concentrations of floatation tailings are under the allowable limit. No obvious increase of heavy metal concentration was observed in continuous leaching procedure. The presence of alkaline compounds after hydrothermal sulfidation might act as mineralogical scavengers of dissolved heavy metal released by sulfide oxidation to avoid the heavy metal pollution.

  16. Hydrothermal synthesis of single crystals of transition metal vanadates in the glaserite phase

    SciTech Connect

    Sanjeewa, Liurukara D.; McMillen, Colin D.; Willett, Daniel; Chumanov, George; Kolis, Joseph W.

    2016-04-15

    A series of transition metal vanadate crystals were prepared using a high temperature (580 °C) hydrothermal method. The compounds all had the general formula A{sub 2}AEM(VO{sub 4}){sub 2} (A=K, Na, Li; AE=Ba, Sr; M=Co, Fe, Mn). They are all variations of the glaserite structural type and range in symmetry from P-3m1 to P-3 to P2{sub 1}/c. Most of the derivatives contain a planar three-fold rotation operation, making them possible spin frustration candidates. Single crystal structural analyses were performed on many of the derivatives to obtain a detailed understanding of the distortions of the tetrahedral building blocks that accommodate the symmetry distortions. A hydrothermal growth method was developed to grow high quality single crystals of sizes up to 2–3 mm/edge. This method can be generalized for large crystal growth to enable magnetic and neutron diffraction studies that require relatively large single crystals. - Highlights: • The hydrothermal synthesis of glaserite-type vanadates is demonstrated. • Synthesis from stoichiometric component reactions yields 0.2–0.5 mm size crystals. • Hydrothermal recrystallization of glaserite powder yields 2–3 mm size crystals. • The structure varies according to the alkali and alkaline earth metals selected. • Ideal (P-3m1) and distorted (P-3 and P2{sub 1}/c) glaserite structures are observed.

  17. Coupling the Alkaline-Surfactant-Polymer Technology and The Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; David Stewart; Bill Jones

    2005-10-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Chromium acetate-xanthan gum rigid gels are not stable to subsequent alkaline-surfactant-polymer solution injection. Resorcinol-formaldehyde gels were stable to subsequent alkaline-surfactant-polymer solution injection. When evaluated in a dual core configuration, injected fluid flows into the core with the greatest effective permeability to the injected fluid. The same gel stability trends to subsequent

  18. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, D.T.

    1992-10-06

    A method is described for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction. 2 figs.

  19. Solubility Behavior and Phase Stability of Transition Metal Oxides in Alkaline Hydrothermal Environments

    SciTech Connect

    S.E. Ziemniak

    2000-05-18

    The solubility behavior of transition metal oxides in high temperature water is interpreted by recognizing three types of chemical reaction equilibria: metal oxide hydration/dehydration, metal oxide dissolution and metal ion hydroxocomplex formation. The equilibria are quantified using thermodynamic concepts and the thermochemical properties of the metal oxides/ions representative of the most common constituents of construction metal alloys, i.e., element shaving atomic numbers between Z = 22 (Ti) and Z = 30 (Zn), are summarized on the basis of metal oxide solubility studies conducted in the laboratory. Particular attention is devoted to the uncharged metal ion hydrocomplex, M{sup Z}(OH){sub Z}(aq), since its thermochemical properties define minimum solubilities of the metal oxide at a given temperature. Experimentally-extracted values of standard partial molal entropy (S{sup 0}) for the transition metal ion neutral hydroxocomplex are shown to be influenced by ligand field stabilization energies and complex symmetry.

  20. Tested Demonstrations. The Stepwise Reduction of Permanganate in Alkaline Conditions: A Lecture Demonstration.

    ERIC Educational Resources Information Center

    Ruoff, Peter; Riley, Megan

    1987-01-01

    Describes a chemistry experiment where an alkaline ice-cold permanganate solution is reduced by adding dropwise a cold diluted hydrogen peroxide solution. Outlines the course of the reduction through the various oxidation states of manganese with their characteristic colors. (TW)

  1. Mechanisms of iron oxide transformation in hydrothermal systems.

    SciTech Connect

    Otake, Tsubasa; Wesolowski, David J; Anovitz, Lawrence {Larry} M

    2010-11-01

    Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H{sub 2}-rich hydrothermal conditions (T = 100-250 C, P{sub H{sub 2}} = 0.05-5 MPa) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to Fe{sub (aq)}{sup 2+} and (2) non-redox transformation of hematite and Fe{sub (aq)}{sup 2+} to magnetite.

  2. Mechanisms of iron oxide transformations in hydrothermal systems.

    SciTech Connect

    Otake, Tsubasa; Wesolowski, David J; Anovitz, Lawrence {Larry} M; Allard Jr, Lawrence Frederick; Ohmoto, Hiroshi

    2010-01-01

    Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H2-rich hydrothermal conditions (T = 100 250 C,) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to and (2) non-redox transformation of hematite and to magnetite.

  3. Hydrothermal alteration and zeolitization of the Fohberg phonolite, Kaiserstuhl Volcanic Complex, Germany

    NASA Astrophysics Data System (ADS)

    Weisenberger, Tobias Björn; Spürgin, Simon; Lahaye, Yann

    2014-11-01

    The subvolcanic Fohberg phonolite (Kaiserstuhl Volcanic Complex, Germany) is an economic zeolite deposit, formed by hydrothermal alteration of primary magmatic minerals. It is mined due to the high (>40 wt%) zeolite content, which accounts for the remarkable zeolitic physicochemical properties of the ground rock. New mineralogical and geochemical studies are carried out (a) to evaluate the manifestation of hydrothermal alteration, and (b) to constrain the physical and chemical properties of the fluids, which promoted hydrothermal replacement. The alkaline intrusion is characterized by the primary mineralogy: feldspathoid minerals, K-feldspar, aegirine-augite, wollastonite, and andradite. The rare-earth elements-phase götzenite is formed during the late-stage magmatic crystallization. Fluid-induced re-equilibration of feldspathoid minerals and wollastonite caused breakdown to a set of secondary phases. Feldspathoid minerals are totally replaced by various zeolite species, calcite, and barite. Wollastonite breakdown results in the formation of various zeolites, calcite, pectolite, sepiolite, and quartz. Zeolites are formed during subsolidus hydrothermal alteration (<150 °C) under alkaline conditions. A sequence of Ca-Na-dominated zeolite species (gonnardite, thomsonite, mesolite) is followed by natrolite. The sequence reflects an increase in and decrease in of the precipitating fluid. Low radiogenic 87Sr/86Sr values indicate a local origin of the elements necessary for secondary mineral formation from primary igneous phases. In addition, fractures cut the intrusive body, which contain zeolites, followed by calcite and a variety of other silicates, carbonates, and sulfates as younger generations. Stable isotope analysis of late-fracture calcite indicates very late circulation of meteoric fluids and mobilization of organic matter from surrounding sedimentary units.

  4. Alkaline and alkaline earth metal phosphate halides and phosphors

    DOEpatents

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  5. Hydrothermal Synthesis and Biocompatibility Study of Highly Crystalline Carbonated Hydroxyapatite Nanorods

    NASA Astrophysics Data System (ADS)

    Xue, Caibao; Chen, Yingzhi; Huang, Yongzhuo; Zhu, Peizhi

    2015-08-01

    Highly crystalline carbonated hydroxyapatite (CHA) nanorods with different carbonate contents were synthesized by a novel hydrothermal method. The crystallinity and chemical structure of synthesized nanorods were studied by Fourier transform infrared spectroscopy (FTIR), X-ray photo-electronic spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The biocompatibility of synthesized CHA nanorods was evaluated by cell viability and alkaline phosphatase (ALP) activity of MG-63 cell line. The biocompatibility evaluation results show that these CHA nanorods are biologically active apatites and potentially promising bone-substitute biomaterials for orthopedic application.

  6. The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

    SciTech Connect

    Fondeur, F.F.

    2001-01-16

    This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

  7. Whole Algae Hydrothermal Liquefaction Technology Pathway

    SciTech Connect

    Biddy, M.; Davis, R.; Jones, S.

    2013-03-01

    This technology pathway case investigates the feasibility of using whole wet microalgae as a feedstock for conversion via hydrothermal liquefaction. Technical barriers and key research needs have been assessed in order for the hydrothermal liquefaction of microalgae to be competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks.

  8. The Potential of Soft Soil Improvement Through a Coupled Technique Between Electro Kinetic and Alkaline Activation of Soft Soil

    NASA Astrophysics Data System (ADS)

    Ahmed, G. E.; Ismail, H. B.; Huat, B. K.; Afshin, A.; Azhar, A. T. S.

    2016-07-01

    Soil stabilization techniques have been in development for decades with different rates of success. Alkaline activation of soft soil is one of those techniques that has proved to deliver some of the best shear strength values with minor drawbacks in comparison with conventional soil stabilization methods. However, environmental considerations have not been taken into account, as major mineral glassy phase activators are poisoning alkaline solutions, such as sodium-, potassium-hydroxide, and sodium-, potassium-silicate, which poses serious hazards to man and environment. This paper addresses the ways of discarding the involvement of the aforementioned alkaline solutions in soft soil stabilization by investigating the potential of a coupled electro kinetic alkaline activation technique for soft soil strengthening, through which the provision of alkaline pH is governed by electro kinetic potential. Uncertainties in regard to the dissolution of aluminosilicate as well as the dominance of acidic front are challenges that need to be overcome.

  9. Hydrothermal vents is Lake Tanganyika, East African Rift system

    SciTech Connect

    Tiercelin, J.J.; Pflumio, C.; Castrec, M.

    1993-06-01

    Sublacustrine hydrothermal vents with associated massive sulfides were discovered during April 1987 at Pemba and Cape Banza on the Zaire side of the northern basin of Lake Tanganyika, East African Rift system. New investigations by a team of ten scuba divers during the multinational (France, Zaire, Germany, and Burundi) TANGANYDRO expedition (August-October 1991) found hydrothermal vents down to a depth of 46 m along north-trending active faults bounding the Tanganyika rift on the western side. Temperatures from 53 to 103 {degrees}C were measured in hydrothermal fluids and sediments. Veins of massive sulfides 1-10 cm thick (pyrite and marcasite banding) were found associated with vents at the Pemba site. At Cape Banza, active vents are characterized by 1-70-cm-high aragonite chimneys, and there are microcrystalline pyrite coatings on the walls of hydrothermal pipes. Hydrothermal fluid end members show distinctive compositions at the two sites. The Pemba end member is a NaHCO{sub 3}-enriched fluid similar to the NaHCO{sub 3} thermal fluids form lakes Magadi and Bogoria in the eastern branch of the rift. The Cape Banza end member is a solution enriched in NaCl. Such brines may have a deep-seated basement origin, as do the Uvinza NaCl brines on the eastern flank of the Tanganyika basin. Geothermometric calculations have yielded temperatures of fluid-rock interaction of 219 and 179 {degrees}C in the Pemba and Cape Banza systems, respectively. Abundant white or reddish-brown microbial colonies resembling Beggiatoa mats were found surrounding the active vents. Thermal fluid circulation is permitted by opening of cracks related to 130{degrees}N normal-dextral faults that intersect the north-south major rift trend. The sources of heat for such hydrothermal systems may relate to the existence of magmatic bodies under the rift, which is suggested by the isotopic composition of carbon dioxide released at Pemba and Cape Banza. 21 refs., 2 figs.

  10. Alkaline buffers release EDRF from bovine cultured aortic endothelial cells.

    PubMed Central

    Mitchell, J. A.; de Nucci, G.; Warner, T. D.; Vane, J. R.

    1991-01-01

    1. Release of endothelium-derived relaxing factor (EDRF) and prostacyclin (PGI2) from bovine cultured aortic endothelial cells (EC) was measured by bioassay and radioimmunoassay, respectively. 2. Bradykinin (BK, 3-30 pmol), adenosine diphosphate (ADP, 2-6 nmol) or the sodium ionophore monensin (40-100 nmol) injected through a column of EC released EDRF. L-Arginine free base (FB; 10-20 mumol) or D-arginine FB (10-20 mumol) injected through the column of EC released similar amounts of EDRF and also caused an increase in pH of the Krebs solution perfusing the EC from 7.5-8.0 to 8.6-9.5. Sodium carbonate (Na2CO3) an alkaline buffer which caused the same changes in the pH of the Krebs solution also induced the same release of EDRF. The hydrochloride salts of L- or D-arginine did not cause either release of EDRF when injected through the column of EC or increases in the pH of the Krebs solution. 3. Inhibitors of either diacylglycerol lipase (RHC 80267) or kinase (R59022) inhibited the release of EDRF induced by BK or ADP but potentiated the release induced by L-arginine FB, monensin (40-100 nmol) or alkaline buffer (Na2CO3). R59022 and RHC 80267 infused through the EC increased the basal release of EDRF. 4. When calcium chloride was omitted from the Krebs solution the release of EDRF induced by alkaline buffer (Na2CO3; pH 8.6-9.5) or L-arginine FB (10-20 mumol) was selectively inhibited when compared to that induced by BK (3-30 pmol) or ADP (2-6 nmol). This inhibition was reversed when calcium (2.5 mM) was restored. 5. NG-monomethyl-L-arginine (NMMA; 30 microM) inhibited release of EDRF induced by BK (10-30 pmol) or alkaline buffers (Na2CO3 or D-arginine FB; pH 8.6-9.5). This inhibition was partially reversed by L- but not D-arginine FB or HCl (30-100 microM). 6. Prostacyclin was released when BK (10 pmol), ADP (2 nmol) or arachidonic acid (30 nmol) were injected through the column of EC. However, monensin (40 nmol) or alkaline buffers (pH 8.6-9.5) did not release

  11. Hydrothermal synthesis of hydroxyapatite rods

    NASA Astrophysics Data System (ADS)

    Zhang, Xing; Vecchio, Kenneth S.

    2007-10-01

    Hydroxyapatite (HAP) rods were synthesized from dicalcium phosphate anhydrous (CaHPO 4, DCPA) and calcium carbonate (CaCO 3) by the hydrothermal method from 120 to 180 °C. Both cuttlebone (aragonite polymorph of CaCO 3) and CaCO 3 chemical (calcite polymorph of CaCO 3) were used as CaCO 3 sources. The nucleation and growth of HAP rods mainly occurred on DCPA particles, while some HAP rods also grew from aragonite particles. The nucleation and growth of β-tricalcium phosphate (β-TCP) particles on the surface of calcite particles were observed at the beginning of the reaction of DCPA and calcite, and some HAP rods were also found to grow out of β-TCP particles. After the hydrothermal reaction at 140 °C for 24 h, most products are HAP with a small amount of β-TCP synthesized as a byproduct. The HAP rods synthesized were ˜200 nm in width and several microns in length. The reaction mechanism and growth process of HAP rods are discussed.

  12. Ongoing hydrothermal activities within Enceladus.

    PubMed

    Hsu, Hsiang-Wen; Postberg, Frank; Sekine, Yasuhito; Shibuya, Takazo; Kempf, Sascha; Horányi, Mihály; Juhász, Antal; Altobelli, Nicolas; Suzuki, Katsuhiko; Masaki, Yuka; Kuwatani, Tatsu; Tachibana, Shogo; Sirono, Sin-iti; Moragas-Klostermeyer, Georg; Srama, Ralf

    2015-03-12

    Detection of sodium-salt-rich ice grains emitted from the plume of the Saturnian moon Enceladus suggests that the grains formed as frozen droplets from a liquid water reservoir that is, or has been, in contact with rock. Gravitational field measurements suggest a regional south polar subsurface ocean of about 10 kilometres thickness located beneath an ice crust 30 to 40 kilometres thick. These findings imply rock-water interactions in regions surrounding the core of Enceladus. The resulting chemical 'footprints' are expected to be preserved in the liquid and subsequently transported upwards to the near-surface plume sources, where they eventually would be ejected and could be measured by a spacecraft. Here we report an analysis of silicon-rich, nanometre-sized dust particles (so-called stream particles) that stand out from the water-ice-dominated objects characteristic of Saturn. We interpret these grains as nanometre-sized SiO2 (silica) particles, initially embedded in icy grains emitted from Enceladus' subsurface waters and released by sputter erosion in Saturn's E ring. The composition and the limited size range (2 to 8 nanometres in radius) of stream particles indicate ongoing high-temperature (>90 °C) hydrothermal reactions associated with global-scale geothermal activity that quickly transports hydrothermal products from the ocean floor at a depth of at least 40 kilometres up to the plume of Enceladus.

  13. Catalytic hydrothermal conversion of dissolved carbon dioxide into methane

    NASA Astrophysics Data System (ADS)

    Yan, Peng; Jin, Fangming; Cao, Jianglin; Wu, Bing; Zhang, Guangyi

    2010-11-01

    This paper aims to convert NaHCO3 (dissolved carbon dioxide in NaOH solution) into methane via hydrothermal catalytic reaction. The effects of various experimental parameters on the conversion efficiency of NaHCO3, e.g., amount of reactant (Zn) and catalyst (Ni), temperature, reaction time etc, were investigated. The results showed that a maximal 43.6% yield of methane was obtained at the optimal conditions: Zn 0.1 mol, Ni 0.06 mol, temperature of 300° C, reaction time of 120 min, filling rate of 35% and NaHCO3 0.01 mol. In the absence of Ni catalyst, CO2 was mostly converted into formic acid (formic acid yield of 87%) and the corresponding methane yield was zero, while in the presence of Ni, the yield of methane increased to 43.6% and the yield of formic acid was only 3%. Based on these results, it was supposed that Ni played a catalytic role in hydrothermal conversion of CO2 into methane and formic acid was the intermediate product during the formation of methane from CO2 in the hydrothermal processes.

  14. Silica nanoparticles as indicator of hydrothermal activities at Enceladus ocean floor

    NASA Astrophysics Data System (ADS)

    Postberg, F.; Hsu, S.; Sekine, Y.; Kempf, S.; Juhasz, A.; Horanyi, M.; Moragas-Klostermeyer, G.; Srama, R.

    2013-12-01

    hydrothermal liquid, probably as it travels upwards towards the surface (e.g., Matson et al., 2012). The temperatures of the near surface waters which fuel the plume are close to 0°C (Schmidt et al. 2008). Formation and stablility of a nano-colloidal silica phase requires alkaline pH (8 - 10) and only tolerates a mild salinity, not higher than a few percent, which agrees with previous compositional measurements of ice grains in Enceladus plume (Postberg et al. 2009, 2011).

  15. Effect of Treatment pH on the End Products of the Alkaline Hydrolysis of TNT and RDX

    DTIC Science & Technology

    2007-06-01

    Comparison of final TOC of TNT alkaline hydrolysis solutions at three pHs........................19 Table 7. Results of ion chromatographic analysis ...25 Table 12. Results of ion chromatographic analysis of unlabeled RDX solutions following extended alkaline hydrolysis at three...8330 explo- sives analysis TOC IC Lime Control ERDC/EL TR-07-4 7 3 Materials and Methods Chemicals Chemicals used in this study included

  16. Closed type alkaline storage battery

    SciTech Connect

    Hayama, H.

    1980-06-10

    The alkaline storage battery employs a metallic hat shaped terminal closure which has a piercing needle as well as a puncturable metallic diaphragm positioned below the piercing needle. The needle is fixed by caulking at its peripheral edge portion to a edge of the closure. A comparatively thick and hard metal plate is placed on the inner surface of the diaphragm and is applied to an open portion of a tubular metallic container which has a battery element. A peripheral edge portion of the closure, the diaphragm and the metallic plate are clamped in airtight relationship through a packing between the caulked end portion and an inner annular step portion of the metallic container of the battery. A lead wire extends from one polarity electrode of the battery element and is connected to a central portion of the metallic plate.

  17. An off-axis hydrothermal vent field near the Mid-Atlantic Ridge at 30 degrees N.

    PubMed

    Kelley, D S; Karson, J A; Blackman, D K; Früh-Green, G L; Butterfield, D A; Lilley, M D; Olson, E J; Schrenk, M O; Roe, K K; Lebon, G T; Rivizzigno, P

    2001-07-12

    Evidence is growing that hydrothermal venting occurs not only along mid-ocean ridges but also on old regions of the oceanic crust away from spreading centres. Here we report the discovery of an extensive hydrothermal field at 30 degrees N near the eastern intersection of the Mid-Atlantic Ridge and the Atlantis fracture zone. The vent field--named 'Lost City'--is distinctly different from all other known sea-floor hydrothermal fields in that it is located on 1.5-Myr-old crust, nearly 15 km from the spreading axis, and may be driven by the heat of exothermic serpentinization reactions between sea water and mantle rocks. It is located on a dome-like massif and is dominated by steep-sided carbonate chimneys, rather than the sulphide structures typical of 'black smoker' hydrothermal fields. We found that vent fluids are relatively cool (40-75 degrees C) and alkaline (pH 9.0-9.8), supporting dense microbial communities that include anaerobic thermophiles. Because the geological characteristics of the Atlantis massif are similar to numerous areas of old crust along the Mid-Atlantic, Indian and Arctic ridges, these results indicate that a much larger portion of the oceanic crust may support hydrothermal activity and microbial life than previously thought.

  18. Primary radical yields in pulse irradiated alkaline aqueous solution

    NASA Technical Reports Server (NTRS)

    Fielden, E. M.; Hart, E. J.

    1969-01-01

    Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

  19. Hydrothermal conversion of chrysotile asbestos using near supercritical conditions.

    PubMed

    Anastasiadou, Kalliopi; Axiotis, Dimosthenis; Gidarakos, Evangelos

    2010-07-15

    The present research investigates, develops and evaluates the transformation of chrysotile asbestos into a non-hazardous material, such as forsterite, using an economically viable and safe method. The aim of this study is to convert fibrous chrysotile asbestos into an anhydrous magnesium silicate with a non-hazardous lamellar morphology using supercritical steam. The treatment method is characterized as hydrothermal in a temperature and pressure range of 300-700 degrees C and 1.75-5.80 MPa, respectively. Small amounts of asbestos (2.5 g) were treated in each experiment. Deionised water was used as the treatment solution. The treatment duration varied from approximately 1-5 h. Additional experiments took place using solutions of distilled water and small amounts of acetic acid, with the aim of attaining optimal treatment conditions. Crystal phases of the samples were determined by X-ray diffraction (XRD). The main phases present in the treated samples were forsterite, enstatite, and chrysotile asbestos. Lizardite and periclase were also found. The morphology of the treated chrysotile asbestos fibers was identified by scanning electron microscope (SEM). The fibrous form of chrysotile asbestos was converted into non-fibrous form of forsterite. In fact, none of the fibrous-needle-like morphology, with length equal to or greater than 5 microm and diameter less than 3 microm, which was responsible for the toxicity of the original material, was visible in the solid phase. The dissolution of magnesium from chrysotile asbestos was measured using volumetric determination by titration with EDTA. Leaching of magnesium into the liquid phase was observed. Clearly, the highest concentrations of dissolved magnesium are observed after hydrothermal treatment of chrysotile asbestos using acetic acid 1% (8.4-14.6%). Lowest concentrations of dissolved magnesium are obtained after hydrothermal treatment of chrysotile asbestos without using additives. Observing the results of the

  20. Microemulsion-mediated hydrothermal synthesis and characterization of nanosize rutile and anatase particles

    SciTech Connect

    Wu, M.; Long, J.; Huang, A.; Luo, Y.; Feng, S.; Xu, R.

    1999-12-21

    Uniform nanoparticles of rutile and anatase were prepared, respectively, by a new approach, a microemulsion-mediated method, in which the microemulsion medium was further treated by hydrothermal reaction. Herein, the combined procedure of microemulsion and hydrothermal synthesis to prepare nanoparticles is referred to as a microemulsion-mediated hydrothermal (MMH) method. This MMH method could lead to the formation of crystalline titania powders under much milder reaction conditions than the normally reported microemulsion-mediated methods, in which posttreatment of calcination was necessary. In this work, a kind of solution was formed by dissolving tetrabutyl titanate into hydrochloric acid or nitric acid, and the solution was dispersed in an organic phase for the preparation of the microemulsion medium. The aqueous cores of water/Triton X-100/hexanol/cyclohexane microemulsions were used as constrained microreactors for a controlled growth of titania particles under hydrothermal conditions. The product of hydrothermal synthesis was separated and dried for characterization. The phase components and the morphologies and grain sizes of products were determined by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). The effects of changing the variables of the reaction conditions, such as the use of acid, the concentrations of acid, the reaction temperatures, and/or the reaction times on the phases and morphologies of the titania product are described.

  1. Evolution of alkaline phosphatases in primates.

    PubMed Central

    Goldstein, D J; Rogers, C; Harris, H

    1982-01-01

    Alkaline phosphatase [orthophosphoric-monoester phosphohydrolase (alkaline optimum), EC 3.1.3.1] in placenta, intestine, liver, kidney, bone, and lung from a variety of primate species has been characterized by quantitative inhibition, thermostability, and immunological studies. Characteristic human placental-type alkaline phosphatase occurs in placentas of great apes (chimpanzee and orangutan) but not in placentas of other primates, including gibbon. It is also present in trace amounts in human lung but not in lung or other tissues of various Old and New World monkeys. However, a distinctive alkaline phosphatase resembling it occurs in substantial amounts in lungs from Old World monkeys but not New World monkeys. It appears that duplication of alkaline phosphatase genes and mutations of genetic elements controlling their tissue expression have occurred relatively recently in mammalian evolution. Images PMID:6950431

  2. Alkaline pH sensor molecules.

    PubMed

    Murayama, Takashi; Maruyama, Ichiro N

    2015-11-01

    Animals can survive only within a narrow pH range. This requires continual monitoring of environmental and body-fluid pH. Although a variety of acidic pH sensor molecules have been reported, alkaline pH sensor function is not well understood. This Review describes neuronal alkaline pH sensors, grouped according to whether they monitor extracellular or intracellular alkaline pH. Extracellular sensors include the receptor-type guanylyl cyclase, the insulin receptor-related receptor, ligand-gated Cl- channels, connexin hemichannels, two-pore-domain K+ channels, and transient receptor potential (TRP) channels. Intracellular sensors include TRP channels and gap junction channels. Identification of molecular mechanisms underlying alkaline pH sensing is crucial for understanding how animals respond to environmental alkaline pH and how body-fluid pH is maintained within a narrow range.

  3. Double-shelled tremella-like NiO@Co3O4@MnO2 as a high-performance cathode material for alkaline supercapacitors

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Ren, Qian; Brett, Dan J. L.; He, Guanjie; Wang, Rongfang; Key, Julian; Ji, Shan

    2017-03-01

    Tremella-like NiO@Co3O4@MnO2 particles of core-double-shelled structure were synthesized by a three-step hydrothermal route and thermal treatment. The hierarchical layered porous structure of the particles has a BET surface area of 179.2 m2 g-1. Galvanostatic cycling in 6.0 M KOH aqueous solution produced capacitance over an ideal cathode potential cycling range. At a high current density of 2 A g-1, NiO@Co3O4@MnO2 has a high specific capacitance of 792.5 F g-1 with > 90% capacity retention over 1000 cycles, and a high rate capability of 68.9% of its initial capacitance was also maintained over a 0.2-4 A g-1 current density increase. We conclude that NiO@Co3O4@MnO2 offers a promising high rate, high specific capacitance cathode material for alkaline supercapacitors, which owes both to its porous architecture and its synergistic mixed oxide core-shell-shell composition.

  4. Arctic Ocean: hydrothermal activity on Gakkel Ridge.

    PubMed

    Jean-Baptiste, Philippe; Fourré, Elise

    2004-03-04

    In the hydrothermal circulation at mid-ocean ridges, sea water penetrates the fractured crust, becomes heated by its proximity to the hot magma, and returns to the sea floor as hot fluids enriched in various chemical elements. In contradiction to earlier results that predict diminishing hydrothermal activity with decreasing spreading rate, a survey of the ultra-slowly spreading Gakkel Ridge (Arctic Ocean) by Edmonds et al. and Michael et al. suggests that, instead of being rare, the hydrothermal activity is abundant--exceeding by at least a factor of two to three what would be expected by extrapolation from observation on faster spreading ridges. Here we use helium-3 (3He), a hydrothermal tracer, to show that this abundance of venting sites does not translate, as would be expected, into an anomalous hydrothermal 3He output from the ridge. Because of the wide implications of the submarine hydrothermal processes for mantle heat and mass fluxes to the ocean, these conflicting results call for clarification of the link between hydrothermal activity and crustal production at mid-ocean ridges.

  5. Dynamics of the Yellowstone hydrothermal system

    USGS Publications Warehouse

    Hurwitz, Shaul; Lowenstern, Jacob B.

    2014-01-01

    The Yellowstone Plateau Volcanic Field is characterized by extensive seismicity, episodes of uplift and subsidence, and a hydrothermal system that comprises more than 10,000 thermal features, including geysers, fumaroles, mud pots, thermal springs, and hydrothermal explosion craters. The diverse chemical and isotopic compositions of waters and gases derive from mantle, crustal, and meteoric sources and extensive water-gas-rock interaction at variable pressures and temperatures. The thermal features are host to all domains of life that utilize diverse inorganic sources of energy for metabolism. The unique and exceptional features of the hydrothermal system have attracted numerous researchers to Yellowstone beginning with the Washburn and Hayden expeditions in the 1870s. Since a seminal review published a quarter of a century ago, research in many fields has greatly advanced our understanding of the many coupled processes operating in and on the hydrothermal system. Specific advances include more refined geophysical images of the magmatic system, better constraints on the time scale of magmatic processes, characterization of fluid sources and water-rock interactions, quantitative estimates of heat and magmatic volatile fluxes, discovering and quantifying the role of thermophile microorganisms in the geochemical cycle, defining the chronology of hydrothermal explosions and their relation to glacial cycles, defining possible links between hydrothermal activity, deformation, and seismicity; quantifying geyser dynamics; and the discovery of extensive hydrothermal activity in Yellowstone Lake. Discussion of these many advances forms the basis of this review.

  6. Hydrothermal carbonization of lignocellulosic biomass.

    PubMed

    Xiao, Ling-Ping; Shi, Zheng-Jun; Xu, Feng; Sun, Run-Cang

    2012-08-01

    Hydrothermal carbonization (HTC) is a novel thermochemical conversion process to convert lignocellulosic biomass into value-added products. HTC processes were studied using two different biomass feedstocks: corn stalk and Tamarix ramosissima. The treatment brought an increase of the higher heating values up to 29.2 and 28.4 MJ/kg for corn stalk and T. ramosissima, respectively, corresponding to an increase of 66.8% and 58.3% as compared to those for the raw materials. The resulting lignite-like solid products contained mainly lignin with a high degree of aromatization and a large amount of oxygen-containing groups. Liquid products extracted with ethyl acetate were analyzed by gas chromatography-mass spectrometry. The identified degradation products were phenolic compounds and furan derivatives, which may be desirable feedstocks for biodiesel and chemical production. Based on these results, HTC is considered to be a potential treatment in a lignocellulosic biomass refinery.

  7. Seawater bicarbonate removal during hydrothermal circulation

    NASA Astrophysics Data System (ADS)

    Proskurowski, G. K.; Seewald, J.; Sylva, S. P.; Reeves, E.; Lilley, M. D.

    2013-12-01

    High temperature fluids sampled at hydrothermal vents represent a complex alteration product of water-rock reactions on a multi-component mixture of source fluids. Sources to high-temperature hydrothermal samples include the 'original' seawater present in the recharge limb of circulation, magmatically influenced fluids added at depth as well as any seawater entrained during sampling. High-temperature hydrothermal fluids are typically enriched in magmatic volatiles, with CO2 the dominant species, characterized by concentrations of 10's-100's of mmol/kg (1, 2). Typically, the high concentration of CO2 relative to background seawater bicarbonate concentrations (~2.3 mmol/kg) obscures a full analysis of the fate of seawater bicarbonate during high-temperature hydrothermal circulation. Here we present data from a suite of samples collected over the past 15 years from high-temperature hydrothermal vents at 9N, Endeavour, Lau Basin, and the MAR that have endmember CO2 concentrations less than 10 mmol/kg. Using stable and radiocarbon isotope measurements these samples provide a unique opportunity to examine the balance between 'original' seawater bicarbonate and CO2 added from magmatic sources. Multiple lines of evidence from multiple hydrothermal settings consistently points to the removal of ~80% of the 'original' 2.3 mmol/kg seawater bicarbonate. Assuming that this removal occurs in the low-temperature, 'recharge' limb of hydrothermal circulation, this removal process is widely occurring and has important contributions to the global carbon cycle over geologic time. 1. Lilley MD, Butterfield DA, Lupton JE, & Olson EJ (2003) Magmatic events can produce rapid changes in hydrothermal vent chemistry. Nature 422(6934):878-881. 2. Seewald J, Cruse A, & Saccocia P (2003) Aqueous volatiles in hydrothermal fluids from the Main Endeavour Field, northern Juan de Fuca Ridge: temporal variability following earthquake activity. Earth and Planetary Science Letters 216(4):575-590.

  8. Hydrothermal vents and the origin of life.

    PubMed

    Martin, William; Baross, John; Kelley, Deborah; Russell, Michael J

    2008-11-01

    Submarine hydrothermal vents are geochemically reactive habitats that harbour rich microbial communities. There are striking parallels between the chemistry of the H(2)-CO(2) redox couple that is present in hydrothermal systems and the core energy metabolic reactions of some modern prokaryotic autotrophs. The biochemistry of these autotrophs might, in turn, harbour clues about the kinds of reactions that initiated the chemistry of life. Hydrothermal vents thus unite microbiology and geology to breathe new life into research into one of biology's most important questions - what is the origin of life?

  9. What Defines a Separate Hydrothermal System

    SciTech Connect

    Lawless, J.V.; Bogie, I.; Bignall, G.

    1995-01-01

    Separate hydrothermal systems can be defined in a variety of ways. Criteria which have been applied include separation of heat source, upflow, economic resource and geophysical anomaly. Alternatively, connections have been defined by the effects of withdrawal of economically useful fluid and subsidence, effects of reinjection, changes in thermal features, or by a hydrological connection of groundwaters. It is proposed here that: ''A separate hydrothermal system is one that is fed by a separate convective upflow of fluid, at a depth above the brittle-ductile transition for the host rocks, while acknowledging that separate hydrothermal systems can be hydrologically interconnected at shallower levels''.

  10. Relationship between enhanced dewaterability and structural properties of hydrothermal sludge after hydrothermal treatment of excess sludge.

    PubMed

    Wang, Liping; Li, Aimin; Chang, Yuzhi

    2017-04-01

    Hydrothermal treatment is an effective method to enhance the deep dewaterability of excess sludge with low energy consumption. In this study, an insight into the relationship between enhanced dewaterability and structural properties of the produced hydrothermal sludge was presented, aiming at better understanding the effect of hydrothermal process on excess sludge dewatering performance. The results indicated that hydrothermal effect induced the transformation of surface water to interstitial and free water by lowering the binding strength between adjacent water and solid particles and that free water became the main form for moisture existence in hydrothermal sludge as temperature was higher than 180 °C. Increase in temperature of hydrothermal treatment generated a significant size reduction of sludge flocs but treated sludge with a higher rigidity, which not only strengthened the network of hydrothermal sludge but also destroyed the binding of EPS with water. Hydrothermal process caused crevice and pore structures of excess sludge to disappear gradually, which was a main driving force of water removal as temperature was below 150 °C. With the temperature of hydrothermal treatment exceeding 180 °C, the morphology of hydrothermal sludge became rough which linked closely to the solid precipitation of condensation polymerization, and further became smooth at higher temperature (210 °C) due to the coal-like structures with higher aromaticities, indicating that hydrothermal reaction pathways began to play a main role in enhanced dewaterability. Hydrothermal treatment led to more alkyl and aromatic carbon, but lower O-alkyl, carboxyl and carbonyl carbon.

  11. Crystalline hydroxyapatite coatings synthesized under hydrothermal conditions on modified titanium substrates.

    PubMed

    Suchanek, Katarzyna; Bartkowiak, Amanda; Gdowik, Agnieszka; Perzanowski, Marcin; Kąc, Sławomir; Szaraniec, Barbara; Suchanek, Mateusz; Marszałek, Marta

    2015-06-01

    Hydroxyapatite coatings were successfully produced on modified titanium substrates via hydrothermal synthesis in a Ca(EDTA)(2-) and (NH4)2HPO4 solution. The morphology of modified titanium substrates as well as hydroxyapatite coatings was studied using scanning electron microcopy and phase identification by X-ray diffraction, and Raman and FTIR spectroscopy. The results show that the nucleation and growth of hydroxyapatite needle-like crystals with hexagonal symmetry occurred only on titanium substrates both chemically and thermally treated. No hydroxyapatite phase was detected on only acid etched Ti metal. This finding demonstrates that only a particular titanium surface treatment can effectively induce the apatite nucleation under hydrothermal conditions.

  12. Hydrothermal synthesis of sodium tungstate nanorods and nanobundles in the presence of sodium sulfate

    SciTech Connect

    Cao Guangxiang; Song Xinyu; Yu Haiyun; Fan Chunhua; Yin Zhilei; Sun Sixiu . E-mail: ssx@sdu.edu.cn

    2006-02-02

    Sodium tungstate nanorods and nanobundles have been successfully prepared, for the first time, through a simple salt-assisted hydrothermal route based on the reaction between Na{sub 2}WO{sub 4} and HCl in aqueous solution. The resultant sodium tungstate nanorods and nanobundles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electronic diffraction (SAED) techniques. The ingredients of the sample have been detected by energy-dispersive spectrum (EDS) method. It is found that hydrothermal temperature and time play important roles in the control of the morphology and size of the products.

  13. Accumulation of formamide in hydrothermal pores to form prebiotic nucleobases

    NASA Astrophysics Data System (ADS)

    Niether, Doreen; Afanasenkau, Dzmitry; Dhont, Jan K. G.

    2016-04-01

    Formamide is one of the important compounds from which prebiotic molecules can be synthesized, provided that its concentration is sufficiently high. For nucleotides and short DNA strands, it has been shown that a high degree of accumulation in hydrothermal pores occurs, so that temperature gradients might play a role in the origin of life [Baaske P, et al. (2007) Proc Natl Acad Sci USA 104(22):9346-9351]. We show that the same combination of thermophoresis and convection in hydrothermal pores leads to accumulation of formamide up to concentrations where nucleobases are formed. The thermophoretic properties of aqueous formamide solutions are studied by means of Infrared Thermal Diffusion Forced Rayleigh Scattering. These data are used in numerical finite element calculations in hydrothermal pores for various initial concentrations, ambient temperatures, and pore sizes. The high degree of formamide accumulation is due to an unusual temperature and concentration dependence of the thermophoretic behavior of formamide. The accumulation fold in part of the pores increases strongly with increasing aspect ratio of the pores, and saturates to highly concentrated aqueous formamide solutions of ˜85 wt% at large aspect ratios. Time-dependent studies show that these high concentrations are reached after 45-90 d, starting with an initial formamide weight fraction of 10-310-3 wt % that is typical for concentrations in shallow lakes on early Earth.

  14. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2002-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  15. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2003-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  16. Recent developments on IME-alkaline water electrolysis

    NASA Astrophysics Data System (ADS)

    Vandenborre, H.; Baetsle, L. H.; Hebel, W.; Leysen, R.; Nackaerts, H.; Spaepen, G.

    Demonstration on a laboratory scale is reported for the substitution of the conventional asbestos diaphragm in alkaline water electrolysis processes by thin sheets of polyantimonic acid and polysulfone. The membranes investigated withstand concentrated KOH solutions at up to 120 C, and have the necessary ion-conducting and gas-separating properties. It was also found that, by increasing the amount of polyantimonic acid in the membrane, electrolyte concentration can be lowered from 30 percent to 5 percent (by weight) without major effect on the cell voltage.

  17. Methanethiol abundance in high-temperature hydrothermal fluids from the Mid-Atlantic Ridge

    NASA Astrophysics Data System (ADS)

    Reeves, E.; Seewald, J. S.; Saccocia, P.; van der Meer, M.

    2008-12-01

    metabolism in highly-reducing alkaline hydrothermal environments invoke CH3SH as a key reactant leading to Acetyl CoA-based (Wood-Ljungdahl) carbon fixation pathways. Results of this study challenge the notion that high-pH, reducing fluids emanating from serpentinite-hosted hydrothermal systems like Lost City were favorable for the production of CH3SH, the establishment of a primitive metabolic cycle and the emergence of microbial life on Earth.

  18. Cripple Creek and other alkaline-related gold deposits in the Southern Rocky Mountains, USA: Influence of regional tectonics

    USGS Publications Warehouse

    Kelley, K.D.; Ludington, S.

    2002-01-01

    Alkaline-related epithermal vein, breccia, disseminated, skarn, and porphyry gold deposits form a belt in the southern Rocky Mountains along the eastern edge of the North American Cordillera. Alkaline igneous rocks and associated hydrothermal deposits formed at two times. The first was during the Laramide orogeny (about 70-40 Ma), with deposits restricted spatially to the Colorado mineral belt (CMB). Other alkaline igneous rocks and associated gold deposits formed later, during the transition from a compressional to an extensional regime (about 35-27 Ma). These younger rocks and associated deposits are more widespread, following the Rocky Mountain front southward, from Cripple Creek in Colorado through New Mexico. All of these deposits are on the eastern margin of the Cordillera, with voluminous calc-alkaline rocks to the west. The largest deposits in the belt include Cripple Creek and those in the CMB. The most important factor in the formation of all of the gold deposits was the near-surface emplacement of relatively oxidized volatile-rich alkaline magmas. Strontium and lead isotope compositions suggest that the source of the magmas was subduction-modified subcontinental lithosphere. However, Cripple Creek alkaline rocks and older Laramide alkaline rocks in the CMB that were emplaced through hydrously altered LREE-enriched rocks of the Colorado (Yavapai) province have 208Pb/204Pb ratios that suggest these magmas assimilated and mixed with significant amounts of lower crust. The anomalously hot, thick, and light crust beneath Colorado may have been a catalyst for large-scale transfer of volatiles and crustal melting. Increased dissolved H2O (and CO2, F, Cl) of these magmas may have resulted in more productive gold deposits due to more efficient magmatic-hydrothermal systems. High volatile contents may also have promoted Te and V enrichment, explaining the presence of fluorite, roscoelite (vanadium-rich mica) and tellurides in the CMB deposits and Cripple Creek as

  19. Volatiles in Hydrothermal Systems: Then and Now

    NASA Astrophysics Data System (ADS)

    Lilley, M. D.

    2004-12-01

    Jack Diamond was one of the principal investigators on the original proposal to dive on the Galapagos hydrothermal system. Jack participated on the cruise and, along with his graduate student (Richard Cobbler), made the first measurements of radon in hydrothermal systems. Louis I. Gordon and the author were also participants on this cruise and we made measurements of methane and hydrogen. In the ensuing 27 years much has been learned about volatiles in hydrothermal systems. For example, we have learned that phase separation and water/rock reactions play major roles in the volatile composition of hydrothermal fluids and that temporal variability is the rule rather than the exception. A summary of progress in this field will be given.

  20. Hydrothermal Manganese Mineralization Near the Samoan Hotspot

    NASA Astrophysics Data System (ADS)

    Hein, J. R.; Staudigel, H.; Koppers, A.; Hart, S. R.; Dunham, R.

    2006-12-01

    The thickest beds of hydrothermal manganese oxides recovered to date from the global ocean were collected from a volcanic cone in the south Pacific. In April 2005, samples were dredged aboard the R.V. Kilo Moana from a volcanic cone on the lower flank of Tulaga seamount (about 2,700 m water depth; 14° 39.222' S; 170° 1.730' W), located 115 km SW of Vailulu'u, the volcanically and hydrothermally active center of the Samoan hotspot. Additional hydrothermal manganese samples were collected off Ofu Island (dredge Alia 107), 72 km to the WSW of Vailulu'u. Manganese-oxide beds up to 9 cm thick are composed of birnessite and 10 Å manganates. Some layers consist of Mn-oxide columnar structures 4 cm long and 1 cm wide, which have not been described previously. The mean Mn and Fe contents of 18 samples are 51 weight percent and 0.76 weight percent, respectively. Elevated concentrations of Li (mean 0.11 wt. percent) are indicators of a hydrothermal origin, and distinguishes these samples, along with the high Mn and low Fe contents, from hydrogenetic Fe-Mn crusts. Other enriched elements include Ba (mean 0.14 percent), Cu (249 ppm), Mo (451 ppm), Ni (400 ppm), Zn (394 ppm), V (214 ppm), and W (132 ppm). Chondrite-normalized REE patterns show large negative Ce anomalies and LREE enrichments, both characteristic of hydrothermal Mn deposits. Small negative Eu anomalies are not typical of hydrothermal deposits and can be explained either by the absence of leaching of plagioclase by the hydrothermal fluids or by the precipitation of Eu-rich minerals, such as barite and anhydrite, at depth. The high base-metal contents indicate that sulfides are not forming deeper in the hydrothermal system or that such deposits are being leached by the ascending fluids. Textures of the thickest Mn deposits indicate that the Mn oxides formed below the seabed from ascending fluids during multiple phases of waxing and waning hydrothermal pulses. The deposits were later exposed at the seafloor by

  1. Chemical environments of submarine hydrothermal systems

    NASA Technical Reports Server (NTRS)

    Shock, Everett L.

    1992-01-01

    Perhaps because black-smoker chimneys make tremendous subjects for magazine covers, the proposal that submarine hydrothermal systems were involved in the origin of life has caused many investigators to focus on the eye-catching hydrothermal vents. In much the same way that tourists rush to watch the spectacular eruptions of Old Faithful geyser with little regard for the hydrology of the Yellowstone basin, attention is focused on the spectacular, high-temperature hydrothermal vents to the near exclusion of the enormous underlying hydrothermal systems. Nevertheless, the magnitude and complexity of geologic structures, heat flow, and hydrologic parameters which characterize the geyser basins at Yellowstone also characterize submarine hydrothermal systems. However, in the submarine systems the scale can be considerably more vast. Like Old Faithful, submarine hydrothermal vents have a spectacular quality, but they are only one fascinating aspect of enormous geologic systems operating at seafloor spreading centers throughout all of the ocean basins. A critical study of the possible role of hydrothermal processes in the origin of life should include the full spectrum of probable environments. The goals of this chapter are to synthesize diverse information about the inorganic geochemistry of submarine hydrothermal systems, assemble a description of the fundamental physical and chemical attributes of these systems, and consider the implications of high-temperature, fluid-driven processes for organic synthesis. Information about submarine hydrothermal systems comes from many directions. Measurements made directly on venting fluids provide useful, but remarkably limited, clues about processes operating at depth. The oceanic crust has been drilled to approximately 2.0 km depth providing many other pieces of information, but drilling technology has not allowed the bore holes and core samples to reach the maximum depths to which aqueous fluids circulate in oceanic crust. Such

  2. Hydrothermal monitoring in a quiescent volcanic arc: Cascade Range, northwestern United States

    USGS Publications Warehouse

    Ingebritsen, S.E.; Randolph-Flagg, N. G.; Gelwick, K.D.; Lundstrom, E.A.; Crankshaw, I.M.; Murveit, A.M.; Schmidt, M.E.; Bergfeld, D.; Spicer, K.R.; Tucker, D.S.; Mariner, R.H.; Evans, William C.

    2014-01-01

    Ongoing (1996–present) volcanic unrest near South Sister, Oregon, is accompanied by a striking set of hydrothermal anomalies, including elevated temperatures, elevated major ion concentrations, and 3He/4He ratios as large as 8.6 RA in slightly thermal springs. These observations prompted the US Geological Survey to begin a systematic hydrothermal-monitoring effort encompassing 25 sites and 10 of the highest-risk volcanoes in the Cascade volcanic arc, from Mount Baker near the Canadian border to Lassen Peak in northern California. A concerted effort was made to develop hourly, multiyear records of temperature and/or hydrothermal solute flux, suitable for retrospective comparison with other continuous geophysical monitoring data. Targets included summit fumarole groups and springs/streams that show clear evidence of magmatic influence in the form of high 3He/4He ratios and/or anomalous fluxes of magmatic CO2 or heat. As of 2009–2012, summit fumarole temperatures in the Cascade Range were generally near or below the local pure water boiling point; the maximum observed superheat was 3 during periods of hourly record. Hydrothermal responses to these small seismic stimuli were generally undetectable or ambiguous. Evaluation of multiyear to multidecadal trends indicates that whereas the hydrothermal system at Mount St. Helens is still fast-evolving in response to the 1980–present eruptive cycle, there is no clear evidence of ongoing long-term trends in hydrothermal activity at other Cascade Range volcanoes that have been active or restless during the past century (Baker, South Sister, and Lassen). Experience gained during the Cascade Range hydrothermal-monitoring experiment informs ongoing efforts to capture entire unrest cycles at more active but generally less accessible volcanoes such as those in the Aleutian arc.

  3. Volcano-Hydrothermal Systems of the Central and Northern Kuril Island Arc - a Review

    NASA Astrophysics Data System (ADS)

    Kalacheva, E.; Taran, Y.; Voloshina, E.; Ptashinsky, L.

    2015-12-01

    More than 20 active volcanoes with historical eruptions are known on 17 islands composing the Central and Northern part of the Kurilian Arc. Six islands - Paramushir, Shiashkotan, Rasshua, Ushishir, Ketoy and Simushir - are characterized by hydrothermal activity, complementary to the fumarolic activity in their craters. There are several types of volcano-hydrothermal systems on the islands. At Paramushir, Shiashkotan and Ketoy the thermal manifestations are acidic to ultra-acidic water discharges associated with hydrothermal aquifers inside volcano edifices and formed as the result of the absorption of magmatic gases by ground waters. A closest known analogue of such activity is Satsuma-Iwojima volcano-island at the Ryukyu Arc. Another type of hydrothermal activity are wide spread coastal hot springs (Shiashkotan, Rasshua), situated as a rule within tide zones and formed by mixing of the heated seawater with cold groundwater or, in opposite, by mixing of the steam- or conductively heated groundwater with seawater. This type of thermal manifestation is similar to that reported for other volcanic islands of the world (Satsuma Iwojima, Monserrat, Ischia, Socorro). Ushishir volcano-hydrothermal system is formed by the absorption of magmatic gases by seawater. Only Ketoy Island hosts a permanent acidic crater lake. At Ebeko volcano (Paramushir) rapidly disappearing small acidic lakes (formed after phreatic eruptions) have been reported. The main hydrothermal manifestation of Simushir is the Zavaritsky caldera lake with numerous coastal thermal springs and weak steam vents. The last time measured temperatures of fumaroles at the islands are: >500ºC at Pallas Peak (Ketoy), 480ºC at Kuntamintar volcano (Shiashkotan), variable and fast changing temperatures from 120º C to 500ºC at Ebeko volcano (Paramushir), 150ºC in the Rasshua crater, and > 300ºC in the Chirpoy crater (Black Brothers islands). The magmatic and rock-forming solute output by the Kurilian volcano-hydrothermal

  4. Hydrous pyrolysis of polycyclic aromatic hydrocarbons and implications for the origin of PAH in hydrothermal petroleum

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.; Shock, E. L.

    1999-01-01

    Polycyclic aromatic hydrocarbons (PAH) are found at high concentrations in thermally altered organic matter and hydrothermally generated petroleum from sediment-covered seafloor hydro-thermal systems. To better understand the factors controlling the occurrence of PAH in thermally altered environments, the reactivities of two PAH, phenanthrene and anthracene, were investigated in hydrothermal experiments. The compounds were heated with water at 330 degrees C in sealed reaction vessels for durations ranging from 1 to 17 days. Iron oxide and sulfide minerals, formic acid, or sodium for-mate were included in some experiments to vary conditions within the reaction vessel. Phenanthrene was unreactive both in water alone and in the presence of minerals for up to 17 days, while anthracene was partially hydrogenated (5-10%) to di- and tetrahydroanthracene. In the presence of 6-21 vol % formic acid, both phenanthrene and anthracene reacted extensively to form hydrogenated and minor methylated derivatives, with the degree of hydrogenation and methylation increasing with the amount of formic acid. Phenanthrene was slightly hydrogenated in sodium formate solutions. The hydrogenation reactions could be readily reversed; heating a mixture of polysaturated phenanthrenes resulted in extensive dehydrogenation (aromatization) after 3 days at 330 degrees C. While the experiments demonstrate that reaction pathways for the hydrogenation of PAH under hydrothermal conditions exist, the reactions apparently require higher concentrations of H2 than are typical of geologic settings. The experiments provide additional evidence that PAH may be generated in hydrothermal systems from progressive aromatization and dealkylation of biologically derived polycyclic precursors such as steroids and terpenoids. Furthermore, the results indicate that PAH initially present in sediments or formed within hydrothermal systems are resistant to further thermal degradation during hydrothermal alteration.

  5. Hydrothermal industrialization: direct heat development. Final report

    SciTech Connect

    Not Available

    1982-05-01

    A description of hydrothermal resources suitable for direct applications, their associated temperatures, geographic distribution and developable capacity are given. An overview of the hydrothermal direct-heat development infrastructure is presented. Development activity is highlighted by examining known and planned geothermal direct-use applications. Underlying assumptions and results for three studies conducted to determine direct-use market penetration of geothermal energy are discussed.

  6. Organic compounds in hydrothermal systems on the Russian Far East: relevance to the origin of life

    NASA Astrophysics Data System (ADS)

    Kompanichenko, Vladimir

    In 70th of the last centur